JP2013204028A - Polyethylene based resin composition and molded body of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyethylene based resin composition which is excellent in molding processing property and can manufacture a molded body excellent in the balance of environmental stress cracking resistance and rigidity, transparency and shock resistance, and to provide molded bodies obtained by subjecting the polyethylene based resin composition to injection molding, compressive injection molding, rotation molding, extrusion molding or blow molding.SOLUTION: A polyethylene based resin composition includes 41 to 99 wt.% of an ethylene type polymer resin (A) satisfying a specific condition (A-1) and 1 to 59 wt.% of an ethylene type polymer (B) which has a specific branched long chain structure featured by elongational viscosity behavior and satisfies specific conditions (B-1) to (B-6), wherein the MFR of the whole composition is 0.1 to 1 g/10 min and a density is 0.950 to 0.965 g/cm. Further, molded bodies of the polyethylene based resin composition are provided.

Description

  The present invention relates to a novel polyethylene-based resin composition and use thereof. More specifically, the present invention is excellent in molding processability, particularly hollow moldability, and is resistant to environmental stress cracking (hereinafter also referred to as “ESCR”) and rigidity. Polyethylene resin that has excellent balance, transparency and impact strength, can be molded with thinner and lighter weight, has a high crystallization speed, excellent high-speed moldability, and can be molded in a high cycle. The present invention relates to a molded article obtained by hollow molding the composition and the polyethylene resin composition.

In recent years, plastic films, sheets, injection molded articles, pipes, extruded molded articles, hollow molded articles and the like have been actively used in various industrial fields. In particular, polyethylene resins (ethylene polymers) are widely used because they are inexpensive and lightweight, and have excellent processability, rigidity, impact strength, transparency, chemical resistance, and recyclability. Especially for hollow bottles generally used as containers for detergents, shampoos and rinses, or food containers such as edible oils, polyethylene resins having excellent moldability, physical properties and chemical properties are widely used. It has been.
In recent years, in order to reduce costs, hollow bottles have been required to be lighter, thinner, and higher cycled, and in these hollow bottle applications, particularly excellent environmental stress crack resistance, impact strength, crystallization. Characteristics such as speed are required. However, in the case of a single ethylene polymer, its melt characteristics are insufficient in terms of fluidity or insufficient in extensional viscosity, for example, and sufficient molding processability can be secured. In many cases, it is difficult or the physical stress crack resistance and the balance of rigidity and the solid physical properties such as impact resistance and transparency are insufficient.

Polyethylene polymerized using a chromium-based catalyst has a relatively wide molecular weight distribution and a molecular structure having a long-chain branched structure. Since the swell ratio is large and the pinch-off portion of the hollow bottle is easily thickened uniformly, it is generally widely used as a hollow molding material.
In addition, polyethylene that has been two-stage polymerized using a titanium-based catalyst has excellent environmental stress resistance compared to polyethylene polymerized using the above-mentioned chromium-based catalyst by selectively copolymerizing a comonomer with a high molecular weight component. As it is possible to impart cracking properties and the molecular weight and molecular weight distribution can be adjusted by controlling low molecular weight components, it is generally widely used as a high environmental stress cracking grade suitable for hollow molding. Has been.
And the polyethylene polymer composition which mixed the polyethylene polymerized in two steps using the titanium-type catalyst and the polyethylene polymerized using the chromium-type catalyst, and made use of the mutual advantage is disclosed (for example, patent document) 1-7).

However, as the weight of containers and the diversification of designs continue to increase, it is necessary to increase the density of polyethylene if the rigidity of the container is to be secured while the container is thinned, that is, the amount of comonomer copolymerization is suppressed. Since there is a need and it is contrary to the maintenance of the environmental stress crack resistance, there is still a demand for a material that has an excellent balance between rigidity and environmental stress crack resistance and can cope with the thinning.
Therefore, a polyethylene resin composition composed of multiple components is disclosed which includes polyethylene using a metallocene catalyst and has improved rigidity and environmental stress crack resistance balance (see, for example, Patent Documents 8 to 13).

However, polyethylene using a metallocene-based catalyst has a relatively narrow molecular weight distribution and a molecular structure having a uniform comonomer distribution. Since it has characteristics such as a low melt tension and a swell ratio, it is limited to use as a specific internal solution or a container having a specific shape.
Furthermore, as described in Patent Document 8, polyethylene using a metallocene-based catalyst has a low melting point and crystallization temperature corresponding to the same density, that is, it is easy to melt due to rigidity and is difficult to crystallize. The phenomenon that the speed is reduced is recognized, and there is a need to further increase the crystallization speed for high-speed molding.
In view of such circumstances, polyethylene having a high crystallization speed capable of achieving further high-speed molding and high cycle while having hollow moldability, high rigidity, impact resistance and the like required for conventional polyethylene resin compositions for containers. There is a need for materials.

As countermeasures to compensate for these problems, improvement in melt characteristics and solid physical properties can be achieved by blending polyethylene using metallocene catalyst with high-pressure polyethylene (HPLD) with excellent moldability and polyethylene using chromium catalyst. (See Patent Documents 14 to 16).
However, although these materials are improved in performance balance to some extent, they do not yet have high-speed moldability, and further improvements are required.
In hollow molding, as the weight of containers and the diversification of designs continue to increase, it is necessary to increase the density of polyethylene if the rigidity of the container is to be secured while the container is thinned. It is becoming increasingly difficult to uniformly increase the thickness of the pinch-off portion by reducing the thickness of the pin. For this reason, the environmental stress crack resistance is greatly reduced, and the target environmental stress crack resistance cannot be ensured. Therefore, there is still a demand for a material that can cope with the thinning.

  Under such circumstances, the problems of conventional ethylene-based resin compositions are solved, and a molded body having excellent molding processability, a balance between environmental stress crack resistance and rigidity, transparency, and impact strength is manufactured. It has been desired to develop a polyethylene resin composition that can be used. In particular, there is a demand for a material that can improve the molding efficiency by increasing the molding cycle and also has high-speed moldability.

JP 59-196345 A JP 59-196346 A Japanese Unexamined Patent Publication No. 60-036547 JP 2004-059650 A JP 2004091739 A JP 2004-168817 A JP 2005-29881 A JP 08-283476 A Japanese Patent Laid-Open No. 08-283477 JP 2006-83370 A JP-A-11-106574 JP 11-199719 A JP 2009-7579 A JP-A-11-140239 WO2007 / 94376 Special table 2009-506163

  In view of the above-mentioned problems of the prior art, the object of the present invention is a polyethylene-based resin that is excellent in molding process characteristics, at the same time, excellent in balance between environmental stress crack resistance and rigidity, and also excellent in transparency and impact strength. Providing a composition, and further, a molded article excellent in environmental stress crack resistance and rigidity balance, transparency and impact strength, obtained by hollow molding of the polyethylene resin composition, and use of the molded article Is to provide. In particular, an object is to provide a material that can improve the molding efficiency by increasing the molding cycle and also has a further high-speed moldability.

  As a result of intensive investigations to achieve the above-mentioned problems, the present inventors satisfy a specific balance of physical properties with a specific ethylene polymer having a specific long-chain branched structure characterized by elongational viscosity behavior. Combined with an ethylene-based composition and blended them so as to have a specific MFR and density, it was found that the obtained polyethylene-based resin composition exhibits good characteristics capable of solving the above-mentioned problems. The present invention has been completed based on these findings.

That is, according to the first invention of the present invention, 41 to 99% by weight of the ethylene polymer resin (A) satisfying the following condition (A-1) and the following conditions (B-1) to (B -6) and an ethylene polymer (B) of 1 to 59% by weight, a melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 1 g / 10 minutes, and a density Is a polyethylene-based resin composition, characterized in that it is 0.950 to 0.965 g / cm ³ .
(A-1) Ethylene polymer satisfying 50 to 90% by weight of ethylene polymer (A1) and the following conditions (A2-1) and (A2-2) based on the whole ethylene polymer resin (A) It consists of 10 to 50% by weight of the polymer (A2).
(A2-1) The melt flow rate (HLMFR _A2 ) at a temperature of 190 ° C. and a load of 21.6 kg is 0.1 g / 10 min or more and less than 5 g / 10 min.
(A2-2) The density (density _A2) is 0.915 to 0.945 g / cm ³ (B-1) MFR (MFR _B ) is 0.01 to 5.0 g / 10 minutes.
(B-2) The density (density _{B 1} ) is 0.900 to 0.960 g / cm ³ .
(B-3) The ratio ([Mw / Mn] _B ) between the weight average molecular weight and the number average molecular weight measured by gel permeation chromatography (GPC) is 2.0 to 6.0.
(B-4) The strain hardening degree ([λmax (2.0)] _B ) measured at a temperature of 170 ° C. and an elongation strain rate of 2 (unit: 1 / second) is 1.2 to 10.0.
(B-5) Strain hardening degree ([λmax (2.0)] _B ) measured at a temperature of 170 ° C. and an elongation strain rate of 2 (unit 1 / second), and an elongation strain rate of 0.1 (unit 1 / unit). strain hardening degree in the case of a second) the ratio of _{([λmax (0.1)] B} ) ([λmax (2.0)] B /[λmax(0.1)] B) is 1.2 to 10.0.
(B-6) A polymer produced by a polymerization reaction of ethylene using a catalyst containing a transition metal.

According to the second invention of the present invention, in the first invention, the ethylene polymer (B) further satisfies the following condition (B-7): Is provided.
(B-7) The content (WC) of a component having a molecular weight of 1 million or more measured by a GPC measurement device in which a differential refractometer, a viscosity detector, and a light scattering detector are combined is 0.01 to 10%, and The branching index (g _{C ′} ) at the molecular weight of 1,000,000 is 0.30 to 0.70.

  According to the third invention of the present invention, in the invention of the first or second invention, the ethylene polymer (B) is produced by copolymerization of ethylene and an α-olefin by a metallocene catalyst. -The polyethylene-type resin composition characterized by being an alpha-olefin copolymer is provided.

  According to the fourth invention of the present invention, in any one of the first to third inventions, the ethylene polymer (B) is produced by vapor phase or slurry copolymerization of ethylene and α-olefin. Provided is a polyethylene resin composition which is an ethylene / α-olefin copolymer.

According to the fifth invention of the present invention, in any one of the first to fourth inventions, the ethylene-based polymer resin (A) further comprises the following conditions (A-2) and (A-3): A polyethylene resin composition characterized by satisfying the above is provided.
(A-2) MFR (MFR _A ) is 0.1 to 1 g / 10 minutes, and HLMFR (HLMFR _A ) is 10 to 50 g / 10 minutes.
(A-3) The density (density _{A 1} ) is 0.950 to 0.965 g / cm ³ .

According to a sixth aspect of the present invention, in any one of the first to fifth aspects, the ethylene-based polymer resin (A) further satisfies the following condition (A-4): A polyethylene resin composition is provided.
(A-4) Melt flow rate ratio (HLMFR _A / MFR _A ) is 60-140.

