JP2003212924A - Polyethylene resin material and molding using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyethylene resin material which can achieve the ensurance of the balance among impact resistance, stress cracking resistance, molding stability, and fluidity and the adjustment of moldability without causing a change in a molecular weight distribution and in a comonomer sequence distribution. <P>SOLUTION: There are provided a polyethylene resin material satisfying the requirements including a density (d) of 0.90-0.97 g/cm<SP>3</SP>, an MFR of 0.001-300 dg/min (as measured at 190°C under a load of 21.18 N) and a parameter of viscosity as measured under shear and heat (SHP) of 0.10-2.5, especially, a polyethylene resin material comprising (A) an ethylene polymer satisfying the requirements including a density of 0.90-0.97 g/cm<SP>3</SP>, an HLMFR (high load melt flow rate) of 0.001-100 dg/min (as measured at 190°C under a load of 211.82 N), a molecular weight distribution (Mw/Mn) of 3.0-8.0, and a comonomer sequence distribution (CSD) of 0-3.0 and 90-10% (B) another ethylene polymer and a molding comprising the polyethylene resin material. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyethylene resin material which has a long-term performance such as impact resistance and stress crack resistance, a high melt elasticity represented by fluidity and strain hardening of extensional flow, and an excellent molding stability. In particular, it relates to a polyethylene resin material containing a novel copolymer of ethylene and α-olefin. More specifically, it contains a moderately high molecular weight ethylene polymer with a narrow composition distribution and has excellent long-term performance such as impact resistance and stress crack resistance, as well as melt represented by strain hardening of fluidity and extensional flow. The present invention relates to a polyethylene-based resin material which has high elasticity and excellent molding stability, and whose melt elasticity is adjusted almost independently of the molecular weight distribution and composition distribution, and which has an excellent balance of various properties.

[0002]

2. Description of the Related Art Recently, it has been widely known that the demand for thinning and weight reduction due to the social trend of resource saving and cost reduction in recent years and the physical properties of these thin and lightweight products are effective in the field of industrial materials. Therefore, polyethylene is required to have long-term performance such as impact resistance and stress crack resistance more than ever before. In order to satisfy these performance requirements, a suitable high molecular weight component having a composition distribution (evaluated by CSD described later) in which so-called short chain branching is uniformly introduced by copolymerization of α-olefin is appropriately contained. Will be required. Further, polyethylene resin materials include, for example, extrusion molding, hollow molding, inflation molding, injection molding,
Although it can be molded by various methods such as vacuum pressure molding, it is strongly required to secure molding stability along with higher fluidization due to the demand for energy saving and cost reduction.

In the molding process, a molten resin forms a free surface which is not restricted by a die, a mold or the like, for example, a hollow molding method, an inflation molding method, a vacuum pressure molding method, an extrusion molding method, a T-die molding method, a laminating molding method or the like. It is known that strain hardening of elongational viscosity, which is a remarkable expression of melt elasticity, greatly contributes to its molding stability. Strain hardening is an elastic phenomenon of a molten resin in which a molecular chain stretched by extensional deformation cannot contract and generates high stress. Since it is relatively fast, the molecular chain is unlikely to be stretched and strain hardening is generally unlikely to occur. However, when two or more long-chain branches are present in one molecule, the main chain between the branch points stretched by extensional deformation is prevented from contracting due to the long relaxation time of the long-chain branch structure. High stress is easily generated. Due to its mechanism, strain hardening does not occur in shear deformation that predominates in the extruder or in the flow path of the molding machine, and is characterized by not significantly affecting the fluidity. Therefore, the long chain branch has an advantage that melt elasticity can be imparted without lowering the fluidity.

The ethylene polymer produced by the Phillips type catalyst has excellent long-chain branching and thus is excellent in molding stability. However, it is said that impact resistance performance and long-term performance are inferior because it is difficult to selectively impart short chain branching to a high molecular weight component and arbitrarily adjust the molecular weight distribution. For conventional Ziegler-Natta type catalysts in which long chain branching is not generated, a method of controlling the molecular weight distribution by multi-stage polymerization or blending to improve moldability has been proposed (JP-A-8-302083 and the like). However, at this time, it is difficult to satisfy both the provision of the ultrahigh molecular weight component that contributes to the development of melt elasticity and the reduction of the gel that causes the appearance defect of the product or the starting point of the destruction. In addition, since the molding stability depends on the ultra-high molecular weight component, the fluidity is never sufficient. In addition, there is a method of imparting long chain branching by a slight amount of crosslinking using peroxide, oxygen, or electron beam, but there is a problem in gel generation or discoloration, addition of a third component such as peroxide, or electron emission. The line treatment process leads to high costs. Further, since crosslinking is also a deterioration phenomenon of the resin, it is difficult to completely prevent secondary deterioration components from accumulating in the manufacturing system, and there is a problem in long-term manufacturing stability.

As described above, melt elasticity is necessary for molding stability, but excessive melt elasticity leaves unnecessary anisotropy and residual stress in the molded product, and impact resistance and long-term performance are extremely deteriorated. There is a case. Since there are a wide variety of polyethylene molding technologies and the molding speed varies greatly depending on the molding method or the scale of the molding machine, the optimum melt elasticity in terms of the balance with the solid physical properties of the molded product is not always constant, and individual adjustment is necessary. Is. However, in the prior art, it was impossible to adjust the melt elasticity without changing the molecular weight distribution or composition distribution, which greatly affects the impact resistance performance and long-term performance.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to secure a comprehensive balance of impact resistance performance, long-term performance such as stress crack resistance, molding stability and fluidity of a polyethylene resin material. In addition, the controllability of the moldability is achieved without changing the molecular weight distribution and the composition distribution.

[0007]

The present inventors have developed a long-term performance such as impact resistance and stress crack resistance by appropriately containing an ethylene copolymer having a narrow composition distribution and a high molecular weight. By controlling the long-chain branching instead of the ultra-high molecular weight to provide melt elasticity that is optimal for molding, it suppresses the deterioration of fluidity and gel formation, and controls long-chain branching almost independently of the molecular weight distribution and composition distribution. By doing so, it was found that the above problems can be solved by ensuring the balance between solid physical properties and moldability, and the present invention has been completed.

That is, according to the first aspect of the present invention, (a) the density is 0.
90 to 0.97 g / cm ³ , (b) 190 ° C., melt flow rate (MFR) under load of 21.18 N is 0.001 to 300 d
g / min, (c) extensional viscosity parameter (SHP) is 0.
The present invention relates to a polyethylene resin material which satisfies the condition of 10 to 2.5.

The second aspect of the present invention is (1) the density is 0.90 to 0.97.
g / cm ³ , (2) High load melt flow rate (HLMFR) under load of 190 ° C, 211.82N is 0.001〜
100 dg / min, (3) molecular weight distribution (Mw / Mn)
Is 3.0 to 8.0, and (4) the comonomer sequence distribution (CSD) is 0 to 3.0, the ethylene polymer (A) is 10 to 90%, and the other ethylene polymer (B) is 90 to 10%. % Of the composition,
(A) Density is 0.90 to 0.97 g / cm ³ , (b) 190 ° C, 2
Melt flow rate (MFR) under a load of 1.18N is 0.
The polyethylene-based resin material according to the first aspect of the present invention satisfies the conditions of 001 to 300 dg / min and (c) extensional viscosity parameter (SHP) of 0.10 to 2.5.

A third aspect of the present invention is the polyethylene resin material according to the second aspect of the present invention, wherein the ethylene (co) polymer (B) has (1) a density of 0.90 to 0.98 g / cm ³ , (2) )
Melt flow rate (MFR) is 1-1000 dg / mi
The present invention relates to a polyethylene resin material satisfying the conditions of n.

A fourth aspect of the present invention is the polyethylene resin according to the third aspect of the present invention, wherein the ethylene (co) polymer (B) has a molecular weight distribution (Mw / Mn) of 3.0 to 8.0. Regarding materials.

The fifth aspect of the present invention is the second to fourth aspects of the present invention.
The polyethylene-based resin material, wherein the ethylene-based polymer (A) is produced using a Ziegler-based catalyst.

A sixth aspect of the present invention is the polyethylene-based resin material according to the fifth aspect of the present invention, wherein the ethylene-based polymer (A) is used.
Is a magnesium compound (M), a titanium compound (T),
Using a Ziegler-based catalyst containing a solid component obtained by treating at least one of solid components containing halogen as an essential component with a first electron donating compound (D1) and / or an organoaluminum compound (A1), if desired. The present invention relates to a polyethylene-based resin material that is a polymerized product. A seventh aspect of the present invention is the use of a Ziegler-based catalyst comprising a solid catalyst component obtained by further treating the sixth solid component of the present invention with a second electron donating compound (D2) and an organoaluminum (A2). The present invention relates to a polymerized polyethylene resin material.

An eighth aspect of the present invention is a polyethylene system wherein the sixth or seventh solid catalyst component of the present invention is a solid catalyst component particle in which the proportion of the solid component having a particle size of 30 μm or less is 95% or more. Regarding resin material.

A ninth aspect of the present invention relates to a molded article comprising the polyethylene resin material according to any one of the first to eighth aspects of the present invention.

The tenth aspect of the present invention relates to the molded article, wherein the ninth molded article of the present invention is a film.

The present invention will be described in detail below. The polyethylene resin material of the present invention is composed of a polyethylene resin material containing an ethylene homopolymer or a copolymer of ethylene and α-olefin, and has a density (a) of 0.90 to 0.
97 g / cm ³ , (b) 190 ° C., melt flow rate (MFR) under load of 21.18 N is 0.001 to 300 dg / m
in, (c) extensional viscosity parameter (SHP) is 0.10 to 2.
A polyethylene resin material having specific parameters that satisfy the conditions of 5.

The above-mentioned copolymer of ethylene and α-olefin is ethylene and has 3 to 20 carbon atoms, preferably 3 to 1 carbon atoms.
It is a copolymer with the α-olefin of 2. 3 to 2 carbon atoms
As the α-olefin of 0, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-
Tetradecene, 1-hexadecene, 1-octadecene,
1-eikosen etc. are mentioned.