  According to the seventh invention of the present invention, in any one of the first to sixth inventions, at least the ethylene polymer (A2) of the ethylene polymer resin (A) is Ti, Zr or Hf. There is provided a polyethylene-based resin composition, which is an ethylene / α-olefin copolymer produced by copolymerization of ethylene and α-olefin using a metallocene-based catalyst containing.

According to an eighth aspect of the present invention, there is provided a polyethylene resin composition characterized by further satisfying the following characteristics (i) to (iii) in any one of the first to seventh aspects: Provided.
Characteristic (i): All notched creep test (FNCT) based on ISO DIS 16770 is 100 hours or more.
Characteristic (ii): The peak top time in isothermal crystallization at 121.5 ° C. measured by a differential scanning calorimeter (DSC) is 200 seconds or less.
Characteristic (iii): tan δ measured at 150 ° C. and 100 rad / sec measured with a rheometer is 0.50 to 0.80.

  Moreover, according to the ninth invention of the present invention, there is provided a molded body obtained by hollow molding the polyethylene resin composition of any one of the first to eighth inventions.

  The polyethylene-based resin composition of the present invention is excellent in molding processing characteristics, and at the same time, has an excellent balance between environmental stress crack resistance and rigidity, and further has an effect of being excellent in transparency and impact strength. The molded product obtained by hollow molding of the resin-based resin composition is also excellent in the balance between environmental stress crack resistance and rigidity, transparency, and impact strength, and thus provides a thin molded product economically advantageously. It is possible.

FIG. 1 is a graph showing the baseline and interval of a chromatogram used in the gel permeation chromatography (GPC) method. FIG. 2 is a plot of the extensional viscosity when an inflection point of the extensional viscosity is observed (a typical example of the ethylene polymer (B) of the example). FIG. 3 is a plot of the extensional viscosity when no inflection point of the extensional viscosity is observed (a typical example of the ethylene polymer resin (A) of the example). FIG. 4 is a graph showing the molecular weight distribution curve calculated from GPC-VIS measurement (branching structure analysis) and the relationship between the branching index (g ′) and the molecular weight (M).

  In the present invention, an ethylene polymer resin (A) satisfying a specific balance of physical properties and a specific ethylene polymer (B) having a specific long chain branched structure characterized by elongational viscosity behavior are specified as follows. The present invention relates to a polyethylene-based resin composition blended to have an MFR and a density, a molded body obtained by molding the polyethylene-based resin composition, and uses of the molded body. Hereinafter, the present invention will be described item by item.

[I] Polyethylene Resin Composition The polyethylene resin composition of the present invention is also referred to as an ethylene polymer resin (A) (hereinafter simply referred to as “component (A)”) that satisfies a specific condition (A-1). ) 41 to 99% by weight and ethylene polymer (B) satisfying specific conditions (B-1) to (B-6) (hereinafter also simply referred to as “component (B)”) 1 to 59% by weight. %, MFR of the whole composition is 0.1 to 1 g / 10 min, and density is 0.950 to 0.965 g / cm ³ .
Moreover, it is preferable that the composition of the present invention further satisfies the following characteristics (i) to (iii).
Characteristic (i): All notched creep test (FNCT) based on ISO DIS 16770 is 100 hours or more.
Characteristic (ii): The peak top time in isothermal crystallization at 121.5 ° C. measured by a differential scanning calorimeter (DSC) is 200 seconds or less.
Characteristic (iii): tan δ at 150 ° C. and 100 rad / sec measured with a rheometer is 0.50 to 0.80 or more.
Below, each component which comprises the polyethylene-type resin composition of this invention, its characteristic, etc. are demonstrated.

1. Ethylene polymer resin (A)
(A) component which is one of the components which comprise the polyethylene-type resin composition of this invention needs to satisfy the following conditions (A-1).
(A-1) Ethylene polymer satisfying 50 to 90% by weight of ethylene polymer (A1) and the following conditions (A2-1) and (A2-2) based on the whole ethylene polymer resin (A) It consists of 10 to 50% by weight of the polymer (A2).
(A2-1) The melt flow rate (HLMFR _A2 ) at a temperature of 190 ° C. and a load of 21.6 kg is 0.1 g / 10 min or more and less than 5 g / 10 min.
(A2-2) The density (density _A2 ) is 0.915 to 0.945 g / cm ³ .

1-1. Blending ratio of ethylene polymer (A1) and ethylene polymer (A2) The blending ratio of polyethylene (A1) and ethylene polymer (A2) in ethylene polymer resin (A) is ethylene polymer resin ( A) The ethylene polymer (A2) is 50 to 10% by weight with respect to the polyethylene (A1) 50 to 90% by weight based on the whole. The ethylene polymer (A2) is preferably 45 to 15% by weight with respect to the polyethylene (A1) 55 to 85% by weight, and more preferably the ethylene polymer (A2) 40 with respect to the polyethylene (A1) 60 to 80% by weight. -20% by weight.
If the blending amount of the ethylene polymer (A2) is less than 10% by weight, the isothermal crystallization time at 121.5 ° C., which can be measured by DSC of the resin composition of the present invention, exceeds 200 seconds, and the As a result, the molding cycle may be reduced. On the other hand, if the blending amount of the ethylene polymer (A2) exceeds 50% by weight, the MFR and density of the resin composition of the present invention are lowered, and the balance of fluidity, rigidity, environmental stress crack resistance and the like is lowered. There is a fear.

Moreover, it is preferable that the ethylene polymer resin (A) contained in the polyethylene resin composition of the present invention further satisfies the following characteristics (A-2) to (A-4).
(A-2) MFR (MFR _A ) is 0.1 to 1 g / 10 minutes, and HLMFR (HLMFR _A ) is 10 to 50 g / 10 minutes.
(A-3) The density (density _{A 1} ) is 0.950 to 0.965 g / cm ³ .
(A-4) Melt flow rate ratio (HLMFR _A / MFR _A ) is 60-140.
1-2. Condition (A-2)
In the present invention, the melt flow rate (MFR _A ) of the component ( _A ) is 0.1 to 1 g / 10 minutes, and the high load melt flow rate (HLMFR _A ) is 10 to 50 g / 10 minutes. MFR _A is preferably 0.1 to 0.7 g / 10 minutes, more preferably 0.2 to 0.5 g / 10 minutes. The HLMFR is preferably 15 to 45 g / 10 minutes, more preferably 20 to 40 g / 10 minutes.
When the MFR _A is less than 0.1 g / 10 minutes, the polyethylene resin composition is inferior in molding processability, particularly melt flowability and spreadability. When the MFR _A is greater than 1 g / 10 minutes, the polyethylene resin composition and the molded article are inferior. The mechanical strength such as impact strength, tear strength, and tensile strength may be lowered, which is not preferable. Further, if HLMFR _A is less than 10 g / 10 minutes, fluidity and moldability may not be ensured, and if HLMFR _A is greater than 50 g / 10 minutes, environmental stress crack resistance may not be ensured.
In this specification, the MFR of the ethylene-based polymer and the polyethylene-based resin composition is compliant with “Testing methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastic” in JIS K7210. In conformity, it means a value when measured under the conditions of 190 ° C. and 2.16 kg load. Similarly, HLMFR is compliant with JIS K7210 “Plastics—Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics” at 190 ° C. and a load of 21.60 kg. The value when measured with.

1-3. Condition (A-3)
The density _A of the ethylene-based polymer resin (A) in the present invention is 0.950 to 0.965 g / cm ³ , preferably 0.955 to 0.960 g / cm ³ .
When the density _A is within this range, the balance between the environmental stress crack resistance and the rigidity and the impact resistance of the polyethylene resin composition and the molded article are excellent. On the other hand, if the density _A is less than 0.950 g / cm ³ , the rigidity decreases, and if the product is a thick molded body such as a pipe or various containers, the product is too soft and deforms. This is not preferable because there is a risk of being pressed. Further, if the density _A is larger than 0.965 g / cm ³ , the environmental stress crack resistance and impact strength may be impaired, which is not preferable.
In addition, in this specification, the density of an ethylene-type polymer and a polyethylene-type resin composition means the value when measured with the following method.

  The pellets were hot-pressed to prepare a press sheet having a thickness of 2 mm. The sheet was placed in a beaker having a capacity of 1000 ml, filled with distilled water, capped with a watch glass, and heated with a mantle heater. After boiling boiling water for 60 minutes, place the beaker on a wooden table and let it cool. At this time, the boiling distilled water after boiling for 60 minutes is adjusted to 500 ml so that the time until it reaches room temperature is not less than 60 minutes. Further, the test sheet is immersed in a substantially central portion in water so as not to contact the beaker and the water surface. After annealing the sheet at a temperature of 23 ° C. and a humidity of 50% for 16 hours to 24 hours, the sheet is punched out to 2 mm in length and width, and tested at 23 ° C., JIS K7112 “Plastic-non-foamed plastic density And the specific gravity measurement method ”.

1-4. Condition (A-4)
The melt flow rate ratio (HLMFR _A / MFR _A ) of the component (A) in the present invention is 60 to 140. Preferably it is 65-130, More preferably, it is 70-120.
If the melt flow rate ratio is less than 60, the viscosity at a high shear rate is high due to the narrow molecular weight distribution, and the moldability may be lowered. On the other hand, if the melt flow rate ratio is larger than 140, the impact resistance may be lowered due to the influence of the molecular weight distribution being too wide.
HLMFR _A and MFR _A are mainly adjusted by the amount of hydrogen, and the density is mainly adjusted by the amount of α-olefin, and can be applied to the ethylene-based polymer resin (A) according to the present invention.
In addition, the measuring method of HLMFR _A and MFR _A is as having shown above.
HLMFR _A / MFR _A can be adjusted by the type of catalyst, the type of cocatalyst, the polymerization temperature, the residence time in the polymerization reactor, the number of polymerization reactors, etc. The speed can be adjusted, and can be increased or decreased preferably by adjusting the mixing ratio of the high molecular weight component and the low molecular weight component, and can be increased by increasing the difference in the average molecular weight of each component.

Moreover, it is preferable that the ethylene polymer resin (A) contained in the polyethylene resin composition of the present invention further satisfies the following property (A-5).
1-5. Condition (A-5)
The component (A) in the present invention is preferably an elongation viscosity η (t) (unit: Pa · second) and an elongation time t (unit: unit) measured at a temperature of 170 ° C. and an elongation strain rate of 2 (unit: 1 / second). In the logarithmic plot (second), an inflection point of the extension viscosity due to strain hardening is observed, the maximum extension viscosity after strain hardening is η _Max (t1), and the approximate straight line of extension viscosity before hardening is η _Linear (t ), The strain hardening degree [λmax (2.0)] _A defined by η _Max (t1) / η _Linear (t1) _A is 1.2 to 5.0, preferably 1.3 to 4.0. More preferably, it is 1.4 to 3.0, and most preferably, the inflection point is not observed or [λmax (2.0)] _A is 1.5 to 2.5.
[Λmax (2.0)] If _A is less than 1.2, the ethylene polymer is not preferable. [Λmax (2.0)] When _A is greater than 5.0, the melt tension and fluidity at the time of molding are excellent, but the environmental stress crack resistance and impact strength of the polyethylene resin composition and the molded body are reduced. This is not preferable.

In general, polyethylene is processed into an industrial product by a molding method that passes through a molten state such as film molding, blow molding, foam molding, etc., but at this time, elongation flow characteristics represented by the above-mentioned elongation viscosity and strain hardening degree are used. It is well known that has a great influence on the ease of formability.
That is, polyethylene having a narrow molecular weight distribution and no long chain branching has poor moldability due to its low melt strength, whereas polyethylene having an ultrahigh molecular weight component or a long chain branching component is strain-hardened (strain Hardening), that is, polyethylene having a characteristic that the extensional viscosity rapidly increases on the high strain side, and polyethylene that exhibits this characteristic remarkably is said to be excellent in moldability. Polyethylene resin having such elongation flow characteristics, for example, the effect of preventing uneven thickness and blow-through of products in film molding and blow molding, enabling high-speed molding, and increasing the closed cell ratio during foam molding There are advantages such as improved strength of the molded product, improved design, lighter weight, improved molding cycle, improved heat insulation, etc., but on the other hand, if the elongational flow characteristics are too strong, The strength anisotropy presumed to be caused by molecular orientation causes a drop in the impact strength of the green body, or the transparency of the green body deteriorates due to a decrease in the surface smoothness of the green body that is presumed to be caused by the property of too high melt elasticity. Inconvenience occurs.
In this way, the long-chain branched structure, which is the main governing factor of the elongational viscosity property, is devised to improve the molding process surface and the disadvantages of the mechanical property of the molded body caused by the elongational flow property of polyethylene. As a result of intensive studies on the polyethylene resin composition to solve the problem, as described above, the ethylene polymer resin (A) satisfying a specific physical property balance and the ethylene heavy polymer having a specific long chain branched structure are used. When the composition (B) is used, the molding process characteristics, particularly the hollow moldability such as the drawdown resistance and the pinch-off formation are excellent, and further, the environmental stress crack resistance, the impact resistance and the rigidity balance are improved, etc. It was found that the mechanical characteristics were also excellent.

Regarding the method for measuring the strain hardening degree, as long as the uniaxial extensional viscosity can be measured, the same value can be obtained in principle by any method. For example, the measurement method and the measuring instrument are disclosed in publicly known document: Polymer 42 (2001) 8663. Details are described.
In the measurement of the ethylene-based polymer according to the present invention, preferred measurement methods and measuring instruments include the following.

Measuring method:
・ Device: Ales manufactured by Rheometrics
-Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
・ Measurement temperature: 170 ℃
-Strain rate: 2 / sec-Preparation of test piece: Press-molded to produce a sheet of 18 mm x 10 mm and thickness 0.7 mm.

Calculation method:
The elongational viscosity at 170 ° C. and a strain rate of 2 / second is plotted as a log-log graph of time t (second) on the horizontal axis and elongation viscosity η (Pa · second) on the vertical axis. On the logarithmic graph, the maximum extension viscosity until strain becomes 4.0 after strain hardening is η _Max (t1) (t1 is the time when the maximum extension viscosity is shown), and the extension viscosity before strain hardening. when the approximate line and η _linear (t), defines the value calculated as _{η Max (t1) / η linear} (t1) strain hardening degree and (.lambda.max). The presence / absence of strain hardening is determined by whether or not there is an inflection point at which the extensional viscosity changes from an upward convex curve to a downward convex curve over time.
2 and 3 are typical plots of elongational viscosity. FIG. 2 shows a case where an inflection point of the extensional viscosity is observed, and η _Max (t1) and η _Linear (t) are shown in the figure. FIG. 3 shows a case where an inflection point of elongational viscosity is not observed.

1-6. Composition of Ethylene Polymer Resin (A) As the component (A) in the present invention, those composed of polyethylene (A1) and ethylene polymer (A2) shown below can be used.

(1) Polyethylene (A1)
As the polyethylene (A1) in the present invention, a homopolymer of ethylene and / or a copolymer of ethylene and an α-olefin can be used. The polyethylene (A1) preferably satisfies the following characteristics (A) to (D).
Characteristic (A): Melt flow rate (MFR _{A1) at a} temperature of 190 ° C. and a load of 2.16 kg is 10 to 500 g / 10 minutes.
Characteristic (B): Melt flow rate (MLMFR _{A1) at a} temperature of 190 ° C. and a load of 11.1 kg is 50 to 1000 g / 10 minutes.
Characteristic (C): Melt flow rate ratio (MLMFR _a1 / MFR _A1) is 2-15.
Characteristic (D): The density _a1 is 0.960 to 0.980 g / cm ³ .

When the MFR _{a1 of the} polyethylene (A1) is less than 10 g / 10 minutes, the molecular weight increases and the fluidity and moldability may not be ensured. On the other hand, if MFR _a1 exceeds 500 g / 10 min, impact resistance may not be ensured due to the effect of increasing the amount of low molecular weight components.
In addition, when the MLMFR _a1 of the polyethylene (A1) is less than 50 g / 10 minutes, the molecular weight increases and the fluidity and moldability may not be ensured. On the other hand, if MLMFR _a1 exceeds 1000 g / 10 min, impact resistance may not be ensured due to an increase in the amount of low molecular weight components.
Furthermore, when MLMFR _a1 / MFR _a1 of polyethylene (A1) is less than 2, due to the influence of the narrow molecular weight distribution, the viscosity at a high shear rate is high, and the moldability may become a problem. On the other hand, when MLMFR _a1 / MFR _a1 exceeds 15, the impact resistance may be lowered due to the influence of the molecular weight distribution being too wide.
If the density _{a1 of the} polyethylene (A1) is less than 0.960 g / cm ³ , the rigidity of the container is inferior and the container is easily deformed at a high temperature, and the container may be deformed and cause leakage due to the influence of the container internal pressure. On the other hand, if the density _a1 exceeds 0.980 g / cm ³ , the environmental stress crack resistance of the container may be inferior.

The polyethylene (A1) according to the present invention is preferably an ethylene polymer (A1) polymerized using a Ziegler catalyst or a metallocene catalyst containing Ti, Zr, or Hf.
A Ziegler catalyst is used as the polymerization catalyst for the ethylene polymer (A1). An example of a preferable catalyst is a solid Ziegler catalyst comprising a Ti and / or V compound and an organometallic compound of Group 1 to Group 3 elements of the periodic table.
Solid Ziegler catalysts include solid catalysts containing titanium (Ti) and / or vanadium (V) and magnesium (Mg), and organometallic compounds that can be used with these components include organoaluminum compounds, Alkyl aluminum is preferred. The amount of the organoaluminum compound used in the polymerization reaction is not particularly limited, but when used, it is preferably in the range of 0.05 to 1000 mol with respect to 1 mol of the transition metal compound.

As an example of a Ziegler catalyst, for example, “catalyst” described in Example 1 of JP-A-63-202602, which is a publicly known publication, is used, and as a polymerization method, JP-A-2004-123955, which is a publicly known publication. A suitable ethylene-based polymer can be produced by taking into consideration the “mixing ratio and conditions of raw materials” described in Example 1 of the publication.
HLMFR and MFR are mainly adjusted by the amount of hydrogen, and the density is mainly adjusted by the amount of α-olefin, and can be applied to the ethylene polymer (A1) according to the present invention.

The ethylene polymer (A1) according to the present invention is preferably an ethylene homopolymer, but ethylene and an α-olefin having 3 to 12 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, It can be obtained by copolymerization with 4-methyl-1-pentene, 1-octene or the like. Also, copolymerization with a diene for the purpose of modification is possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, and the like.
The comonomer content during the polymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, an ethylene / α-olefin copolymer is used. The α-olefin content is 0 to 1 mol%, preferably 0 to 0.1 mol%, more preferably 0 to 0.01 mol%.

  The ethylene polymer (A1) according to the present invention can be produced by a production process such as a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method, preferably a slurry polymerization method. Among the polymerization conditions for the ethylene polymer, the polymerization temperature can be selected from the range of 0 to 300 ° C. In slurry polymerization, polymerization is performed at a temperature lower than the melting point of the produced polymer. The polymerization pressure can be selected from the range of atmospheric pressure to about 10 MPa. From an aliphatic hydrocarbon such as hexane, heptane and isobutane, an aromatic hydrocarbon such as benzene, toluene and xylene, an alicyclic hydrocarbon such as cyclohexane and methylcyclohexane, etc., in a state where oxygen, water, etc. are substantially cut off. It can be produced by carrying out slurry polymerization of ethylene and α-olefin in the presence of a selected inert hydrocarbon solvent.

  The ethylene polymer (A1) according to the present invention can be composed of a plurality of components. The ethylene polymer (A1) may be a polymer that is successively polymerized in a multistage polymerization reactor using one type of catalyst, and may be used in a single stage or multistage polymerization reactor using a plurality of types of catalysts. The polymer manufactured by the above may be used, and the polymer polymerized using one type or a plurality of types of catalysts may be used.

  The so-called multistage polymerization method in which polymerization is successively performed in a plurality of reactors connected in series is a manufacturing condition for producing a high molecular weight component in the first polymerization zone (first reactor) as long as the claims are satisfied. In the order of transferring the obtained polymer to the next reaction zone (second-stage reactor) and producing low molecular weight components in the second-stage reactor, In the first polymerization zone (first stage reactor), polymerization is carried out using production conditions for producing low molecular weight components, and the resulting polymer is transferred to the next reaction zone (second stage reactor). However, either order of producing the high molecular weight component in the second stage reactor may be used.

  The ethylene used for the ethylene polymer (A1) may be ethylene produced from crude oil derived from ordinary fossil raw materials, or may be ethylene derived from plants. Examples of the plant-derived ethylene and polyethylene include ethylene and polymers thereof described in JP-T 2010-511634. Plant-derived ethylene and its polymers have the property of carbon neutral (does not use fossil raw materials and does not lead to an increase in carbon dioxide in the atmosphere), and can provide environmentally friendly products.

(2) Ethylene polymer (A2)
The ethylene polymer (A2) in the present invention is polymerized by using a metallocene catalyst containing Ti, Zr, or Hf, and has a melt flow rate (HLMFR _{A2) at} a temperature of 190 ° C. and a load of 21.6 kg. _{) Of} 0.2 g / 10 min or more and less than 5 g / 10 min, and a density _a2 of 0.915 to 0.945 g / cm ³ can be used.

The HLMFR _a2 of the ethylene polymer (A2) is 0.1 g / 10 min or more and less than 5 g / 10 min, preferably 0.2 to 1.0 g / 10 min, more preferably 0.3 to 0.7 g / min. The range is 10 minutes. If this MFR _a2 is less than 0.1 g / 10 min, in the final resin composition, MFR _a2 cannot be achieved within the specified range, and the fluidity may be lowered. On the other hand, if this MFR _a2 is 5 g / 10 min or more, in the final resin composition, the environmental stress crack resistance cannot be achieved, the crystallization rate decreases, and the isothermal temperature at 121.5 ° C. can be measured by DSC. The crystallization time is increased, and as a result, the molding cycle may be lowered.