The density of the polyethylene resin material is 0.90-0.
97 g / cm ^3, preferably 0.91~0.96g / cm ^3.
If the density is less than 0.90 g / cm ³ , the rigidity and ESCR may decrease, and if it exceeds 0.97 g / cm ³ , the impact resistance may decrease.

The melt flow rate (MFR) of polyethylene resin material at 190 ° C. under a load of 21.18 N is
0.001 to 300 dg / min, preferably 0.003 to
100 dg / min, more preferably 0.01 to 30 dg /
It is min. If the MFR is less than 0.001 dg / min,
There is a risk that the fluidity will decrease and the moldability will deteriorate. Also, M
When FR exceeds 300 dg / min, there is a concern that the impact resistance may decrease.

The extensional viscosity parameter (SHP) of the polyethylene resin material of the present invention is 0.10 to 2.5, preferably 0.1.
It is 5 to 2.2, more preferably 0.20 to 2.0, but the optimum SHP value varies depending on the molding method and molding conditions. However, if the extensional viscosity parameter (SHP) is less than 0.10, melt elasticity is insufficient, and if it exceeds 2.5, excessive residual stress and anisotropy occur in the molded product, resulting in impact resistance and stress crack resistance. In many cases, problems will occur in the long-term performance of.

Here, the extensional viscosity parameter (SHP) is a strain hardening in extensional viscosity, that is, a parameter obtained by measuring the viscosity at a constant strain rate at a specific temperature for maintaining a molten state (for details, refer to “Examples”). )), Which indicates the degree of elasticity development, and a large SHP value indicates strong strain hardening, and a small SHP value indicates weak strain hardening.

In addition, such a polyethylene-based resin material is obtained by adding the following high-molecular-weight ethylene-based polymer (A)
It is preferable to contain 0 to 90% by mass, preferably 15 to 85% by mass, and more preferably 20 to 80% by mass.

Here, the ethylene-based polymer (A) is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-hexene and 4-methyl-1-.
Pentene, 3-methyl-1-pentene, 1-octene,
1-decene, 1-tetradecene, 1-hexadecene, 1
-Octadecene, 1-eicosene and the like.

The density of the ethylene polymer (A) is 0.90-0.
97 g / cm ^3, preferably 0.91~0.96g / cm ^3, more preferably 0.92~0.95g / cm ^3.

High load melt flow rate (H) of ethylene polymer (A) at 190 ° C. under a load of 211.82 N
LMFR) is 0.001 to 10 dg / min, preferably 0.003 to 3 dg / min, more preferably 0.01 to
It is 1 dg / min. HLMFR is 0.001 dg / mi
When it is less than n, gel is remarkably generated in the composition as a cause of appearance failure of the product or a starting point of breakage, 10 dg / m
If it exceeds in, there is a concern that the long-term physical properties such as impact resistance and stress crack resistance may deteriorate.

The molecular weight distribution of the ethylene polymer (A) is
The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC is 3.0 to 8.0, preferably 3.5 to 7.5, and more preferably 4.0 to 7.0. M
If w / Mn is less than 3.0, the content of high molecular weight components suitable for long-term performance such as impact resistance and stress crack resistance is low, so in order to ensure this, the average molecular weight must be increased. Therefore, there is concern that gel may be generated and fluidity may be reduced. Further, when Mw / Mn exceeds 8.0, a component having a remarkably high molecular weight with respect to the average molecular weight is contained, and thus gelation is also concerned.

The comonomer sequence distribution (CSD) of the ethylene polymer (A) is 0.
To 3.0, preferably 0 to 2.5, more preferably 0.
2.0. Here, CSD means a comonomer insertion state in an ethylene-based polymer (for details, refer to the section of “Example”). When the CSD value is large, the comonomer is more block-inserted, and the CSD value is larger. A smaller value indicates that the comonomer is more alternately (or randomly) inserted. Therefore, the smaller the CSD value, the better the composition distribution. When the CSD exceeds 3.0, the thickness distribution of the crystalline lamella is excessively widened and the low crystalline rubber-like component is present as a phase separation, so that long-term performance such as stress crack resistance is deteriorated.

When a balance with the fluidity is required, the ethylene polymer composition contains 10 to 90% by mass, preferably 15 to 85% by mass of the ethylene copolymer (A).
90% by mass of a low molecular weight ethylene polymer (B) satisfying the following conditions:
It is desirable that the amount is 0% by mass, preferably 85 to 15% by mass, and more preferably 20 to 80% by mass.

Here, the density of the ethylene polymer (B) is 0.90 to 0.98 g / cm ³ . When the composition is required to have rigidity, it is preferably 0.94 to 0.98 g / cm ³ . The ethylene polymer (B) has a melt flow rate (MFR; measured at 190 ° C. and a load of 21.18 N) of 1 to 100.
0 dg / min, preferably 3 to 700 dg / min,
More preferably, it is 1 to 500 dg / min. MFR
If less than 1 dg / min, the fluidity of the polyethylene resin material may decrease, and if more than 1000 dg / min, long-term physical properties such as impact resistance and stress crack resistance may deteriorate.

When further impact resistance and long-term performance are required, the ethylene polymer (B) has a molecular weight distribution (Mw / Mn) of 3.0 to 8.0, more preferably 3.0 to 7.
5, and more preferably 3.0 to 7.0.

The method for polymerizing the ethylene polymer (A) or other ethylene polymer (B) used in the polyethylene resin material of the present invention is not particularly limited, and a liquid phase such as a slurry polymerization method or a solution polymerization method is used. Although any polymerization method such as a polymerization method and a gas phase polymerization method is possible, a liquid phase polymerization method is preferable. Further, not only batch polymerization, but also continuous polymerization and batch polymerization can be applied.

The above liquid phase polymerization method is usually carried out in a hydrocarbon solvent. Hydrocarbon solvents include propane, butane,
Inert hydrocarbons such as isobutane, hexane, octane, decane, cyclohexane, benzene, toluene and xylene may be used alone or as a mixture. The polymerization temperature is generally 0 to 300 ° C, and practically 20 to 200 ° C. The polymerization pressure is atmospheric pressure to 10 MPa, preferably 0.3
~ 5 MPa. If necessary, a chain transfer agent such as hydrogen may be allowed to coexist in the polymerization system in order to adjust the molecular weight.

The polyethylene resin material of the present invention can be produced not only by blending but also by a multistage polymerization method in which a plurality of polymerization vessels are connected. The catalyst for producing the ethylene polymer (A) or the polymer (B) used in the polyethylene resin material of the present invention is not particularly limited, but is preferably produced using a Ziegler catalyst, which will be described below. It can be easily produced by using the catalyst.

(I) Solid catalyst component There are various methods for preparing the solid catalyst component in the Ziegler catalyst, and the solid catalyst component obtained by any method can be used as the solid catalyst component in the present invention. For example, it may be a solid catalyst component obtained by a method in which a magnesium salt such as magnesium chloride is mixed with titanium halide in a slurry or a solution, and then the solid catalyst component is precipitated or precipitated. It may also be a solid catalyst component obtained by finely granulating a solid inorganic magnesium compound by a mechanical operation and treating it with a titanium compound. Preferably, the ethylene polymer (A) or (B) contains at least one selected from the group consisting of a magnesium compound (M), a titanium compound (T), and a solid component containing halogen as an essential component, and optionally a first electron. Donor compound (D1) and / or organoaluminum compound (A
It is produced using a Ziegler type catalyst containing the solid component (1) treated in 1).

Further, more preferably, the solid component (1) is further treated with a second electron-donating compound (D2) to produce a solid catalyst component and a Ziegler type catalyst composed of organic aluminum (A2). It is what is done.

As the solid catalyst component, a solid inorganic magnesium compound containing a halogen atom such as magnesium halide described below is pulverized by a physical or mechanical treatment in an inert gas atmosphere, and further treated with a titanium compound. Or a solid catalyst component obtained by co-pulverization with a titanium compound. In the following,
The solid catalyst component obtained by this method will be described. First, the constituent components will be described.

(1) Structure of solid catalyst component (i) The magnesium compound (M) is preferably an inorganic magnesium compound containing a solid halogen atom. Specific examples include compounds represented by the following general formula (1) or (2).

Embedded image Mg (X ¹ ) ₂ (1) Mg (OH) X ¹ (2) where X ¹ is a halogen atom. Mg (X ¹ ) ₂ represented by the general formula (1) is preferable, specifically magnesium fluoride, magnesium chloride, magnesium bromide and magnesium iodide, and particularly preferable is magnesium chloride.

(Ii) The titanium compound (T) is preferably a titanium compound containing a halogen atom, and specific examples thereof include compounds represented by the general formula (3) or (4).

Embedded image Ti (OR ¹ ) _m (X ² ) _4-m (3) Ti (OR ² ) _n (X ² ) _3-n (4) where R ¹ and R ² have 1 to 20 carbon atoms. An alkyl group of
An aryl group having 6 to 20 carbon atoms, an aryl group having an alkyl group having 1 to 20 carbon atoms, or an alkyl group having an aryl group having 6 to 20 carbon atoms, X ² is a halogen atom, and m is 0 or It is an integer of 1 to 3, and n is 0 or an integer of 1 to 2.

A tetravalent titanium compound represented by the general formula (3) is preferable. Specific examples include titanium halides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide; alkoxytitaniums such as tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium and tetraphenoxytitanium; ethoxytitanium trichloride. And alkoxytitanium halides such as butoxytitanium trichloride, phenoxytitanium trichloride, dibutoxytitanium dichloride and tributoxytitanium chloride. These titanium compounds may be used alone or in combination of two or more. A titanium halide compound is preferable, and titanium tetrachloride is particularly preferable. Halogen is preferably chlorine, but since it is usually supplied from the sources of (i) magnesium compound (M) and (ii) titanium compound (T), it need not be added separately.

(Iii) The first electron-donating compound (D1) includes ethers, alcohols, phenols, ketones, aldehydes, carboxylic acids, esters, acid amides, acid anhydrides and the like. Examples thereof include oxygen compounds, nitrogen-containing compounds such as ammonia, amines and nitriles, and sulfur-containing compounds such as thiols.