The density _a2 of the ethylene polymer (A2) is 0.915 to 0.945 g / cm ³ , preferably 0.920 to 0.935 g / cm ³ , more preferably 0.925 to 0.930 g / cm ³ . ³ . If the density _a2 is less than 0.915 g / cm ³ , the density range in the final resin composition cannot be achieved, and the rigidity may be insufficient. On the other hand, if the density _a2 exceeds 0.945 g / cm ³ , the environmental stress crack resistance may be reduced in the final resin composition.

  The ethylene polymer (A2) is preferably polymerized with a metallocene catalyst containing Ti, Zr, or Hf. Examples of the metallocene catalyst include a combination of a complex called a metallocene catalyst in which a ligand having a cyclopentadiene skeleton is coordinated to a transition metal and a promoter. Specific examples of the metallocene catalyst include a complex catalyst in which a ligand having a cyclopentadiene skeleton such as methylcyclopentadiene, dimethylcyclopentadiene, and indene is coordinated to a transition metal containing Ti, Zr, Hf, and the like. Examples of the catalyst include a combination of organic metal compounds of Group 1 to Group 3 elements such as aluminoxane, and a supported type in which these complex catalysts are supported on a carrier such as silica.

In the present invention, the metallocene catalyst used for the polymerization of the ethylene-based polymer (A2) includes the following components (a) and (b), and a catalyst that is combined with the component (c) as necessary. It is.
Component (a): Metallocene complex Component (b): Compound that reacts with component (a) to form a cationic metallocene compound Component (c): Fine particle carrier

1) Component (a)
As the component (a), a metallocene compound of a Group 4 transition metal is used. Specifically, compounds represented by the following general formulas (I) to (VII) are used.
^{_{(C 5 H 5-a R}} 1 a) (C 5 H 5-b R 2 b) MXY (I)
^{_{Q 1 (C 5 H 4-}} c R 1 c) (C 5 H 4-d R 2 d) MXY (II)
^{_{Q 2 (C 5 H 4-}} e R 3 e) ZMXY (III)
^{_{(C 5 H 5-f R}} 3 f) ZMXY (IV)
^{_{(C 5 H 5-f R}} 3 f) MXYW (V)
^{_{Q 3 (C 5 H 5-}} g R 4 g) (C 5 H 5-h R 5 h) MXY (VI)
^{_{Q 4 Q 5 (C 5 H}} 3-i R 6 i) (C 5 H 3-j R 7 j) MXY (VII)

Here, Q ¹ , Q ⁴ and Q ⁵ are binding groups that bridge two conjugated five-membered ring ligands, Q ² is a binding group that bridges conjugated five-membered ring ligands and Z groups, Q ³ is a bonding group that bridges R ⁴ and R ⁵ , M is a transition metal of Group 3-12 of the periodic table, X, Y, and W are each independently hydrogen, halogen, C 1-20 Hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing carbon atom having 1 to 20 carbon atoms Z represents oxygen, a ligand containing sulfur, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms. Indicates. M is a Group 4 transition metal such as Ti, Zr, or Hf.

R1 to R7 are each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, an oxygen-containing hydrocarbon group, or a silicon-containing hydrocarbon. A hydrogen group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group is shown. Among these, it is preferable that at least one of R ^{1 to} R ⁵ is a heterocyclic aromatic group. Among the heterocyclic aromatic groups, a furyl group, a benzofuryl group, a thienyl group, and a benzothienyl group are preferable, and a furyl group and a benzofuryl group are more preferable. These heterocyclic aromatic groups include hydrocarbon groups having 1 to 20 carbon atoms, halogen groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups, silicon-containing hydrocarbon groups, and phosphorus-containing carbon groups. Although it may have a hydrogen group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, in that case, a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing hydrocarbon group are preferable. Also, two adjacent R ¹ , 2 R ² , 2 R ³ , 2 R ⁴ , 2 R ⁵ , 2 R ⁶ , or 2 R ⁷ are bonded to each other. Thus, a ring having 4 to 10 carbon atoms may be formed. a, b, c, d, e, f, g, h, i, and j are 0 ≦ a ≦ 5, 0 ≦ b ≦ 5, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, and 0 ≦ e ≦, respectively. 4, 0 ≦ f ≦ 5, 0 ≦ g ≦ 5, 0 ≦ h ≦ 5, 0 ≦ i ≦ 3, 0 ≦ j ≦ 3.

A binding group Q ¹ , Q ⁴ , Q ⁵ that bridges between two conjugated five-membered ring ligands, a binding group Q ² that bridges a conjugated five-membered ring ligand and a Z group, and R Specific examples of Q ³ that crosslinks ⁴ and R ⁵ include the following. Methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenyl Silicon-containing crosslinking groups such as silylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisylylene group, germanium-containing crosslinking group, alkylphosphine, amine, etc. . Among these, an alkylene group, an alkylidene group, a silicon-containing crosslinking group, and a germanium-containing crosslinking group are particularly preferably used.

  Specific Zr complexes represented by the above general formulas (I), (II), (III), (IV), (V), (VI) and (VII) are exemplified below. Alternatively, a compound substituted with Ti can be used in the same manner. In addition, the metallocene complexes represented by the general formulas (I), (II), (III), (IV), (V), (VI) and (VII) are compounds represented by the same general formula or different general formulas. It can be used as a mixture of two or more compounds represented by the formula.

Compounds of general formula (I) Biscyclopentadienylzirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (2-methyl-4,5-benzoin Denyl) zirconium dichloride, bisfluorenylzirconium dichloride, bis (4H-azurenyl) zirconium dichloride, bis (2-methyl-4H-azurenyl) cyclopentadienylzirconium dichloride, bis (2-methylbiscyclopentadienylzirconium) Dichloride, bis (2-methyl-4-phenyl-4H-azurenyl) zirconium dichloride, bis (2-methyl-4- (4-chlorophenyl) -4H-azurenyl) zirconium dichloride, bis (2-furylcyclo) Pentadienyl) zirconium dichloride, bis (2-furylindenyl) zirconium dichloride, bis (2-furyl-4,5-benzoindenyl) zirconium dichloride.

Compounds of general formula (II) Dimethylsilylene bis (1,1′-cyclopentadienyl) zirconium dichloride, dimethylsilylene bis [1,1 ′-(2-methylindenyl)] zirconium dichloride, dimethylsilylene bis [1, 1 '-(2-methyl-4-phenyl-indenyl)] zirconium dichloride, ethylene bis [1,1'-(2-methyl-4,5-benzoindenyl)] zirconium dichloride, dimethylsilylene bis [1,1 '-(2-Methyl-4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1,1'-(2-methyl-4-phenyl-4H-azurenyl)] zirconium dichloride, dimethylsilylenebis {1,1'- [2-Methyl-4- (4-chlorophenyl) -4H-azurenyl]} zirconium dic Lido, dimethylsilylene bis [1,1 '- (2-ethyl-4-phenyl -4H- azulenyl)] zirconium dichloride, ethylene bis [1,1' - (2-methyl -4H- azulenyl)] zirconium dichloride.
Dimethylsilylenebis [1,1 ′-(2-furylcyclopentadienyl)] zirconium dichloride, dimethylsilylenebis {1,1 ′-[2- (2-furyl) -4,5-dimethyl-cyclopentadienyl] ]} Zirconium dichloride, dimethylsilylenebis {1,1 ′-{2- [2- (5-trimethylsilyl) furyl] -4,5-dimethyl-cyclopentadienyl}} zirconium dichloride, dimethylsilylenebis {1,1 '-[2- (2-furyl) indenyl]} zirconium dichloride, dimethylsilylenebis {1,1'-[2- (2-furyl) -4-phenyl-indenyl]} zirconium dichloride, dimethylsilylenebis {1, 1 ′-[2- (2- (2- (5-methyl) furyl) -4-phenyl-indenyl]} zirconium dichloride, di Tylsilylenebis {1,1 ′-[2- (2- (5-methyl) furyl) -4- (4-isopropyl) phenyl-indenyl]} zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium Dichloride, isopropylidene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium dichloride, diphenylmethylene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium Dichloride, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium dichloride, dimethylsilylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) [9- (2, 7-t-butyl) fluorenyl] zirconium dichloride.

Compound of general formula (III) (t-Butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)-(tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl-zirconium dichloride, (ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -methylenezirconium dichloride, (t-butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silane Zirconium dichloride, (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dichloride, (phenyl) Ruphosphide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl.

Compound of general formula (IV) (cyclopentadienyl) (phenoxy) zirconium dichloride, (2,3-dimethylcyclopentadienyl) (phenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (phenoxy) zirconium dichloride, (Cyclopentadienyl) (2,6-di-t-butylphenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (2,6-di-i-propylphenoxy) zirconium dichloride.

Compounds of general formula (V) (cyclopentadienyl) zirconium trichloride, (2,3-dimethylcyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (cyclopentadienyl) Zirconium triisopropoxide, (pentamethylcyclopentadienyl) zirconium triisopropoxide.

Compound of general formula (VI) Ethylene bis (7,7'-indenyl) zirconium dichloride, dimethylsilylene bis {7,7 '-(1-methyl-3-phenylindenyl)} zirconium dichloride, dimethylsilylene bis {7, 7 ′-[1-methyl-4- (1-naphthyl) indenyl]} zirconium dichloride, dimethylsilylenebis [7,7 ′-(1-ethyl-3-phenylindenyl)] zirconium dichloride, dimethylsilylenebis {7 , 7 '-[1-Isopropyl-3- (4-chlorophenyl) indenyl]} zirconium dichloride.

Illustrative examples of complexes comprising compound (i) secondary carbon of general formula (VII):
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CHMe ₂ ) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CHMe ₂ ) _{2} 2 ZrMe 2, (Me} 2 Si) 2 {η 5 -C 5 H-3,5- (CHMe 2) 2} 2 Zr (n-C 4 H 9) 2, (Me 2 Si) 2 {η _{^{5 -C 5 H-3,5- (CHMe}} 2) 2} 2 Zr (CH 2 C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) _{-5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2, rac- (Me 2 Si) 2 {η ^{_{5 -C 5 H-3- (CHMe}} 2) -5-Me} 2 Zr (n-C 4 H 9) 2, rac- (M ^{_{2 Si) 2 {η 5 -C}} 5 H-3- (CHMe 2) -5-Me} 2 Zr (CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H _{-3- (CHMe 2) -5-Me} } 2 ZrCl 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2, meso- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- (CHMe 2) -5-Me} 2 Zr (n-C 4 H 9) 2, meso- (Me 2 Si) 2 {η 5 -C 5 _{H-3- (CHMe 2) -5} -Me} 2 Zr (CH 2 C 6 H 5) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- (2- _adamantyl) 2} _{2 ZrCl 2, (Me 2 Si} ) 2 {η 5 -C 5 H-3,5- (2- _adamantyl) 2} _{ZrMe 2, (Me 2 Si)} 2 {η 5 -C 5 H-3,5- (2- _{adamantyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η 5 - C ₅ H-3,5- (2- _{adamantyl) 2} 2 Zr (CH 2} C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (2- adamantyl) -5-Me} 2ZrCl2, rac- ( Me2Si) 2 {η5-C5H-3- (2- _{adamantyl) -5-Me} 2 ZrMe 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H- 3- _{(2-adamantyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (2- adamantyl) -5- Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ ,

meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (2-adamantyl) -5-Me} ₂ ZrCl ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- _{(2-adamantyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (2- _{adamantyl) -5-Me} 2 Zr (} n-C 4 H _{9) 2, meso- (Me 2} Si) 2 {η 5 -C 5 H-3- (2- _{adamantyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, (Me 2 Si) 2 {Η ⁵ -C ₅ H-3,5- (cyclohexyl) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (cyclohexyl) ₂ } ₂ ZrMe ₂ , (Me ^{_{2 Si) 2 {η 5 -C}} 5 H-3,5- ( _{cyclohexyl) 2 2 Zr (n-C 4 H} 9) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- ( _{cyclohexyl) 2} 2 Zr (CH 2} C 6 H 5) 2, rac- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- ( _{cyclohexyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( cyclohexyl) -5 _{-Me} 2 ZrMe 2, rac- (} Me 2 Si) 2 {η 5 -C 5 H-3- ( _{cyclohexyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, rac- (Me 2 ^{_{Si) 2 {η 5 -C 5}} H-3- ( _{cyclohexyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3 - _{(cyclohexyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 ^{_{i) 2 {η 5 -C 5}} H-3- ( _{cyclohexyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( cyclohexyl) -5-Me } ₂ Zr (n-C ₄ H ₉ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (cyclohexyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ .

(Ii) Examples of compounds containing tertiary carbon:
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CMe ₃ ) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (CMe ₃ ) _{2} 2 ZrMe 2, (Me} 2 Si) 2 {η 5 -C 5 H-3,5- (CMe 3) 2} 2 Zr (n-C 4 H 9) 2, (Me 2 Si) 2 {η ^{_{5 -C 5 H-3,5- (CMe}} 3) 2} 2 Zr (CH 2 C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe 3) _{-5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe 3) -5-Me} 2 ZrMe 2, rac- (Me 2 Si) 2 {η ^{_{5 -C 5 H-3- (CMe}} 3) -5-Me} 2 Zr (n-C 4 H 9) 2, rac- (Me 2 Si) 2 ^{_{η 5 -C 5 H-3- (}} CMe 3) -5-Me} 2 Zr (CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe _{3) -5-Me} 2 ZrCl} 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CMe 3) -5-Me} 2 ZrMe 2, meso- (Me 2 Si) 2 {Η ⁵ -C ₅ H-3- (CMe ₃ ) -5-Me} ₂ Zr (nC ₄ H ₉ ) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- ( _{CMe 3) -5-Me} 2} Zr (CH 2 C 6 H 5) 2,
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (1-adamantyl) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (1- _{adamantyl) 2} 2 ZrMe 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- (1- _{adamantyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) ₂ {η ⁵ -C ₅ H-3,5- (1-adamantyl) ₂ } ₂ Zr (CH ₂ C ₆ H ₅ ) 2, rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1-adamantyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1-adamantyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ^{_{2 Si) 2 {η 5 -C}} 5 H-3- (1- _{adamantyl) -5-Me} 2 Zr (} n- _{C 4 H 9) 2, rac-} (Me 2 Si) 2 {η 5 -C 5 H-3- (1- _{adamantyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- (1- _{adamantyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (1- _{adamantyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (1- _{adamantyl) -5-Me} 2 Zr (} n-C 4 H 9) 2 , Meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1-adamantyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (1,1- _{dimethylpropyl) 2} 2 ZrCl 2, (} Me 2 Si) ₂ {η ⁵ —C ₅ H-3,5- (1,1-dimethylpropyl) ₂ } ₂ ZrMe ₂ , (Me ₂ Si) ₂ {η ⁵ —C ₅ H-3,5- (1, _{1-dimethylpropyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- (1,1- _{dimethylpropyl) 2}} 2 Zr ( _{CH 2 C 6 H 5) 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (1,1- _{dimethylpropyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si ) ₂ {η ⁵ -C ₅ H-3- (1,1-dimethylpropyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1, _{1-dimethylpropyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, rac- (Me 2 Si) 2 _{^{η 5 -C 5 H-3- (}} 1,1- _{dimethylpropyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H- 3- (1,1-dimethylpropyl) -5-Me} ₂ ZrCl ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1,1-dimethylpropyl) -5-Me} _{2 ZrMe 2, meso- (Me 2} Si) 2 {η 5 -C 5 H-3- (1,1- _{dimethylpropyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, meso- ( Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (1,1-dimethylpropyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ .

(Iii) Examples of compounds containing an alkylsilyl group:
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (dimethylsilyl) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (dimethylsilyl) _{2} 2 ZrMe 2, (Me} 2 Si) 2 {η 5 -C 5 H-3,5- ( _{dimethylsilyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η _⁵ -C ⁵ H-3,5- _{(dimethylsilyl) 2} 2 Zr (CH 2} C 6 H 5) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( dimethylsilyl) _{-5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{butyldimethylsilyl) -5-Me} 2 ZrMe 2} , rac- (Me 2 Si) 2 {η _⁵ -C ⁵ H-3- _{(butyldimethylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , meso- (Me ₂ Si) ₂ { η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ ZrCl ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} _{2 ZrMe 2, meso- (Me 2 Si} ) 2 {η 5 -C 5 H-3- ( _{butyldimethylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, meso- (Me 2 Si) 2 {Η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- ( _{trimethylsilyl) 2} 2 ZrCl 2, (} Me 2 Si) 2 {η 5 -C 5 H-3 5- _{(trimethylsilyl) 2} 2 ZrMe 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- ( _{trimethylsilyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si ) ₂ {η ⁵ -C ₅ H-3,5- (trimethylsilyl) ₂ } ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- ( _{trimethylsilyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{trimethylsilyl) -5-Me} 2 ZrCl 2} , rac- (Me 2 Si) 2 { η ⁵ -C ₅ H-3- (trimethylsilyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (trimethylsilyl) -5-Me} ₂ Zr ( _{n-C 4 H 9) 2} , rac- ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- ( _{trimethylsilyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H 3- _{(trimethylsilyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{trimethylsilyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 ^{_{Si) 2 {η 5 -C 5}} H-3- ( _{trimethylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3 - _{(trimethylsilyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- ( diphenyl _{silyl) 2}} 2 ZrCl 2, ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3,5 (Diphenyl _{silyl) 2} 2 ZrMe 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- ( diphenyl _{silyl) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si ) ₂ {η ⁵ -C ₅ H-3,5- (diphenylsilyl) ₂ } ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (Diphenylsilyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (diphenylsilyl) -5-Me} ₂ ZrMe ₂ , rac- (Me ₂ Si ) ₂ {η ⁵ -C ₅ H-3- (diphenylsilyl) -5-Me} ₂ Zr (n-C ₄ H ₉ ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3 - (diphenyl _{silyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) _{, Meso- (Me 2 Si) 2} {η 5 -C 5 H-3- ( _{butyldiphenylsilyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- _{(butyldiphenylsilyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{butyldiphenylsilyl) -5-Me} 2 Zr (} n-C 4 H 9) ₂ , meso- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (diphenylsilyl) -5-Me} ₂ Zr (CH ₂ C ₆ H ₅ ) ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (phenylmethyl _{silyl) 2} 2 ZrCl 2, (} Me 2 Si) 2 {η 5 -C 5 H-3,5- ( phenylmethyl _{silyl) 2}} 2 ZrMe 2, ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3,5- ( Fe _{Rumechirushiriru) 2} 2 Zr (n-} C 4 H 9) 2, (Me 2 Si) 2 {η 5 -C 5 H-3,5- ( phenylmethyl _{silyl) 2} 2 Zr (CH 2} C 6 H 5 ) ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (phenylmethylsilyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H 3- (phenylmethyl _{silyl) -5-Me} 2 ZrMe 2} , rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( phenylmethyl _{silyl) -5-Me} 2 Zr (} n- _{C 4 H 9) 2, rac-} (Me 2 Si) 2 {η 5 -C 5 H-3- ( phenylmethyl _{silyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, meso- ( ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- ( Fenirumechi _{Silyl) -5-Me} 2 ZrCl2,} meso- (Me2Si) 2 {η5-C5H-3- ( phenylmethyl _{silyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C ₅ H-3- (phenylmethyl _{silyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( phenylmethyl silyl) _{-5-Me} 2 Zr (CH} 2 C 6 H 5) 2, a.

Among these, a compound of a combination of secondary carbon and primary carbon is preferable, and rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (CHMe ₂ ) — is more preferable. _{5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2, meso- (Me 2 Si) 2 {η 5 _{-C 5 H-3- (CHMe 2} ) -5-Me} 2 ZrCl 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2 Rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- _{(dimethylsilyl) -5-Me} 2 ZrMe 2} , meso _{(Me 2 Si) 2 {η} 5 -C 5 H-3- ( _{butyldimethylsilyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( dimethyl silyl ) -5-Me} ₂ ZrMe ₂ .
In addition, the compound which replaced the silylene group of the compound of these specific examples with the germylene group is illustrated as a suitable compound.
As a special example of the metallocene complex, JP-A-7-188335 and Journal
of American Chemical Society, 1996, Vol. 11
Transition metal compounds having a ligand containing one or more elements other than carbon in the 5-membered ring or 6-membered ring disclosed in US Pat.
An example of a metallocene complex having a heterocyclic hydrocarbon group as a substituent is disclosed in Japanese Patent No. 3675509.

In the present invention, a metallocene complex having a heterocyclic aromatic group as a substituent among metallocene complexes is preferable. When the said compound is used, the effect of this invention can be exhibited in the more outstanding form.
Among metallocene complexes having a heterocyclic aromatic group as a substituent, it is more preferable to use a compound of general formula (II), a compound of general formula (III), and a compound of general formula (VI), Most preferred are compounds of general formula (II). Moreover, what has a furyl group and a thienyl group is still more preferable.

  Furthermore, these metallocene complexes can be used as a mixture of two or more. In addition, a plurality of types can be used in combination with the metallocene complex described above.

2) Component (b)
As a method for producing the ethylene polymer (A2) according to the present invention, as an essential component of the catalyst for olefin polymerization, in addition to the component (a), the metallocene compound (component (a), hereinafter simply referred to as the component (a). a compound (component (b), hereinafter may be simply referred to as b)), and a fine particle carrier (component (c), Hereinafter, it may be simply referred to as “c”).

One of the compounds (b) that react with the metallocene compound (a) to form a cationic metallocene compound is an organoaluminum oxy compound.
The organoaluminum oxy compound has Al—O—Al bonds in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy compound is usually a product obtained by reacting an organoaluminum compound with water.
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. Preference is given to using aromatic hydrocarbons.

As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any compound represented by the following general formula (4) can be used, but trialkylaluminum is preferably used.
R ⁵ _t AlX ³ _3-t formula (4)
(In the formula (4), R ⁵ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and X ³ represents a hydrogen atom or a halogen atom. Represents an atom, and t represents an integer of 1 ≦ t ≦ 3.)