The preferred first electron donating compound (D1) is
Although not particularly limited, it is preferably a heterocyclic compound containing an oxygen atom and / or a nitrogen atom in the ring. More preferably, it is a 4-membered to 8-membered heterocyclic compound in which all the hydrocarbon groups have at most 32 carbon atoms and contain oxygen atoms and / or nitrogen atoms in the ring. Specific examples include oxetane, furan, tetrahydrofuran, 1,3-dioxolane, 2-methyloxolane, 2,5-dimethyloxolane, 3-methyloxolane, pyran, tetrahydropyran, 2-methyloxane, 2,6-. Dimethyloxane, morpholine, 2,4,6-trimethyloxane,
Oxygen-containing heterocyclic compounds such as 1,4-dioxane, 2-methyl-1,4-dioxane, benzofuran, coumaran, benzopyran, chroman, isochromene and isoclaman, and pyridine, pyritadine, pyrimidine, pyrazine, triazinequinoline and isoquinoline. A nitrogen-containing heterocyclic compound is mentioned. Among these, a 4-membered to 8-membered heterocyclic compound containing an oxygen atom in the ring is preferable, and tetrahydrofuran is particularly preferable.

(Iv) The organoaluminum compound (A1) is an organoaluminum compound represented by the general formula (5).

Embedded image Al (R ³ ) _a (X ³ ) _3-a (5) Here, R ³ is an aliphatic, alicyclic or aromatic hydrocarbon group having at most 12 carbon atoms, X ³ is a halogen atom or a hydrogen atom, and a is an integer of 1 to 3.

Specifically, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum,
Tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum,
Diethyl aluminum chloride, di-normal butyl aluminum chloride, diisobutyl aluminum chloride, di-normal hexyl aluminum chloride,
Examples include dinormal octyl aluminum chloride, ethyl aluminum dichloride, normal butyl aluminum dichloride, normal hexyl aluminum dichloride, normal octyl dichloride, diethyl aluminum hydride, dinormal butyl aluminum hydride, dinormal hexyl aluminum hydride, and dinormal octyl aluminum hydride. it can.

These organoaluminum compounds may be used alone or in combination of two or more. Preferably, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum, trinormal octyl aluminum, diethyl aluminum chloride, dinormal butyl aluminum chloride,
Dinormal hexyl aluminum chloride and dinormal octyl aluminum chloride are preferable, and triethyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum, trinormal octyl aluminum, and diethyl aluminum chloride are particularly preferable.

(Iv) The second electron-donating compound (D2) includes ethers, alcohols, phenols, ketones, aldehydes, carboxylic acids, esters, acid amides, acid anhydrides and the like. Examples thereof include oxygen compounds, nitrogen-containing compounds such as ammonia, amines and nitriles, and sulfur-containing compounds such as thiols. Preferably, it is a heterocyclic compound containing an oxygen atom and / or a nitrogen atom in the ring. More preferably, it is a 4-membered to 8-membered heterocyclic compound in which all the hydrocarbon groups have at most 32 carbon atoms and contain oxygen atoms and / or nitrogen atoms in the ring. Specific examples include oxetane, furan, tetrahydrofuran, 1,3-dioxolane, 2-methyloxolane, 2,5-dimethyloxolane, 3-methyloxolane, pyran, tetrahydropyran, 2-methyloxane, 2,6-. Dimethyloxane, morpholine, 2,
4,6-trimethyloxane, 1,4-dioxane, 2
-Oxygenated heterocyclic compounds such as methyl-1,4-dioxane, benzofuran, coumarane, benzopyran, chroman, isochromene, and isoclaman, and pyridine, pyritadine, pyrimidine, pyrazine, triazinequinoline,
Examples thereof include nitrogen-containing heterocyclic compounds such as isoquinoline.
Among these, a 4-membered to 8-membered heterocyclic compound containing an oxygen atom in the ring is preferable, and a 4-membered to 8-membered heterocyclic compound containing an oxygen atom in the 1-atom ring is particularly preferable. Tetrahydrofuran is an example.

(2) Method for preparing solid catalyst component The particle size distribution of the solid catalyst component containing magnesium compound, titanium compound and halogen as essential components is 30 μm.
The abundance ratio of particles having a particle diameter of m or less is preferably 95% or more. The lower limit of the particle size is not particularly limited, but if the particle size is too small, it is inconvenient for treatment and operation. Usually 0.1
It is preferably at least μm. In order to enhance the polymerization activity, it is preferable to treat with the first electron donating compound D1 after the physical atomization.

This particle size is obtained by the method described in the section "Measurement of abundance ratio of particles" in Examples described later. By adopting such a particle size distribution, it is possible to improve the α-olefin composition distribution of the ethylene polymer produced using the obtained catalyst. As a specific effect, the comonomer sequence distribution (CSD) showing the degree of compositional distribution described below for the obtained ethylene-based polymer is 0 to 3.0, preferably 0 to 2.5.

The process of preparing the solid catalyst component will be described in more detail below. The magnesium compound is pulverized by physical and mechanical treatments. Specifically, it is a physical or mechanical operation such as dry or wet pulverization and classification. Preferably, wet grinding is essential, and dry grinding can be appropriately used in combination. When dry crushing is adopted, wet crushing is performed after dry crushing. That is, in this case, first, the magnesium compound is dry-milled. Here, dry grinding means grinding without adding a solvent. The purpose of this dry pulverization is to activate the magnesium compound by increasing the surface area and reducing the crystallinity.

Dry pulverization can be carried out, for example, according to the method described in “Powder Engineering Handbook” (Powder Engineering Society ed. Unit operation for handling microfluids 1. Crushing (Pages 486 to 513)
Can be done in the manner shown in. Specifically, it is usually carried out at around room temperature using a crusher such as a ball mill, a vibration ball mill, and an impact crusher.
Generally, the crushing time may be 30 minutes or more, but a preferable range for production is 1 hour to 100 hours.

An ethylene copolymer having a good composition distribution which can be used in the present invention can be produced without dry pulverization, but dry pulverization is preferably carried out beforehand in terms of high activity.

In the present invention, the physical and mechanical treatment of the magnesium compound means a method of finely granulating the magnesium compound by a mechanical operation such as classification or wet pulverization. According to this physical method, particles having a particle size of 30 μm or less can be classified to 95% or less so as to show an effect equal to or higher than that of a catalyst component by a chemical method using a large amount of an electron donating compound or the like. . For classification, refer to V. of the Powder Engineering Handbook (Powder Engineering Society, edited by Nikkan Kogyosha, 1986). Unit operation for handling microfluids 2. Classification (514th to 535th
There are dry classification, wet classification and sieving shown on page. Either method can be adopted.

Examples of dry classification include a method using a dry classifier such as a gravity classifier, an inertia classifier, a centrifugal classifier, an elbow jet, and a fluidized bed classifier. For wet classification, a gravity type gravity settling tank, mechanical classifier, hydraulic classifier,
A method using a wet classifier such as a centrifugal hydrocyclone or a centrifugal classifier can be used. As the sieving, a method using a vibrating screen and a shifter is mainly used.

The wet pulverization is a method of making particles fine by using a solvent, and is described in V. of Powder Engineering Handbook (edited by Japan Society of Powder Engineering: Nikkan Kogyo Publishing, 1986). Unit operation for handling microfluids 1. Examples include a method of using a wet high-speed rotary mill as shown in pulverization (Table 1.10 on page 505),
There are disc rotation type and gap flow type. By performing wet pulverization, the agglomerated particles are separated and the abundance ratio of the solid catalyst component having a particle diameter of 30 μm or less is 9
It can be 5% or more. As an industrial method, a method by wet pulverization is preferable because it has a small catalyst loss and can shorten the process.

As a specific preferable wet pulverization method, a wet high speed rotary mill (colloid mill, mixer, etc.) can be used to perform pulverization in a solvent in a high shear state. The number of revolutions for obtaining a high shear state varies depending on the apparatus used and cannot be specified unconditionally, but when a colloid mill is used, for example, 1000 rpm or more is preferable, and 2000 rpm or more is more preferable. At this time, while controlling the particle size with a particle size distribution measuring device or the like, wet pulverization is performed until the abundance ratio of particles having a particle size of 30 μm or less to all particles is 95% or more.

As the solvent used for wet pulverization or classification, an inert solvent which does not chemically react with the magnesium compound is used. Specifically, the boiling point is 10 to 3
Aliphatic hydrocarbons (for example, i-pentane, n-
Organic solvents such as hexane, n-heptane, n-octane, etc., aliphatic cyclic hydrocarbons (eg, cyclohexane etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene etc.) are preferable.

Thus, the magnesium component (M), the titanium compound (T), and the halogen, which are solid components as the main components of the polyolefin production catalyst, are essential components, and if necessary, the first electron-donating compound (D1). ) And / or the organoaluminum compound (A1) is treated to produce a solid catalyst component, and its particle size distribution is such that the existence ratio of particles having a particle size of 30 μm or less is 95% or more, and usually 0.1 μm. The above makes it possible to improve the composition distribution of the obtained ethylene polymer.

As a method for treating the magnesium compound with the electron donating compound (D1) as needed, an inert solvent is used as a diluent and the electron donating compound (D1) is used.
1) to the magnesium compound (M) in a molar ratio (D1
/ M) is preferably added so that 0.01 <D1 / M <0.5. When D1 / M is 0.01 or less, the polymerization activity is low, and the powder properties of the polymer are poor. D1 / M is
If it is 0.5 or more, the settling property of the solid component is poor and washing is difficult, and the elongation-based viscosity parameter of the obtained ethylene polymer is substantially 0 (zero) and the moldability is poor. D
As 1 / M, 0.02 <D1 / M <0.4 is preferable, and 0.0
5 <D1 / M <0.3 is more preferable.

The processing temperature is generally from -20 ° C to 200 ° C.
And preferably 0 ° C to 100 ° C. The treatment time varies depending on the treatment temperature, but is generally 1 minute to 24 hours, preferably 2 minutes to 12 hours, and more preferably 5 minutes to 6 hours. As the processing apparatus, the magnesium compound after the wet pulverization may be transferred to an apparatus other than the wet pulverizer and the solvent may be added to the mixture while the electron donating compound is added to perform the treatment. It is preferable to add an electron-donating compound while performing the treatment, because the process can be shortened.