  Other specific examples of the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound include borane compounds and borate compounds.

3) Component (c)
Examples of the fine particle carrier as the component (c) include an inorganic carrier, a particulate polymer carrier, and a mixture thereof. As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof can be used.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.

(I) After contacting the metallocene compound (a) with the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound, the fine particle carrier (c) is contacted.
(II) After contacting the metallocene compound (a) with the fine particle carrier (c), the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound is contacted.
(III) The metallocene compound (a) is contacted with the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound and the fine particle carrier (c).

When an organoaluminum oxy compound is used as the compound (b) that reacts with the metallocene compound (a) to form a cationic metallocene compound, the aluminum of the organoaluminum oxy compound relative to the transition metal (M) in the metallocene compound (a) is used. The atomic ratio (Al / M) is usually in the range of 1 to 100,000, preferably 5 to 1000, more preferably 50 to 200, and when a borane compound or a borate compound is used, transition in the metallocene compound The atomic ratio (B / M) of boron to metal (M) is usually selected within the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10.
Further, when a mixture of an organoaluminum oxy compound, a borane compound, and a borate compound is used as the compound (b) for generating a cationic metallocene compound, for each compound in the mixture, the transition metal (M) It is desirable to select at the same usage ratio as above.

  The amount of the fine particle carrier (c) used is preferably 0.0001 to 5 mmol, more preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, per 0.0001 to 5 mmol of the transition metal in the metallocene compound (a). It is 1g per hit.

  As an example of producing a metallocene catalyst, for example, by referring to “catalyst” and “mixing ratio and conditions of raw materials” described in JP-T-2002-535339 and JP-A-2004-189869, which are publicly known publications, Can be manufactured. The index of the polymer can be controlled by various polymerization conditions, and can be controlled by, for example, the methods described in JP-A-2-269705 and JP-A-3-21607.

  The ethylene polymer (II) is a homopolymer of ethylene, or ethylene and an α-olefin having 3 to 12 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene. , 1-octene and the like. Also, copolymerization with a diene for the purpose of modification is possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, and the like. The comonomer content during the polymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, an ethylene / α-olefin copolymer is used. The α-olefin content is 0 to 40% by mole, preferably 0 to 30% by mole (however, 0% is excluded).

2. Ethylene polymer (B)
(B) component which is one of the components which comprise the polyethylene-type resin composition of this invention satisfy | fills all the conditions (B-1)-(B-6) demonstrated below.

2-1. Condition (B-1)
The melt flow rate (MFR _B ) of the component (B) in the present invention is from 0.01 to 1.5 g / 10 minutes, preferably from 0.05 to 1.0 g / 10 minutes, more preferably from 0.1 to 0.00. 8 g / 10 min.
When the MFR _B is less than 0.01 g / 10 min, the molding processability of the polyethylene resin composition, particularly the melt flowability and the spreadability, is inferior, and furthermore, it is difficult to uniformly mix with the ethylene polymer resin (A). Therefore, it is not preferable because poor appearance such as gels, butts and fish eyes occur and impact strength decreases. If MFR _B is greater than 1.5 g / 10 min, the effect of improving the mechanical strength such as impact strength, tear strength, and tensile strength of the polyethylene resin composition and the molded article is not sufficiently exhibited.
In addition, MFR _B says the value when it measures on the conditions similar to the above-mentioned conditions (A-2).

2-2. Condition (B-2)
The density _B of the component (B) in the present invention is 0.900 to 0.960 g / cm ³ , preferably 0.920 to 0.960 g / cm ³ , more preferably 0.940 to 0.960 g / cm ³ . is there.
When the density _B is in this range, the balance between impact strength and rigidity of the polyethylene resin composition and the molded article is excellent. On the other hand, if the density _B is less than 0.900 g / cm ³ , the rigidity decreases, and if the product is a thick molded body such as a pipe or various containers, the product is too soft and deforms. This is not preferable because there is a risk of being pressed. In addition, it is preferable because it is difficult to handle even at room temperature when it is subjected to a blending process with the ethylene polymer resin (A), and it may cause product stickiness of the polyethylene resin composition. Furthermore, the compatibility with the ethylene polymer resin (A) is lowered, and the impact strength due to phase separation may be deteriorated. Further, if the density _B is larger than 0.960 g / cm ³ , the impact strength may be impaired, which is not preferable.
The density _B refers to a value when measured under the same conditions as the above condition (A-3).

HLMFR _B and MFR _B are mainly adjusted by the amount of hydrogen, and density _B is mainly adjusted by the amount of α-olefin, and can be applied to the ethylene polymer (B) according to the present invention.

2-3. Condition (B-3)
The ratio ([Mw / Mn] _B ) of the weight average molecular weight (Mw _B ) and the number average molecular weight (Mn _B ) of the component (B) in the present invention is 2.0 to 6.0, preferably 2.5 to 5. 0.5, more preferably 2.9 to 4.5, and still more preferably 3.2 to 4.0.
[Mw / Mn] If _B is less than 2.0, it may be difficult to mix with the ethylene-based polymer resin (A) and should be avoided. [Mw / Mn] If _B is greater than 6.0, the effect of improving the impact strength of the polyethylene resin composition or the molded article may be insufficient, or may become sticky.
[Mw / Mn] _B can be adjusted by the type of catalyst, the type of cocatalyst, the polymerization temperature, the residence time in the polymerization reactor, the number of polymerization reactors, and the like. It can be adjusted by the step speed, etc., preferably by adjusting the mixing ratio of the high molecular weight component and the low molecular weight component, and can be increased by increasing the difference in the average molecular weight of each component.

In this specification, including [Mw / Mn] _B , the Mw and Mn of the ethylene polymer and the polyethylene resin composition were measured by gel permeation chromatography (GPC) as follows. Say.
That is, the conversion from the retention capacity to the molecular weight is performed using a standard curve prepared in advance with standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is generated by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. The following numerical value is used for the viscosity formula [η] = K × Mα used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

The measurement conditions for GPC are as follows.
Apparatus: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are performed as illustrated in FIG.

2-4. Condition (B-4)
Component (B) in the present invention has a strain hardening degree [λmax (2.0)] _B of 1.2 to 10.0, preferably 1.7 to 8.0, and more preferably 2.4 to 6.0. More preferably, it is 3.0-5.0.
[Λmax (2.0)] When _B is less than 1.2, the flowability and melt tension of the ethylene polymer, the polyethylene resin composition, and the molded body become insufficient, and the molding process characteristics deteriorate. [Λmax (2.0)] If _B is greater than 10.0, the fluidity and melt tension are excellent, but the impact strength of the polyethylene resin composition and the molded article may be lowered, which is not preferable. In addition, [λmax (2.0)] _B is a value when measured under the same condition as the above condition (A-5).
The influence of the elongation flow characteristics of polyethylene on the molding processability and the mechanical properties of the molded body is as already described in general terms in the above-mentioned condition (A-5). In order to solve the improvement in the molding processing surface and the overcoming of the disadvantages in the mechanical properties of the molded product caused by the elongation flow characteristics of the long chain by devising the long chain branch structure which is the main governing factor of the elongation viscosity characteristics As a result of earnest studies on the polyethylene resin composition, the ethylene polymer resin (A) having a small long-chain branched structure was used as the high MFR main component, that is, the low molecular weight side main component of the resin composition. defined extended strain hardening degree in B-4) [λmax (2.0 )] often ethylene polymer having long chain branching structure typified the (B) low MFR main component or high of the resin composition _B When it is used as the main component on the side of the molecular weight, it can be seen that not only the molding process characteristics are improved but also the mechanical characteristics, particularly the rigidity and impact strength, are excellent. When the strain rate dependency of the elongation strain hardening degree is different from that conventionally used, it has the characteristics represented by the following conditions (B-5), the molding process characteristics and mechanical characteristics of the polyethylene resin composition: In any case, it was found that the improvement effect was extremely excellent.

2-5. Condition (B-5)
The component (B) in the present invention was measured in the same manner with [λmax (2.0)] _B defined in the above (B-4) and an elongation strain rate of 0.1 (unit: 1 / second) [ λmax (0.1)] Ratio to _B [λmax (2.0) / λmax (0.1)] _B is 1.2 to 10.0, preferably 1.3 to 5.0, more preferably 1. .4 to 4.0, and more preferably 1.5 to 3.0.
[Λmax (2.0) / λmax (0.1)] When _B is less than 1.2, the melted state of the ethylene polymer, the polyethylene resin composition or the molded body is not uniform or is not thermally stable. This is not preferable because there is a possibility that the structure has a stable structure or there is a possibility that the impact strength is lowered due to the strength anisotropy of the molded product due to the presence of a very long long-chain branched structure. [Λmax (2.0) / λmax (0.1)] When _B is greater than 10.0, although the melt tension and fluidity during molding are excellent, the impact strength of the polyethylene-based resin composition and the molded body is low. It is not preferable because it may decrease.

2-6. Condition (B-6)
(B) component in this invention is a polymer manufactured by the polymerization reaction of ethylene using the catalyst containing a transition metal, Preferably, it mentions later 2-9. A polymer produced by a polymerization reaction of ethylene using a catalyst containing a transition metal described in detail in the section of the production method of the ethylene-based polymer (B), more preferably a catalyst containing a transition metal was used. It is a polymer produced by a coordinated anionic polymerization reaction of ethylene.
Today, various radical polymerization initiators are well known as ethylene polymerization catalysts that do not contain transition metals. Specifically, peroxides such as dialkyl peroxide compounds, alkyl hydroperoxide compounds, benzoyl peroxide, and hydrogen peroxide are used. Products, azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, etc., but the ethylene polymer produced by radical polymerization reaction using these radical polymerization initiators has a long chain branched structure. Including a large amount, when used with a component of a polyethylene-based resin composition, although it has an effect on the molding process characteristics, it is not preferable because the long-chain branched structure increases too much and the strength of the composition and the molded body is reduced. The MFR of the ethylene-based polymer (B) is sufficiently lowered, the density is sufficiently reduced, the preferred α-ole Since copolymerization of fin is or was not feasible, it is not possible to sufficiently improve the strength of the composition and molded article, which is not preferable. Even if the catalyst contains a transition metal, if the polymerization reaction proceeds substantially by radical polymerization like a so-called redox system such as hydrogen peroxide / ferrous chloride or cerium salt / alcohol, It is not regarded as a catalyst containing a transition metal in the present invention.