As a method of treating the titanium compound to obtain the solid catalyst component, an inert solvent is used as a diluent and
Alternatively, the titanium compound itself is used as a solvent, and the titanium compound (T) is preferably added in an amount such that the molar ratio (T / M) to the magnesium compound (M) is 0.01 <T / M <10. More preferably 0.1 <T / M
<5. If the treatment amount of the titanium compound is small, the polymerization activity is low, and if the treatment amount of the titanium compound is large, many washing steps for removing unnecessary titanium compounds are required.

The treatment temperature of the titanium compound cannot be unconditionally specified because it depends on the solvent used and the reaction pressure, but when n-hexane is used as the solvent, it is preferably 0 ° C. to 100 ° C., more preferably 20 ° C. ℃ ~ 8
0 ° C is preferred. When n-decane is used as a solvent, it is preferably 0 ° C to 150 ° C, more preferably 20 ° C to
120 ° C. is preferred. The treatment time varies depending on the treatment temperature, but is generally 5 minutes to 48 hours, preferably 10 minutes to 24 hours, and more preferably 20 minutes to 12 hours.

Although various methods can be adopted as a specific method for treating the titanium compound, the magnesium compound (or the magnesium compound treated with the electron-donating compound (D1)) and the solvent are placed in a stirring treatment device. A method in which the titanium compound is added and treated while transferring and stirring is preferable. The treatment may be performed by adding a titanium compound while performing wet pulverization in a wet pulverizer.
However, when the titanium compound is corrosive, it is necessary to select a corrosive resistant wet crusher, which causes a cost problem. Therefore, a device other than a wet pulverizer is selected as the agitable treatment device.

The solid catalyst component obtained as a result of the treatment with the titanium compound may be stored in a slurry state or may be stored in a solid state by a method such as dry-up or drying. Industrially, a method of storing in a slurry state without using a method such as dry-up or drying is preferable. As described above, a solid catalyst component consisting of a magnesium compound, a titanium compound and a solid component containing halogen as an essential component is obtained. It can be manufactured.

However, the ethylene-based polymer obtained here has a considerably good composition distribution (CSD) with respect to α-olefin, but has an extensional viscosity parameter (SHP).
May be too large. Excessive melt elasticity may leave unnecessary anisotropy and residual stress in the molded product, resulting in extremely reduced impact resistance and long-term performance. Also, since there are a wide variety of polyethylene molding technologies, and the molding speed varies greatly depending on the molding method or the scale of the molding machine, the optimum melt elasticity is not always constant in terms of the balance with the solid physical properties of the molded product, and it can be adjusted individually. is necessary. Therefore, in the present invention, a solid catalyst comprising a magnesium compound (M), a titanium compound (T), and a solid component containing halogen as an essential component in order to adjust the extensional viscosity parameter (SHP) of the obtained polymer, if necessary. The component is treated with the second electron donating compound (D2).

In the conventional method, the treatment with an electron-donating compound or the like is rarely performed after the treatment of the solid catalyst component with the titanium compound because of the outflow of the titanium component.
However, in the present invention, the treatment with the second electron donating compound (D2) is carried out while preventing the outflow and loss of the titanium component as much as possible. Therefore, the target of the treatment with the second electron-donating compound (D2) is a solid catalyst component composed of a magnesium compound (M), a titanium compound (T), and a solid component containing halogen as an essential component,
Preferably, the catalyst particles have a particle size distribution such that the existence ratio of the solid catalyst component having a particle size of 30 μm or less is 95% or more. Further, such a solid catalyst component is obtained by physically and mechanically pulverizing a magnesium compound into fine particles.

Examples of the electron-donating compound (D2) to be treated include oxygen-containing compounds such as ethers, alcohols, phenols, ketones, aldehydes, carboxylic acids, esters, acid amides and acid anhydrides. , Ammonia,
Examples thereof include nitrogen-containing compounds such as amines and nitriles and sulfur-containing compounds such as thiols. Since the solid catalyst component already contains the titanium component, it is preferable to select the titanium component so that the titanium component does not flow out or be lost as much as possible.

Preferred are heterocyclic compounds containing an oxygen atom and / or a nitrogen atom in the ring. More preferably, it is a 4-membered to 8-membered heterocyclic compound in which the total hydrocarbon group has at most 32 carbon atoms and contains oxygen atoms and / or nitrogen atoms in the ring. Specific examples include oxetane, furan, tetrahydrofuran, 1,3-dioxolane, 2-methyloxolane, 2,5-dimethyloxolane, 3-methyloxolane, pyran, tetrahydropyran, 2-methyloxane, 2,6-. Dimethyloxane,
Morpholine, 2,4,6-trimethyloxane, 1,4
-Oxygen-containing heterocyclic compounds such as dioxane, 2-methyl-1,4-dioxane, benzofuran, coumarane, benzopyran, chroman, isochromene, and isoclaman, and nitrogen-containing heterocycles such as pyridine, pyritazine, pyrimidine, pyrazine, triazinequinoline, and isoquinoline. Examples include cyclic compounds.

Among these, 4-membered to 8-membered heterocyclic compounds containing an oxygen atom in the ring are preferable, and the oxygen atom is 1
A 4-membered to 8-membered heterocyclic compound contained in the atomic ring is particularly preferable, and specific examples thereof include tetrahydrofuran.
The second electron-donating compound (D2) may be the same as or different from the electron-donating compound (D1) used if necessary, but it is necessary to prepare an ethylene polymer having a good composition distribution. It is preferred that D1 and D2 are the same compound.

The ratio (D2) of the amount of the electron donating compound (D2) treated to the magnesium compound (M) in the solid component.
The extensional viscosity parameter (SHP) described later can be adjusted by changing the (/ M molar ratio). The amount of the electron-donating compound (D2) to be treated is
The value of the extensional viscosity parameter (SHP) varies depending on the desired physical properties of the product or molding stability and cannot be determined unconditionally. However, when targeting a range of about 0.10 to 1.4 as the extensional viscosity parameter (SHP), D2 /
It is preferable to adopt an amount in the range of about 0 <D2 / M <100 as the M molar ratio. The extension viscosity parameter (SHP) decreases as the D2 / M molar ratio increases. In other words, the extensional viscosity parameter (SHP) can be adjusted by the treatment with the second electron donating compound D2. By setting the extensional viscosity parameter (SHP) to an appropriate value, good product properties or molding stability will be exhibited.

The treatment temperature cannot be unconditionally specified because it depends on the solvent used and the reaction pressure.
For example, when n-hexane is used as a solvent, 0
C. to 100.degree. C. is preferable, and 20.degree. C. to 80.degree. C. is more preferable. When n-decane is used as a solvent,
0 ° C to 150 ° C is preferable, and 20 ° C to 120 ° C is more preferable. The treatment time varies depending on the treatment temperature, but is generally 5 minutes to 48 hours, preferably 10 minutes to 24 hours, and more preferably 20 minutes to 12 hours.

By treating with the second electron-donating compound (D2) as described above, the solid catalyst component of the present invention is obtained. In order to further increase the polymerization activity, it can be preferably further treated with an organoaluminum compound (A1). As a method of treating with the organoaluminum compound (A1), an inert solvent is used as a diluent, and the organoaluminum compound (A1) has a molar ratio (A1 / M) to the magnesium compound (M) of 0.01 <A.
It is preferable to add and treat in an amount of 1 / M <100.

The treatment temperature varies depending on the solvent used and the reaction pressure and cannot be specified unconditionally.
-When hexane is used as a solvent, 0 ° C to 120 ° C.
C. is preferable, and 20.degree. C. to 80.degree. C. is more preferable. Moreover, when using n-decane as a solvent, it is 0 degreeC-1.
50 ° C is preferable, and 20 ° C to 120 ° C is more preferable. The treatment time varies depending on the treatment temperature, but generally 5
Minutes to 48 hours, preferably 10 minutes to 24 hours, and more preferably 20 minutes to 12 hours.

After the treatment with the organoaluminum compound (A1), an aliphatic hydrocarbon having a boiling point of 10 to 300 ° C. (eg, i-pentane, n-hexane, n-heptane, n-
Octane, etc.), aliphatic cyclic hydrocarbons (eg, cyclohexane), aromatic hydrocarbons (eg, benzene, etc.)
You may wash using inert solvents, such as toluene and xylene.

Since the washing temperature varies depending on the solvent used and the reaction pressure, it cannot be unconditionally specified.
100 degreeC is preferable and 20 to 80 degreeC is further preferable. Further, when n-decane is used as a solvent, 0
C. to 150.degree. C. is preferable, and 20.degree. C. to 120.degree. C. is more preferable. The washing time varies depending on the washing temperature, but is generally 1 minute to 10 hours, preferably 2 minutes to 5 hours, and more preferably 5 minutes to 2 hours. The number of washings varies depending on the concentration of the residual metal component in the solution, but generally 2
It is performed more than once, preferably three times or more.

When the solid component is treated with the electron-donating compound (D2) and the organoaluminum compound (A1), the component may be pulverized depending on the treatment amount. Therefore, when washing is required, the settling property of the component is poor and the washing may take a long time. In that case, the use of a sedimentation aid can improve the sedimentation property and shorten the cleaning time. That is, the washing time can be shortened by using the sedimentation aid even if it is pulverized by the treatment with the electron donating compound (D2), the organoaluminum compound (A1) and the like.

The compound used as the sedimentation aid is
Examples thereof include silane compounds having an alkoxy group and polyether compounds. Here, the silane compound having an alkoxy group is a compound represented by the general formula (6).