2-7. Condition (B-7)
In addition to the above conditions (B-1) to (B-6), the component (B) in the present invention is further measured by a GPC measurement device that combines a differential refractometer, a viscosity detector, and a light scattering detector. The content (WC) of the component having a molecular weight of 1 million or more is preferably 0.01 to 10%, and the branching index (g _{C ′} ) at the molecular weight of 1 million is preferably 0.30 to 0.70. . The WC value is more preferably 0.02 to 8.0%, still more preferably 0.05 to 6.0%, particularly preferably 0.09 to 4.0%, and the gC ′ value is More preferably, it is 0.30-0.59, More preferably, it is 0.35-0.55, Most preferably, it is 0.35-0.50.
If the WC value is smaller than 0.01%, the moldability of the polyethylene resin composition may be insufficient. When the WC value is larger than 10%, the molding processability of the polyethylene resin composition is improved, but the impact strength of the molded article may be lowered, which is not preferable.
Moreover, since gC _' value is larger than 0.70, there exists a possibility that the moldability of this polyethylene-type resin composition may be inadequate, and is unpreferable. If the g _{C ′} value is less than 0.30, the moldability of the polyethylene resin composition is improved, but the impact strength of the molded article may be lowered, which is not preferable. Even if the g _{C ′} value is within a preferable range, if the WC value is larger than 10%, the melt fluidity becomes too low, which may hinder the production and processing of the resin composition. It is not preferable. In the present invention, the WC value and g _{C ′} value of an ethylene-based polymer are measured by the molecular weight distribution curve calculated from the following GPC-VIS measurement and the evaluation method of the long chain branching amount using the branching index (g ′). is there.

[Branch structure analysis by GPC-VIS]
Waters Alliance GPCV2000 was used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). In addition, as a light scattering detector, a DAWN-E manufactured by Wyatt Technology, a multi-angle laser light scattering detector (MALLS) was used. The detectors were connected in the order of MALLS and RIVisometer. The mobile phase solvent is 1,2,4-trichlorobenzene (added with the antioxidant Irganox 1076 at a concentration of 0.5 mg / mL). The flow rate is 1 mL / min. As a column, two Tosoh Corporation GMHHR-H (S) HT were connected and used. The temperature of the column, sample injection section, and each detector is 140 ° C. The sample concentration was 1 mg / mL. The injection volume (sample loop volume) is 0.2175 mL. In order to obtain the absolute molecular weight (M) obtained from MALLS, the radius of inertia (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, data processing software ASTRA (version 4.73.04) attached to MALLS was used. The calculation was performed with reference to the following documents.

References:
1. Developments in polymer characterization, vol. 4). Essex: Applied Science; 1984. Chapter 1.
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000)
4). Macromolecules, 33, 6945-6952 (2000)

[Calculation of branching index (g _C '), etc.]
The branching index (g ′) is a ratio (η _branch / η) between the intrinsic viscosity (η _branch ) obtained by measuring a sample with the above Viscometer and the intrinsic viscosity (η _lin ) obtained separately by measuring a linear polymer. _lin ).
When long chain branching is introduced into a polymer molecule, the radius of inertia is reduced compared to a linear polymer molecule of the same molecular weight. Since the intrinsic viscosity becomes smaller as the radius of inertia becomes smaller, the ratio (η _branch / η) of the intrinsic viscosity (η _branch ) of the branched polymer to the intrinsic viscosity (η _lin ) of the linear polymer having the same molecular weight as long chain branching is introduced. _lin ) becomes smaller. Therefore, when the branch index (g ′ = η _branch / η _lin ) is a value smaller than 1, it means that a branch is introduced, and as the value decreases, the introduced long chain branch increases. It means to go. In particular, in the present invention, the absolute molecular weight obtained from MALLS is the content ratio (%) of the component having a molecular weight of 1 million or more to the total component amount measured by RI as the content (WC) of the component having a molecular weight of 1 million or more. The above-mentioned g ′ at a molecular weight of 1,000,000 is calculated as g _C ′ as an absolute molecular weight obtained from MALLS.
FIG. 4 shows an example of the analysis result by the GPC-VIS. The left side of FIG. 4 shows the molecular weight distribution curve measured based on the molecular weight (M) obtained from MALLS and the concentration obtained from RI, and the right side of FIG. 4 shows the branching index (g ′) at the molecular weight (M). . Here, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) was used as the linear polymer.

2-8. Composition of ethylene polymer (B) The component (B) in the present invention is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin which is a copolymerization component used here include propylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, pentene-1, hexene-1 and heptene. -1, octene-1, decene-1, tetradecene-1, hexadecene-1, octadecene-1, eicosene-1. These α-olefins may be used alone or in combination of two or more. Among these, more preferable α-olefins are those having 3 to 10 carbon atoms, specifically, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, pentene-1, and hexene-1. , Heptene-1, octene-1, decene-1, and the like. More preferable α-olefins are those having 4 to 8 carbon atoms, specifically, butene-1, 3-methylbutene-1, 4-methylpentene-1, pentene-1, hexene-1, heptene-1, octene. -1 etc. are mentioned. Particularly preferred α-olefins are butene-1, hexene-1 and octene-1. Among the olefin polymerization catalysts described later, even during ethylene homopolymerization, α-olefins such as 1-butene and 1-hexene by ethylene oligomerization reaction are by-produced in the polymerization system, or “Chain”. A reaction called “-walking reaction”, in which a short chain branching such as a methyl group or an ethyl group occurs in an olefin polymer main chain from an isomerization reaction of an active center metal-terminal carbon bond at an olefin polymerization growth terminal, is well known today. The short chain branched structure in the ethylene homopolymer resulting from these reactions may be indistinguishable from the short chain branched structure generated by the co-polymerization of α-olefin.
Therefore, the ethylene homopolymer referred to in the present invention refers to a polymer produced as a result of polymerization carried out without supplying an α-olefin as a comonomer from the outside, and an ethylene / α-olefin copolymer refers to an external Refers to a polymer produced as a result of the polymerization carried out by supplying the α-olefin from the ethylene, and the term ethylene-based polymer refers to an ethylene homopolymer and an ethylene / α-olefin copolymer (other than the α-olefin described below, a comonomer). Including the case of using as a).

  The proportion of ethylene and the α-olefin in the ethylene polymer (B) of the present invention is about 75 to 99.5% by weight of ethylene and about 0.5 to 25% by weight of α-olefin, preferably about ethylene. 78 to 97% by weight, α-olefin of about 3 to 22% by weight, more preferably ethylene of about 80 to 96% by weight, α-olefin of about 4 to 20% by weight, still more preferably ethylene of about 82 to 95% by weight. %, Α-olefin about 5 to 18% by weight. When the ethylene content is within this range, the balance between the rigidity and impact strength of the polyethylene resin composition and the molded article is good.

  The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. Of course, a small amount of a comonomer other than ethylene or α-olefin can be used. In this case, styrenes such as styrene, 4-methylstyrene, 4-dimethylaminostyrene, 1,4-butadiene, 1,5- It has polymerizable double bonds such as dienes such as hexadiene, 1,4-hexadiene and 1,7-octadiene, cyclic compounds such as norbornene and cyclopentene, oxygen-containing compounds such as hexenol, hexenoic acid and methyl octenoate. A compound can be mentioned. However, it goes without saying that when the dienes are used, they must be used within the range where the long-chain branched structure does not develop, that is, within the range satisfying the above conditions (B-4) and (B-5).

2-9. Method for Producing Ethylene Polymer (B) The component (B) in the present invention satisfies the above-mentioned conditions (B-1) to (B-6), or preferably all of (B-7) in addition thereto. An ethylene polymer having the above composition is produced and used. The production is carried out by a method of homopolymerizing ethylene or copolymerizing with the above-mentioned α-olefin using an olefin polymerization catalyst.
Various types of olefin polymerization catalysts are known today, and the ethylene polymer (B) can be prepared within the scope of the composition of the catalyst components and the contrivance of polymerization conditions and post-treatment conditions. Although not limited in any way, (ii) metallocene catalysts and (IV) post-metallocene catalysts can be cited as technical examples suitable for the production of the ethylene-based polymer (B) and satisfying the economical efficiency at the industrial level. Of these, (ii) metallocene catalysts are preferred.

(Ii) Metallocene catalyst As an example of a polymerization catalyst suitable for the production of the ethylene polymer (B), a metallocene catalyst which is an olefin polymerization catalyst comprising a metallocene transition metal compound and a promoter component (for example, “next generation by metallocene catalyst”) Polymer industrialization technology (upper and lower volume; see 1994, published by Inter Research Co., Ltd.) is relatively inexpensive, highly active, excellent in polymerization process suitability, and has a narrow molecular weight distribution and copolymer composition distribution. It is used because a polymer is obtained.
Details of those suitably used for the production of the ethylene polymer (B) will be described later.

(IV) Post-metallocene catalyst An example of a polymerization catalyst suitable for the production of the ethylene polymer (B) is an olefin polymerization catalyst using a homogeneous metal complex (non-metallocene complex) other than the metallocene transition metal compound described above. Post-metallocene catalysts (for example, “Polyethylene Technology Reader; Published by 2001 Industrial Research Council Co., Ltd.”, “Living Polymerization with Homogeneous Transition Metal Catalysts; Published by 1999 IPC Co., Ltd.”, “Catalyst Dictionary”; 2004 (See “Issues by Industrial Research Committee”, etc.), which is relatively inexpensive and excellent in activity, and is further used because an ethylene polymer having a narrow molecular weight distribution and a narrow copolymer composition distribution is obtained.
Among them, JP-T-10-513289, JP-T 2002-521538, JP-T 2000-516295, JP-T 2000-514132, Macromolecules, 1996, p5241, JACS, 1997, 119, p3830, JACS , 1999, 121, p5798, Organometallics, 1998, p3155, etc., and a ligand having at least two N atoms is bonded to a transition metal of Groups 3 to 11 of the periodic table through the two N atoms. A transition metal bisimide compound, an iminoamide compound, a bisamide compound having a 4- to 8-membered chelate structure containing the transition metal formed, and at least two disclosed in JP-A-6-1362048 Having O or S atoms Transition metal bishydrocarbyl having a 4- to 8-membered ring chelate structure comprising the transition metal formed by bonding a ligand to the transition metal of Groups 3 to 11 of the periodic table through the two O atoms or S atoms Oxy compounds, bishydrocarbylthio compounds, at least one N atom, S atom or P atom disclosed in JP 2000-514132 A, JP 2003-535107 A, JP 2007-77395 A, etc. And a ligand having a carboxyl group (COO) containing the transition metal formed by bonding with a transition metal of Groups 3 to 11 of the periodic table through the N atom, S atom or P atom and the carboxyl group. ~ Iminocarboxylate compounds, thiocarboxylate compounds, phosphine cals of transition metals with 8-membered ring chelate structure Xylate compounds and ligands having at least one P atom or N atom and carbonyl group (CO) disclosed in JP-T-2004-517933 and the like are periodically controlled through the P atom or N atom and carbonyl group. Β-keto-phosphine compounds, β-keto-imide compounds, β-keto-phosphine compounds of transition metals having a 4- to 8-membered chelate structure containing the transition metal formed by binding to a transition metal of Group 3 to 11 in Table A keto-amide compound or a ligand having at least one P atom or N atom and O atom disclosed in JP-A No. 64-14217, JP-A-2004-517933, etc. Transition having a 4- to 8-membered chelate structure containing the transition metal formed by bonding with a transition metal of Groups 3 to 11 of the periodic table through an N atom and an O atom Transfer metal γ-oxy-phosphine compounds, γ-oxy-imide compounds, γ-oxy-amide compounds, JP-A 6-184214, JP-A 10-195090, JP 2002-521534, JP A ligand having at least one P atom and a sulfonic acid residue (SO ³ ) disclosed in Japanese Unexamined Patent Publication No. 2007-46032, Japanese Patent Application Laid-Open No. 2007-77395, and the like passes through the P atom and the sulfonic acid residue. A transition metal γ-sulfonato-phosphine compound having a 4- to 8-membered chelate structure containing the transition metal formed by binding to a transition metal of Groups 3 to 11 of the periodic table, and JP-A-11-315109 , Chemical Communications (2003), (18), 2272-2273, etc. A 4- to 8-membered ring chelate structure containing the transition metal formed by bonding a ligand having an enoxy group to a transition metal of Groups 3 to 11 of the periodic table through the N atom and an O atom of the phenoxy group. The transition metal having a phenoxyimine compound and a phenoxyamine compound are preferably used.
As these nonmetallocene complex catalysts, those having Ti, Zr, Hf, V, Cr, Fe, Co, Ni, Pd whose central metal is group 4B of the periodic table are more preferably used because of high activity, More preferably, the central metal is Ti, Zr, Hf, Fe, Ni, or Pd. However, these post metallocene catalysts tend to have a long-chain branched structure in the produced ethylene polymer, a short-chain branched structure centered on methyl branches, or a broad molecular weight distribution. Therefore, when using as the ethylene polymer (B) of the present invention, it is necessary to pay particular attention to satisfying the above conditions (B-2) to (B-5).