X ⁴ _p X ⁵ _q Si (OR ⁴ ) _r (6) (In the formula, X ⁴ and X ⁵ are each independently a halogen atom, a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, Aryl group, aminoaryl group, acetoxyalkyl group, cyanoalkyl group, acetoxy group, acryloxyalkyl group,
An acryloxy group, an allyl group, an allyloxy group, an aminoalkyl group, a benzoyloxyalkyl group or an allylaminoalkyl group, R ⁴ is an alkyl group having 1 to 24 carbon atoms or an aryl group, and p and q are 0 or 1, r
Is an integer of 1 to 4 and satisfies the relational expression of p + q + r = 4. )

Preferred representative examples are tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane,
Acetoxymethyltrimethoxysilane, acetoxymethyltriethoxysilane, acetoxypropyltrimethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) trimethoxysilane, 3- (N-allylamino) propyltrimethoxy Silane, allyldimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, 4-aminobutyltriethoxysilane, N- (2-aminoethyl) -3
-Aminoisobutylmethyldimethoxysilane, N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, (3-aminophenoxy) propyltrimethoxysilane, aminophenyltrimethoxysilane, 3-aminopropylmethyldi Ethoxysilane, 3-
Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, benzoyloxypropyltrimethoxysilane, benzyltriethoxysilane, 5-
(Bicycloheptenyl) triethoxysilane, bis (3
-Cyanopropyl) dimethoxysilane, bis (2-hydroxyethyl) -3-aminopyropyrtriethoxysilane, bromophenyltrimethoxysilane, chlorophenyltrimethoxysilane, 3-bromopropyltriethoxysilane, 3-bromopropyltrimethoxysilane, 1
1-bromoundecyltrimethoxysilane, butenyltriethoxysilane, n-butyltrimethoxysilane, t
-Butylvinyloxytrimethoxysilane, 2-chloroethylmethyldimethoxysilane, 2-chloroethyltriethoxysilane, 2- (chloromethyl) allyltrimethoxysilane, chloromethylmethyldiisopropoxysilane, chloromethylmethyldiethoxysilane, ((Chloromethyl) phenylethyl) trimethoxysilane, (p-
(Chloromethyl) phenyltrimethoxysilane, (p-chloromethyl) phenyltrin-propoxysilane, chloromethyltriethoxysilane, chloromethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, 3 -Chloropropyltrimethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-
Cyanopropyltriethoxysilane, 3-cyanopropyltrimethoxysilane, 11-cyanoundecyltrimethoxysilane, [2- (3-cyclohexenyl) ethyl] triethoxysilane, [2- (3-cyclohexenyl) ethyl] tri Methoxysilane, cyclohexylethyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyltrimethoxysilane, (3-cyclopentadienylpropyl) triethoxysilane, cyclopentyltrimethoxysilane, n-decylmethyltriethoxysilane, dicyclopentyldimethoxysilane, di Ethoxydichlorosilane, diethoxyvinylsilane, 1,1-diethoxy-1-silacyclopenter 3-
Ene, (N, N-diethyl 3-aminopropyl) trimethoxysilane, diethyldiethoxysilane, diisopropyldimethoxysilane, dimethoxymethylchlorosilane, 3-dimethylaminopropyldiethoxymethylsilane, N, N-dimethylaminopropyl) trimethoxy Silane, dimethyldiethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, dodecylmethyldiethoxysilane, docosenyltriethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, 2- (3,4-Epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 5,6-epoxyhexyltriene Kishishiran, ethyltrimethoxysilane, n- hexyl triethoxysilane, hexyl trimethoxysilane, isobutyl triethoxysilane, isobutyl trimethoxysilane, methacryloxy methyl triethoxy silane, methacryloxy methyl trimethoxy silane, methacryloxypropyl triethoxysilane,
Methacryloxypropyltrimethoxysilane, 3-methoxypropyltrimethoxysilane, n-methylaminopropyltrimethoxysilane, methyldiethoxysilane,
Methyldimethoxysilane, methyltriethoxysilane,
Methyltrimethoxysilane, 3-morpholinopropyltrimethoxysilane, n-octadecyltriethoxysilane, 1,7-octadienyltriethoxysilane, n
-Octylmethyldiethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, pentyltriethoxysilane, phenethyltrimethoxysilane, n-phenylaminopropyltrimethoxysilane, phenyldiethoxysilane, phenylmethyldimethoxysilane, Phenyltriethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane,
Propyltriethoxysilane, p-tolyltrimethoxysilane, triethoxychlorosilane, triethoxyfluorosilane, triethoxysilane, 2- (trimethoxysilylethyl) pyridine, 2- (trimethylsiloxy)
Furan, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylphenyldiethoxysilane,
Examples thereof include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriisopropoxysilane and vinyltriphenoxysilane.

The molecular weight of the polyether compound is 400 to
It is 1000 and generally 600 to 8000. As the polyether compound, those having a long ether bond and being linearly connected and having a flexible molecular chain are preferable. Preferred representatives include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyisobutylene glycol, polyethylene oxide, polypropylene oxide, polyisobutylene oxide, so-called crown ethers, polystyrene oxide, and polyphenylene glycol.

When a precipitation aid is used, the solid catalyst component is preliminarily added to the solid catalyst component before treatment with the electron-donating compound (D2), the organoaluminum compound (A1) used as necessary, and the like. Need to be processed.

As a treatment method, it is preferable that the solid component is made into a slurry state with an inert solvent and then added.
The treatment temperature is generally in the range of -20 to 140 ° C, preferably 0 to 100 ° C, particularly preferably 20 to 8 ° C.
It is 0 ° C. The amount of treatment is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, based on 1 mol of the magnesium compound in the solid component. If it is less than 0.01, the sedimentation effect is low, and conversely, even if it is added in excess of 10 moles, the sedimentation effect does not increase more than the amount added, and therefore, the larger the amount, the more it is disadvantageous in terms of cost.

The obtained solid catalyst component may be stored in a slurry state, or may be stored in a solid state by a method such as dry-up or drying. Industrially, a method of storing in a slurry state without using a method such as dry-up or drying is preferable.

(3) Ethylene (co) polymerization Catalyst The ethylene (co) polymerization catalyst comprises (I) a solid catalyst component and (II) an organoaluminum compound (A2). Compound (A2)
It can be obtained by contacting with and during the polymerization.

(II) Organoaluminum Compound The organoaluminum compound (A2) has the general formula (7)

Embedded image An organoaluminum compound represented by Al (R ⁵ ) _a (X ⁶ ) _3-a (7) is used. Here, R ⁵ is an aliphatic, alicyclic or aromatic hydrocarbon group having at most 12 carbon atoms, X ⁶ is a halogen atom or a hydrogen atom, and a is an integer of 1 or more and 3 or less. is there.

As specific examples, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum,
Diethyl aluminum chloride, di-normal butyl aluminum chloride, di-normal hexyl aluminum chloride, di-normal octyl aluminum chloride, ethyl aluminum dichloride, normal butyl aluminum dichloride, normal hexyl aluminum dichloride, normal octyl dichloride,
Examples thereof include diethyl aluminum hydride, di-normal butyl aluminum hydride, di-normal hexyl aluminum hydride, and di-normal octyl aluminum hydride.

These organoaluminum compounds (A2)
Can be used alone or in combination of two or more. It may also be the same as the organoaluminum compound (A1).
From the point that the extensional viscosity parameter (SHP) becomes large, in the general formula (7), R ⁵ is a hydrocarbon group having 4 to 8 carbon atoms, triisobutylaluminum in which a is 0, trinormalhexylaluminum, and trinormaloctylaluminum. Etc. are preferable, and triisobutylaluminum is more preferable.

The amount ratio of (I) the solid catalyst component and (II) the organoaluminum compound (A2) are brought into contact with each other. The molar ratio of aluminum (Al) contained in (A2) is preferably 0.5 to 500, more preferably 1 to 100.

If necessary, the polyethylene resin material of the present invention contains an antioxidant, a heat stabilizer, an acid absorbent, a weathering agent, a lubricant, an antiblocking agent, an antifogging agent, an antistatic agent, a nucleating agent. Further, various additives such as flame retardants and pigments may be included.

The polyethylene resin material of the present invention can be molded into various molded bodies in the same manner as conventional polyethylene resin materials. A molded article made of the polyethylene resin material of the present invention has a comprehensive balance of impact resistance, long-term performance such as stress crack resistance, molding stability and fluidity, and has a molecular weight distribution and a controllability of moldability. It can be achieved without changing the composition distribution, and it can be extruded, blown, blown, vacuum-pressure formed,
It can be molded by various methods such as injection molding, T-die molding and laminate molding, and can be used for various purposes such as pipes, tanks, drums, bottles, films and sheets.

[0089]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. The methods for measuring various physical properties of the solid component of the catalyst and the ethylene polymer used in Examples and Comparative Examples are as follows.

1. Measurement of the ratio of particles having a particle size of 0.9 to 175 μm: Using a JEOL HELOS SYSTEM, under a nitrogen atmosphere,
A magnesium compound or a solid catalyst component in a hexane slurry state was measured in a measurement range of a particle size of 0.9 to 175 μm by a circulation system with a focal length of 100 mm. Here, the circulation-type measurement uses SUCELL (the name of a circulation system for measuring slurry) as a sample dispersion unit, and the dispersion tank is sufficiently dehydrated and degassed with nitrogen.
After adding ml, the switch of the SUCELL pump is set to the F side and hexane is circulated uniformly, the optical axis is aligned, the reference measurement is performed, and then the solid component is added to perform the measurement.

2. Sieving with a sieve (150 μm or more) In order to measure the ratio of particles with a particle size of 150 μm or more, a standard sieve (sieve mesh) of Iida Manufacturing Co. (IIDA MANUFACTURING Co) whose mass has been measured in advance under a nitrogen atmosphere. Opening 150μm, wire diameter 104μ
Through m), a solid component, which had been slurried with hexane and whose mass was previously measured, was passed through. The sieve was thoroughly washed with hexane and dried. Weigh the sieve again,
The amount of increase in mass was determined to determine the amount of particles having a particle size of 150 μm or more. From the mass of the solid component before passing through the sieve and the mass increase of the sieve, the ratio of particles having a particle size of 150 μm or more was determined. The ratio of the magnesium compound and the solid catalyst component was also determined by the same method as in 1 and 2 above.

3. Melt flow rate (MFR) According to JIS K-7210, Table 1, condition 7, the temperature is 1
The measurement was performed at 90 ° C. and a load of 21.18 N. 4. High load melt flow rate (HLMFR) According to JIS K-7210, Table 1, condition 7, the temperature is 1
The measurement was performed at 90 ° C. and a load of 211.8N.

5. Density Measured according to JIS K-7112. 6. Molecular Weight Distribution (Mw / Mn) The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured under the following conditions using a GPC device (150C) manufactured by WATERS, and Mw / Mn was obtained. Column: Shodex-HT806M, solvent: 1,2,4-trichlorobenzene, temperature: 135 ° C.

7. Comonomer Sequence Distribution (CSD) This is an index showing the composition distribution, and was measured by 13 C-NMR under the following conditions. Device: JNM-GSX400 manufactured by JEOL Ltd., pulse width: 8.0 μsec (flip angle = 40 °), pulse repetition time: 5 seconds, number of integrations: 5000 times or more, solvent and internal standard: 1,2,4- Trichlorobenzene / benzene-d6 / hexamethyldisiloxane (mixing ratio: 30/10/1), measurement temperature: 120 ° C., sample concentration: 0.3 g / ml, and the spectrum obtained by the measurement was (1) ethylene / 1- For butene copolymers, see Macromolecules, 15, 353-360 (1
982) (Eric T. Hsieh and James C. Randall), (2)
For ethylene / 1-hexene copolymer, see Macromol
ecules, 15, 1402-1406 (1982) (Eric T. Hsieh and Ja
The triad fraction (molar fraction) was determined according to the reference of mes C. Randall). Then, it was converted into a dyad fraction (molar fraction) and CSD was determined according to the following equation.

## EQU1 ## CSD = ([CC] × [EE]) / (1/2
([EC] + [CE])) In formula ² , C: comonomer, E: ethylene, [CC]: mole fraction of continuous comonomer (C), [EC] and [CE]: ethylene (E) And the comonomer (C) are alternating, the mole fraction of [EE]: ethylene (E) is continuous. Here, when the CSD value is high, the comonomer is more block-wise inserted, and when the CSD value is low, the comonomer is more alternately (or randomly) inserted. It can be said that the smaller the CSD, the better the composition distribution.

8. Stretching viscosity parameter (SHP) Strain rate is obtained by preheating ethylene-based polymer in the shape of a strand with uniform diameter for 15 minutes in a constant temperature bath at 150 ° C.
The extensional viscosity is measured at a temperature of 150 ° C. so as to be 0.05 / sec. FIG. 1 shows an example of measurement of extensional viscosity. The viscosity growth curve obtained in this measurement has a linear portion 1 and a non-linear portion 2 when strain hardening occurs. When the slope of the linear part 1 and the slope of the tangent line of the non-linear part 2 in the logarithmic graph of the time t and the extensional viscosity η are expressed as S1 and S2, respectively, SHP is calculated by SHP = 0.512 × (S2-S1) ( Here the coefficient 0.512 is a constant.) In addition, S
1 is d (log η) in the range of 1 <logt <1.5
The minimum value of / d (logt), S2 is the maximum value of d (log η) / d (logt) in the range of 1 <logt. According to this definition, when strain hardening does not occur, generally S1 ≧ S2 and SHP becomes 0 or a negative value.
In this case, SHP = 0.

9. Tensile Impact Strength According to ASTM D1822, using S-type test piece, 23
It was measured at ° C. 10. Environmental stress crack resistance (ESCR) According to ASTM D1693, the temperature was 50 ° C., and the measurement was carried out with a 10% aqueous solution of surfactant Nonion NS-210 manufactured by NOF CORPORATION. For the measurement of tensile impact strength and environmental stress crack resistance (ESCR), a test piece cut out from a 2 mm thick sheet compression-molded at a temperature of 180 ° C was used.

Example 1: 1-1: Preparation of solid catalyst component 200 g of anhydrous MgCl ₂ (manufactured by Maruyasu Kogyo Co., Ltd.) was used as a container for a vibrating ball mill (stainless steel, cylindrical type, internal volume 1 L, stainless ball mill 10 mm in diameter). Apparent volume 6
0% filling). This was attached to a vibrating ball mill having an amplitude of 10 mm and a frequency of 30 Hz, and dry grinding was carried out for 48 hours. The ratio of particles having a particle size of 30 μm or less in the dry pulverized product of anhydrous MgCl ₂ obtained was 82%. 23. Of the dry pulverized product of anhydrous MgCl ₂ (M) obtained next.
8 g (Mg: 250 mmol) in a nitrogen atmosphere in a wet crusher (trade name: OSTERIZER BLENDERS, manufactured by US Sunbeam Co., Ltd.) (model number OB-1) having a glass bottle (model number BV-1) with an internal volume of about 1 L. Add 300 ml of hexane
10 in high shear state (rotation speed 16800 rpm)
Wet milling was performed in a hexane slurry for minutes. Further, while performing wet pulverization, 4.1 ml (50 mmol) of tetrahydrofuran (D1) was added. The wet pulverization was performed for 10 minutes at room temperature. 50 parts of the obtained component
Put it in a 0 ml flask and dip it in an oil bath equipped with a temperature controller while stirring TiCl ₄ ((T)
Wako Pure Chemical Industries, Ltd .: Purity 99 mass% or more) 5.5 ml (T
i: 50 mmol) was added at room temperature. The mixture was reacted at room temperature for 2 hours with stirring. Next, hexane washing was performed 5 times. The ratio of particles having a particle size of 30 μm or less in the solid component obtained at this time was 99%. Furthermore, while stirring, at room temperature, 5.6 ml of tetraethoxysilane (Si: 25 mm
ol) was added, the temperature was raised to 50 ° C., and stirring was carried out at 50 ° C. for 1 hour. Further tetrahydrofuran (D2) 2.7
ml (34 mmol) was added, and the mixture was stirred at 50 ° C. for 1 hour. Next, hexane washing was performed 5 times. Next, 25.2 ml (100 mmol) of triisobutylaluminum (Al) (manufactured by Toso Akzo Co., Ltd.) was added with stirring, and the mixture was stirred at room temperature for 1 hour. Next, hexane washing was performed 3 times to obtain a solid catalyst component. Particle size of the obtained solid catalyst component 30μ
The ratio of m or less was 99%.

1-2: Production of polymer (A) Triisobutylaluminum (A2) 1.0 mm was placed in a stainless steel autoclave equipped with a stirrer and having an internal volume of 1.5 liters.
ol, 600 ml of isobutane, and 20 g of 1-hexene were added, the temperature was raised to 80 ° C. with stirring, and the hydrogen partial pressure was 0 at the gauge pressure of the pressure gauge installed in the autoclave.
Hydrogen was introduced so that the pressure would be 007 MPa. 23.0 mg of the solid catalyst component prepared above was slurried with a small amount of hexane, then pressurized with ethylene and introduced into an autoclave to initiate polymerization. Polymerization was carried out for 60 minutes while continuing the supply of ethylene so that the ethylene partial pressure would be 0.2 MPa with the gauge pressure of the pressure gauge installed in the autoclave. After 60 minutes from the start of the polymerization, the supply of ethylene was stopped, the stirring was stopped, the unreacted gas in the autoclave was discharged, and the polymerization was stopped. No fouling was observed in the autoclave, and there were no lumps in the ethylene polymer, and all were obtained as powder. The ethylene polymer was vacuum dried at 60 ° C. for 4 hours. Density measured for the obtained ethylene polymer, high load melt flow rate (HLMFR),
The results of molecular weight distribution (Mw / Mn) and CSD are shown in Table 1.

1-3: Preparation of polymer B To a stainless steel autoclave with an internal volume of 1.5 liter equipped with a stirrer, 1.0 mmol of triisobutylaluminum and 600 ml of isobutane were added, and 90
The temperature was raised to 0 ° C., and hydrogen was introduced so that the hydrogen partial pressure was 1.2 MPa as a gauge pressure of a pressure gauge installed in the autoclave. 23.0 mg of the solid catalyst component prepared above was slurried with a small amount of hexane, then pressurized with ethylene and introduced into an autoclave to initiate polymerization. The ethylene partial pressure is 0.2 with the gauge pressure of the pressure gauge installed in the autoclave.
Polymerization was carried out for 60 minutes while continuing to supply ethylene so that the pressure became MPa. After 60 minutes from the start of the polymerization, the supply of ethylene was stopped, the stirring was stopped, the unreacted gas in the autoclave was discharged, and the polymerization was stopped. No fouling was observed in the autoclave, and there were no lumps in the ethylene polymer, and all were obtained as powder. The ethylene polymer was vacuum dried at 60 ° C. for 4 hours. The density and melt flow rate (MF) of the obtained ethylene-based polymer were measured.
The results of R) are shown in Table 1.

1-4: Blend of Polymers A and B Polymers A and B were mixed at the ratio shown in Table 1, and then 0.2% of an antioxidant (Irganox B225, manufactured by Ciba-Geigy) was added as an additive. It was prepared by kneading at Labo Plastomill (Toyo Seiki Seisakusho Co., Ltd.) for 7 minutes at 190 ° C. in a nitrogen atmosphere. Density, melt flow rate (MFR), CSD, SHP, TIS, ESCR of the obtained composition
The measurement results of are shown in Table 1.

Example 2: 2-1: Preparation of solid catalyst component 23.8 g (Mg: 250 mmol) of the dry pulverized product of anhydrous MgCl ₂ (M) obtained in Example 1 was used in an internal volume of nitrogen atmosphere. Put it in a wet crusher (trade name: OSTERIZER BLENDERS, manufactured by US Sunbeam Co.) having a glass bottle (model number BV-1) of about 1 L (model number OB-1) and add hexane 3
00 ml was added, and high shear state (rotation speed 16800 rp
m) was wet milled in hexane for 10 minutes. 4.1 ml (50 mmol) while performing wet pulverization
Tetrahydrofuran (D1) was added. The wet pulverization was performed for 10 minutes at room temperature. The obtained solid component was put into a 500 ml flask, and the TiCl ₄ was stirred with the flask immersed in an oil bath equipped with a temperature controller.
((T) Wako Pure Chemical Industries, Ltd .: purity 99 mass% or more) 5.5
ml (Ti: 50 mmol) was added at room temperature. The mixture was reacted at room temperature for 2 hours with stirring. Then wash with hexane 5
I've done it. Furthermore, while stirring, 5.6 ml of tetraethoxysilane (Si: 25 mmol) was added at room temperature, the temperature was raised to 50 ° C., and stirring was carried out at 50 ° C. for 1 hour. Further, tetrahydrofuran (D2) 20.2 ml (250 mm
ol) was added, and the mixture was stirred at 50 ° C. for 1 hour. Next, hexane washing was performed 5 times. The ratio of particles having a particle size of 30 μm or less in the solid component obtained at this time was 99%. Next, while stirring, triisobutylaluminum (A
1) (Tosoh Akzo) 25.2 ml (100 mmol)
Was added, and the mixture was stirred at room temperature for 1 hour. Then wash with hexane for 3
The solid catalyst component was obtained by repeating the operation. The ratio of particles having a particle size of 30 μm or less in the obtained solid catalyst component was 99%.

2-2: Production of Polymer A Polymerization was carried out under the same conditions and method as in Example 1 except that 21.0 mg of the solid catalyst component prepared above was used.
No fouling was observed in the autoclave, and there were no lumps in the ethylene polymer, and all were obtained as powder. The ethylene polymer was vacuum dried at 60 ° C. for 4 hours.
Table 1 shows the measured density, high load melt flow rate (HLMFR), molecular weight distribution (Mw / Mn), and CSD of the obtained ethylene polymer.

2-3: Production of Polymer B Polymerization was carried out under the same conditions and method as in Example 1, except that 21.0 mg of the solid catalyst component prepared above was used.
No fouling was observed in the autoclave, and there were no lumps in the ethylene polymer, and all were obtained as powder. The ethylene polymer was vacuum dried at 60 ° C. for 4 hours.
Table 1 shows the results of the density and melt flow rate (MFR) measured for the obtained ethylene-based polymer.

2-4: Blend of Polymers A and B A composition was prepared under the same conditions and method as in Example 1 except that the above polymers A and B were mixed in the ratio shown in Table 1. The density and melt flow rate (M
Table 1 shows the measurement results of FR), CSD, SHP, TIS, and ESCR.

Example 3: 3-1: Preparation of solid catalyst component The catalyst was prepared 20 times by the same preparation method as in Example 1, mixed and used in the following two-stage polymerization.

3-2: Two-stage polymerization In the first-stage polymerization reactor having an internal volume of 150 liters, dehydrated and purified isobutane was added at a rate of 150 liters / hr, and triisobutylaluminum (A2) was added at a rate of 200 mmol / hr. Is continuously fed at a rate of 4.0 g / hr, and the contents of the polymerization vessel are discharged at a required rate,
At 12 ℃, ethylene is 12kg / hr, 1-hexene is
4.3 liter / hr, hydrogen was supplied at 0.48 g / hr, the ethylene concentration in the liquid phase was 0.55% by mass, the concentration ratio of hydrogen to ethylene was 0.55 × 10 ⁻³ (w / w), and the concentration of 1-hexene was ethylene. The first stage copolymerization was continuously carried out in a liquid filled state under the conditions that the ratio was kept at 5.3 (w / w), the total pressure was 4.1 MPa, and the average residence time was 1 hour. Ethylene / 1 produced by copolymerization
-Hexene copolymer (density, high load melt flow rate (HLMFR), molecular weight distribution (Mw / Mn), CS
D is the isobutane slurry containing Table 1) as it is, and the whole amount is added to a second-stage polymerization vessel having an internal volume of 300 liters and an inner diameter of
Introduced through a continuous pipe of mm, supplying 50 liters / hr of isobutane and hydrogen without adding a catalyst, discharging 12 kg / hr of ethylene and hydrogen at 90 ° C. while discharging the contents of the polymerization vessel in the required time. 115 g / hr
At a rate of 2, the ethylene concentration is 1.6% by mass, the hydrogen concentration ratio to ethylene is 44 × 10 ⁻³ (w / w), the total pressure is 4.1 MPa, and the residence time is 1.5 hours. Stage polymerization was carried out. Isobutane was flushed from the discharge from the second-stage polymerizer to obtain an ethylene-based polymer mixture. 0.2 phr of Irganox B225 manufactured by Ciba-Geigy Co., Ltd. was added to the obtained ethylene-based polymer mixture as an antioxidant.
Add 0.1 phr of calcium stearate as an acid absorbent, and set the temperature to 19 with a KTX 37 mmφ co-directional twin screw extruder (L / D = 32) manufactured by Kobe Steel, Ltd.
Granulation was performed under the conditions of 0 ° C. and screw rotation speed of 200 rpm. The density and melt flow rate (MF) of the obtained composition
R), CSD, SHP, TIS, ESCR measurement results are shown in Table 1.

Comparative Example 1: 1-1: Preparation of solid catalyst component 4.37 mol of anhydrous aluminum chloride and 3.06 mol of diphenyldiethoxysilane were placed in a 20 liter reaction vessel together with 8 liters of toluene and stirred at 60 ° C. for 30 minutes. After the reaction, 8.75 mol (1 kg) of magnesium ethylate was added, and the mixture was reacted at 90 ° C for 1.5 hours, then cooled to 40 ° C, the supernatant was drawn off, washed with n-hexane several times, and TiC was added.
2.5 liter of l ₄ was added and reacted at 90 ° C. for 1.5 hours. After cooling the unreacted TiCl ₄ to 40 ° C. or lower, the solid catalyst was washed with n-hexane, and the dilution rate was reduced to 1/1000 or less.

1-2: Two-stage polymerization In a first-stage polymerization reactor having an internal volume of 150 liters, dehydrated and purified isobutane was added at a rate of 150 liters / hr, triisobutylaluminum was added at a rate of 200 mmol / hr, and 4.0 g of the solid catalyst component was added. 12 kg / hr of ethylene, 4.2 liter / hr of 1-hexene and 0.41 g / hr of hydrogen at 80 ° C. while continuously discharging the contents of the polymerization vessel at a required rate. , 0.55 mass% ethylene concentration in the liquid phase, 0.50 x ethylene concentration ratio of hydrogen
10 ^-3 (w / w), the ratio of 1-hexene to ethylene concentration
The first stage copolymerization was continuously carried out in a liquid-filled state under the conditions of 5.2 (w / w), a total pressure of 4.1 MPa, and an average residence time of 1 hour. Ethylene / 1-hexene copolymer produced by copolymerization (density, high load melt flow rate (HL
MFR), molecular weight distribution (Mw / Mn), CSD is shown in Table 1), and the internal volume of the isobutane slurry is 30 as it is.
The total amount was introduced into a 0 liter second-stage polymerization vessel through a continuous tube having an inner diameter of 50 mm, 50 liters / hr of isobutane and hydrogen were supplied without adding a catalyst, while discharging the content of the polymerization vessel in the required time, At 90 ° C., ethylene was supplied at a rate of 12 kg / hr and hydrogen was supplied at a rate of 90 g / hr,
Second stage polymerization was carried out under conditions of an ethylene concentration of 1.4% by mass, a hydrogen concentration ratio of ethylene to 42 × 10 ⁻³ (w / w), a total pressure of 4.1 MPa and a residence time of 1.5 hours. Isobutane was flushed from the discharge from the second-stage polymerizer to obtain an ethylene-based polymer mixture. To the obtained ethylene-based polymer mixture, 0.2 hpr of Irganox B225 manufactured by Ciba-Geigy Co., Ltd. as an antioxidant and 0.1 hpr of calcium stearate as an acid absorber were added, and KTX 37 mmφ same direction twin screw type manufactured by Kobe Steel Ltd. Granulation was carried out using an extruder (L / D = 32) under the conditions of a set temperature of 190 ° C. and a screw rotation speed of 200 rpm. Density, melt flow rate (MFR), CSD, S of the obtained composition
Table 2 shows the measurement results of HP, TIS and ESCR.

Example 4: 4-1: Two-stage polymerization 1.0 mmol of triisobutylaluminum and 600 ml of isobutane were added to a stainless steel autoclave equipped with a stirrer and having an internal volume of 1.5 liter, and the mixture was stirred at 90%.
The temperature was raised to 0 ° C., and hydrogen was introduced so that the hydrogen partial pressure was 1.2 MPa as a gauge pressure of a pressure gauge installed in the autoclave. 13.0 mg of the solid catalyst component prepared in Example 1 was slurried with a small amount of hexane, pressurized with ethylene and introduced into an autoclave to initiate polymerization. The ethylene partial pressure is the gauge pressure of the pressure gauge installed in the autoclave.
6 while continuing to supply ethylene so that the pressure becomes 0.2 MPa
Polymerization was carried out for 0 minutes. 60 minutes after the start of polymerization, the ethylene supply was stopped, the stirring was stopped, and the unreacted gas in the autoclave was discharged. The amount of heavy reaction was determined by the cumulative amount of ethylene fed. Further, the MFR of the component B polymer obtained under the same conditions in another experiment was 300 dg / min,
The density was 0.97 g / cm ³ and the Mw / Mn was 6. Next, triisobutylaluminum (1.0 mmol) and isobutane (600 ml) were added, the temperature was raised to 80 ° C. while stirring, and 20 g of 1-hexene had a hydrogen partial pressure of 0.007 MPa corresponding to a gauge pressure of a pressure gauge installed in the autoclave. The ethylene-hydrogen mixed gas prepared as described above was introduced under pressure and introduced into the autoclave to initiate polymerization. The ethylene partial pressure is the gauge pressure of the pressure gauge installed in the autoclave.
Polymerization was carried out while continuing to supply ethylene so that the pressure became 0.2 MPa. 45 minutes after the start of the polymerization, the cumulative amount of ethylene supply became the same as that of the component B. Therefore, after 45 minutes, the ethylene supply was stopped, the stirring was stopped, the unreacted gas in the autoclave was discharged, and the polymerization was stopped. did. No fouling was observed in the autoclave, and no lumps were present in the ethylene-based polymer mixture, and all were obtained as powder. The ethylene-based polymer mixture was vacuum dried at 60 ° C. for 4 hours. An antioxidant (Irganox B225, manufactured by Ciba Geigy) was added to the obtained ethylene-based polymer mixture as an additive.
0.2% was added, and the mixture was kneaded in a Labo Plastomill (Toyo Seiki Seisakusho Co., Ltd.) at 190 ° C. for 7 minutes in a nitrogen atmosphere. The density and melt flow rate (MF) of the obtained composition
R), CSD, SHP, TIS, ESCR measurement results are shown in Table 1.

Example 5: 5-1: Production of Polymer B Example 18 was repeated except that 18 mg of the solid catalyst component prepared in Comparative Example 1 was used and hydrogen was introduced so that the partial pressure of hydrogen was 1.1 MPa. Polymerization was carried out under the same conditions and method as in.
No fouling was observed in the autoclave, and there were no lumps in the ethylene polymer, and all were obtained as powder. The ethylene polymer was vacuum dried at 60 ° C. for 4 hours.
Table 1 shows the results of the density and melt flow rate (MFR) measured for the obtained ethylene-based polymer.

Example 1 was the same as Example 1 except that the polymer A obtained in Example 1 and the polymer B were mixed in the ratio shown in Table 1.
A composition was prepared under the same conditions and method as described above. Density, melt flow rate (MFR), CSD, S of the obtained composition
Table 1 shows the measurement results of HP, TIS and ESCR.

Example 6: 6-1: Preparation of polymer A Using 23 mg of the catalyst of Example 1, 3 g of 1-hexene was added, and hydrogen was introduced so that the partial pressure of hydrogen was 0.015 MPa. The same conditions and methods as in Example 1 were used. No fouling was found inside the autoclave,
The ethylene polymer had no lumps and was obtained as a powder. The ethylene polymer was vacuum dried at 60 ° C. for 4 hours. The density measured for the obtained ethylene-based polymer,
Table 1 shows the results of high load melt flow rate (HLMFR), molecular weight distribution (Mw / Mn), and CSD.

6-2: Production of polymer B Using 23 mg of the catalyst of Example 1, the hydrogen partial pressure was 0.6 MPa.
All were carried out under the same conditions and method as in Example 1 except that hydrogen was introduced so as to be a. No fouling was observed in the autoclave, and there were no lumps in the ethylene polymer, and all were obtained as powder. 60 ethylene polymer
It was vacuum dried at 4 ° C for 4 hours. Table 1 shows the results of the density and melt flow rate (MFR) measured for the obtained ethylene-based polymer.

6-3: Blend of Polymers A and B A composition was prepared under the same conditions and method as in Example 1 except that the above polymers A and B were mixed in the ratio shown in Table 1. The density and melt flow rate (M
Table 1 shows the measurement results of FR), CSD, SHP, TIS, and ESCR.

Comparative Example 2: 2-1: Preparation of Polymer A All except that 18 mg of the catalyst of Comparative Example 1 was used, 2 g of 1-hexene was added, and hydrogen was introduced so that the hydrogen partial pressure was 0.015 MPa. The same conditions and methods as in Example 1 were used. No fouling was found inside the autoclave,
The ethylene polymer had no lumps and was obtained as a powder. The ethylene polymer was vacuum dried at 60 ° C. for 4 hours. The density measured for the obtained ethylene-based polymer,
Table 2 shows the results of high load melt flow rate (HLMFR), molecular weight distribution (Mw / Mn), and CSD.

2-2: Production of Polymer B 18 mg of the catalyst of Comparative Example 1 was used, and the hydrogen partial pressure was 0.6 MPa.
All were carried out under the same conditions and method as in Example 1 except that hydrogen was introduced so as to be a. No fouling was observed in the autoclave, and there were no lumps in the ethylene polymer, and all were obtained as powder. 60 ethylene polymer
It was vacuum dried at 4 ° C for 4 hours. Table 2 shows the results of the density and melt flow rate (MFR) measured for the obtained ethylene polymer.

2-2: Blend of Polymers A and B A composition was prepared under the same conditions and method as in Example 1 except that the above polymers A and B were mixed in the ratio shown in Table 2. The density and melt flow rate (M
Table 2 shows the measurement results of FR), CSD, SHP, TIS, and ESCR.

[0118]

[Table 1]

[0119]

[Table 2]

From Examples 1 to 5 and Comparative Example 1, the ethylene polymers obtained in Examples 1 to 5 exhibited the same impact resistance and stress crack resistance as Comparative Example 1, and had a high melt elasticity. It can be seen that the molding stability is excellent. Further, from Example 6 and Comparative Example 2, the ethylene-based copolymer obtained in Example 4 exhibits the same impact resistance and stress crack resistance as Comparative Example 2, and has high melt elasticity and excellent molding stability. I understand.

Example 7: Using the composition granulated in Example 3, an inflation film was formed under the following conditions to obtain a film having a thickness of 20 μm. Extruder: Placo ENF-75 Co., Ltd., setting temperature: 190 ° C, screw rotation speed: about 40 rp
m, die: 120φ SPNL of Tommy Machinery Co., Ltd., die diameter: 120 mm, lip gap: 0.7 mm, take-up speed: 60 m / min, frost line height: 1150
mm, film folding diameter 450 mm, stable body diameter: 90 mm.

Table 3 shows the physical properties of the film and bubble stability during molding. The tensile properties of the film are JI
Measured according to SK7127, the tear strength of the film is J
Measured according to ISK7128-2 (Elmendorf tear method), the impact fracture mass of the film by the dirt method is JIS
It measured according to K7124-1 (Staircase method).
The film thickness deviation was obtained by continuously measuring the film thickness in the bubble circumferential direction and calculating the difference between the maximum value and the minimum value. When the thickness deviation of the film is large, wrinkles and sagging occur in the film raw film, which causes various problems such as printability and slitability in the secondary processing step of the film or a decrease in bag making speed during film bag making and heat seal failure. Is likely to occur. The bubble stability was evaluated according to the following criteria. ◯: Stable molding is possible although slight movement occurs in the bubble. Δ: Bubbles move up and down, and film width changes. X: Bubbles are not stable and stable molding is impossible.

Comparative Example 3: Using the composition granulated in Comparative Example 1, an inflation film was formed in the same manner as in Example 7 and various physical properties were measured. Table 3 shows the film physical properties and bubble stability during molding.

[0124]

[Table 3]

Generally, film formability and strength are in a trade-off relationship. Here, if the moldability is emphasized, the film strength becomes low, which is a practical problem, but Example 7 having SHP is used.
The film formed in (1) maintains a practical level of impact fracture mass, has a small thickness deviation compared to Comparative Example 3, and has a significantly high formability (bubble stability), so that the product loss rate is very high. Low. Therefore, it has an extremely large economic effect.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a method for measuring an extensional viscosity parameter (SHP).

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takamasa Tsuyuki             2-3-2 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa               Japan Polyolefin Co., Ltd.             Research and Development Center (72) Inventor Yoshimitsu Ishihara             10-1 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa             R & D Center, Polyolefin Co., Ltd.             -In (72) Inventor Masakazu Yamamoto             10-1 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa             R & D Center, Polyolefin Co., Ltd.             -In (72) Inventor Kei Takahashi             2-3-2 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa               Japan Polyolefin Co., Ltd.             Research and Development Center F-term (reference) 4F071 AA15 AA15X AA20X AA21X                       AA76 AA80 AA81 AA82 AA88                       AF13 AF23 AH03 AH04 AH05                       BC01 BC04                 4J002 BB03W BB03X BB05W BB05X                       GG01 GG02 GL00                 4J028 AA01A AB01A AC02A BA00B                       BA01A BA01B BB00B BB01A                       BB01B BC14A BC14B BC15A                       BC15B BC16A BC16B BC17A                       BC17B BC27A BC27B CB22A                       CB27A CB42A CB72A EB02                       EB04 EB05 EB07 EB09 EB10                       EC01 EC02 GA06 GA07 GA08                       GA26                 4J100 AA03Q AA04Q AA15Q AA16Q                       AA17Q AA18Q AA19Q AA20P                       AA21Q CA01 CA04 DA04                       DA09 DA13 DA14 DA15 DA43                       FA09 JA58 JA67

Claims (10)

[Claims] 1. (a) A density of 0.90 to 0.97 g / cm ³ ,
(B) The melt flow rate (MFR) under load of 190 ° C. and 21.18 N is 0.001 to 300 dg / min, (c)
A polyethylene resin material characterized in that the extensional viscosity parameter (SHP) satisfies the condition of 0.10 to 2.5. 2. A density of 0.90 to 0.97 g / cm ³ ,
(2) High load melt flow rate (HLMFR) under load of 190 ° C and 211.82N is 0.001-100dg /
min, (3) molecular weight distribution (Mw / Mn) is 3.0 to 8.0,
(4) Composition of ethylene-based polymer (A) of 10 to 90% and other ethylene-based polymer (B) of 90 to 10% satisfying the condition of comonomer sequence distribution (CSD) of 0 to 3.0. (A) Density is 0.
90 to 0.97 g / cm ³ , (b) 190 ° C., melt flow rate (MFR) under load of 21.18 N is 0.001 to 300 d
g / min, (c) extensional viscosity parameter (SHP) is 0.
The polyethylene resin material according to claim 1, which satisfies the condition of 10 to 2.5. 3. The ethylene-based (co) polymer (B) comprises:
The polyethylene resin material according to claim 2, which satisfies the following conditions: (1) a density of 0.90 to 0.98 g / cm ³ and (2) a melt flow rate (MFR) of 1 to 1000 dg / min. 4. The polyethylene resin material according to claim 3, wherein the ethylene (co) polymer (B) has a molecular weight distribution (Mw / Mn) of 3.0 to 8.0. 5. The polyethylene resin material according to claim 1, which is produced by using a Ziegler catalyst. 6. The ethylene-based polymer (A) contains at least one selected from the group consisting of a magnesium compound (M), a titanium compound (T), and a solid component containing halogen as an essential component, and optionally a first electron donor. The polyethylene resin material according to claim 5, wherein the polyethylene resin material is polymerized by using a Ziegler catalyst containing a solid component obtained by treating with the compound (D1) and / or the organoaluminum compound (A1). 7. The solid component of claim 6 is further polymerized by using a Ziegler-based catalyst comprising a solid catalyst component obtained by treating the solid component with a second electron-donating compound (D2) and an organic aluminum (A2). The polyethylene resin material according to claim 5. 8. The polyethylene-based resin material according to claim 6, wherein the solid catalyst component is solid catalyst component particles in which the presence ratio of the solid component having a particle size of 30 μm or less is 95% or more. 9. A molded body made of the polyethylene resin material according to claim 1. 10. The molded article is a film.
The molded article according to.