  Regarding the production of the ethylene-based polymer (B) of the present invention, when conducting polymerization or copolymerization of ethylene, slurry polymerization, solution polymerization, bulk polymerization in a liquid monomer, liquid phase polymerization such as suspension polymerization, or Any method such as a gas phase polymerization method can be employed. In the case of the slurry polymerization method, both a slurry polymerization method using a pipe loop reactor and a slurry polymerization method using an autoclave reactor can be used. The industrial polymerization process is described in detail in Kazuo Matsuura and Naotaka Mikami, “Polyethylene Technology Reader”, p. 148, 2001, Industrial Research Committee. As the polymerization method, a slurry polymerization method or a gas phase polymerization method is preferable, and a gas phase polymerization method is more preferable.

  The liquid phase polymerization method is usually performed in a hydrocarbon solvent. As the hydrocarbon solvent, inert hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, decane, cyclohexane, benzene, toluene, and xylene, or liquid monomers are used. It is done. As the gas phase polymerization method, a commonly known polymerization method such as a fluidized bed or a stirring bed can be employed in the presence of an inert gas, and a so-called condensing mode in which a medium for removing heat of polymerization coexists may be employed. .

  The polymerization temperature is generally 0 to 300 ° C, practically 50 to 270 ° C, and more preferably 60 to 110 ° C in slurry polymerization or suspension polymerization, although it varies depending on the polymerization process employed. Yes, it is 100 to 250 ° C. for solution polymerization or bulk polymerization in liquid ethylene, and 60 to 100 ° C. for gas phase polymerization. The catalyst concentration and olefin concentration in the reactor may be any concentration sufficient to allow the polymerization to proceed. The ethylene concentration can be in the range of about 1% to about 10% based on the weight of the reactor contents in the case of slurry polymerization, suspension polymerization, and solution polymerization. It can be set as the range of 0.1-10 MPa. Further, it is possible to carry out the polymerization in the presence of hydrogen, which is a general means for adjusting the MFR of the ethylene polymer resin (A). Hydrogen generally functions as a so-called chain transfer agent for adjusting the molecular weight. The MFR can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst. In order to reduce the long chain branching amount of the ethylene polymer resin (A), it is preferable that the ethylene concentration and the hydrogen concentration are high.

  As a polymerization method, not only single-stage polymerization in which an olefin polymer is produced using one reactor, but also at least two in order to improve the production amount or more precisely control the molecular weight distribution and comonomer composition distribution. It is also possible to carry out multistage polymerization by connecting two or more reactors in series or / and in parallel. In the case of multistage polymerization, serial multistage polymerization is preferred in which a plurality of reactors are connected and the reaction mixture obtained by polymerization in the first stage reactor is continuously supplied to the second and subsequent reactors. In the serial multistage polymerization method, the polymerization reaction mixture in the preceding reactor is transferred to the subsequent reactors by continuous discharge through a connecting pipe. Moreover, even if a component for the purpose of removing moisture, a so-called scavenger, is added to the polymerization system, the polymerization can be carried out without any trouble. As such a scavenger, organoaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, the aforementioned organoaluminum oxy compounds, organozinc compounds and organomagnesium compounds are used, but organoaluminum compounds are most common.

  The olefin polymerization catalyst containing a transition metal that satisfies the economical efficiency at the industrial level, suitable for the production of the ethylene polymer (B) in the present invention, is (ii) a metallocene catalyst having a molecular weight distribution as compared with other catalysts. And an ethylene polymer having a narrow copolymer composition distribution is produced, which is particularly suitable from the viewpoint of improving the mechanical properties and transparency of the polyethylene resin composition and the molded product.

That is, as a result of diligent studies by the inventors to achieve the object of the present invention, an example of an olefin polymerization catalyst that produces a long-chain branched structure suitable as the ethylene polymer (B) of the present invention is an example. As a result, a method using a complex having a bridged (cyclopentadienyl) (indenyl) ligand or the like as recently discovered as an essential catalyst component (the invention of Japanese Patent Application No. 2010-268037, etc.) As an example, a method using a complex having a benzoindenyl ligand or the like as a catalyst component (Japanese Patent Application Laid-Open No. 2006-2098, etc.) has been reached. Or a complex having a bis (azurenyl) ligand or a bridged bis (cyclopentadienyl) ligand, an organoaluminum oxy compound, and a cation It was led to a method of using a catalyst with a mixture of borane compounds or borate compound is a compound to produce sexual metallocene compound.
An example of an olefin polymerization catalyst comprising a complex having a crosslinked (cyclopentadienyl) (indenyl) ligand or the like that generates a long-chain branched structure suitable as the ethylene polymer (B) of the present invention is an essential component. Specific examples of the olefin polymerization catalyst comprising the following essential component (a-1), component (b) and preferred component (c) are shown below.
Component (a-1): Metallocene compound represented by general formula (1) Component (b): Compound that reacts with the metallocene compound of component (a-1) to form a cationic metallocene compound Component (c): Fine particle carrier

i) Component (a-1)
The essential component (a-1) is preferably a metallocene compound represented by the following general formula (a-1-1).

[In the formula (a-1-1), M represents a transition metal of Ti, Zr or Hf. X ¹ and X ² are each independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen or nitrogen, or a hydrocarbon having 1 to 20 carbon atoms. A group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. Q ₁ and Q ₂ represent a carbon atom, a silicon atom or a germanium atom. R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and four R ^{1 s} may form a ring together with Q ₁ and Q ₂ bonded thereto. . m is 0 or 1, and when m is 0, Q ₁ is directly bonded to a conjugated 5-membered ring containing R ² and R ³ . R ² is a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, An oxygen-containing hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms is shown, but even when a plurality of R ² is a hydrocarbon group or the like, they are bonded as in the following R ^4. It does not form a ring with the carbon atom. R ³ represents a saturated or unsaturated divalent hydrocarbon group having 4 or 5 carbon atoms that forms a condensed ring with respect to the 5-membered ring to be bonded. R ⁴ is an atom or group bonded to the carbon atom of R ³ , and each independently represents a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, or a C 1 to 18 carbon atom containing 1 to 6 silicon atoms. A silicon-containing hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. n represents an integer of 0 to 10, and when n is 2 or more, R ⁴ may form a ring together with the carbon atoms to which it is bonded. R ⁵ is a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, An oxygen-containing hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms is shown, but even when a plurality of R ⁵ are hydrocarbon groups or the like, they are bonded as R ^4. It does not form a ring with the carbon atom.

  The metallocene compound as the essential component (a-1) is preferably one represented by the following general formula (a-1-2).

  The metallocene compound as the essential component (a-1) is more preferably one represented by the following general formula (a-1-3).

Particularly preferable examples of the metallocene compound as the component (a-1) are shown below.
Dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (cyclo Pentadienyl) (3-phenylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (4-phenylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (benzo [e] indenyl) zirconium dichloride, Isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-t-butylindenyl ) Zirconium dichloride, isopropylidene (cyclopentadienyl) (3-t-butylindenyl) zirconium dichloride, dimethylgermylene (cyclopentadienyl) (indenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3) -T-butylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (indenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (3-methylindenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (3-t-butylindenyl) hafnium dichloride, dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (4-t-butyl) Cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) zirconium dimethyl, and the like.

ii) Component (b)
Illustrated as an olefin polymerization catalyst comprising, as an essential component, a complex having a bridged (cyclopentadienyl) (indenyl) ligand or the like that generates a long-chain branched structure suitable as the ethylene polymer (B) of the present invention. In addition to the essential component (a-1), the olefin polymerization catalyst reacts with the metallocene compound (component (a-1), hereinafter may be simply referred to as a)) as a cation by reacting with the component (a-1). A compound (component (b), hereinafter may be simply referred to as “b”) that forms a metallic metallocene compound. The compound (b) that reacts with the metallocene compound (a-1) to form a cationic metallocene compound is preferably the same compound as the compound that reacts with the aforementioned component (a) to form a cationic metallocene compound.

iii) Component (c)
Illustrated as an olefin polymerization catalyst comprising, as an essential component, a complex having a bridged (cyclopentadienyl) (indenyl) ligand or the like that generates a long-chain branched structure suitable as the ethylene polymer (B) of the present invention. The olefin polymerization catalyst contains the component (b) in addition to the essential component (a-1), and preferably contains a fine particle carrier (component (c), hereinafter may be simply referred to as c).

Examples of the fine particle carrier as the component (c) include an inorganic carrier, a particulate polymer carrier, and a mixture thereof. As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof can be used.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.

(4) Mixing of each component constituting the polyethylene resin composition of the present invention The above polyethylene resin composition for containers is pelletized by mechanical melt mixing with a pelletizer or a homogenizer according to a conventional method, and then variously molded. It can be molded by a machine to obtain a desired molded product.
In addition, the container polyethylene resin composition obtained by the above-mentioned method includes, in addition to other olefin polymers and rubbers, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, and an antistatic agent in accordance with conventional methods. , Anti-fogging agents, anti-blocking agents, processing aids, color pigments, crosslinking agents, foaming agents, inorganic or organic fillers, flame retardants, and other known additives can be blended.
As additives, for example, one or more antioxidants (phenolic, phosphorus, sulfur), lubricants, antistatic agents, light stabilizers, ultraviolet absorbers, and the like can be used in combination as appropriate. As filler, calcium carbonate, talc, metal powder (aluminum, copper, iron, lead, etc.), silica, diatomaceous earth, alumina, gypsum, mica, clay, asbestos, graphite, carbon black, titanium oxide, etc. can be used. Of these, calcium carbonate, talc and mica are preferably used. In any case, the polyethylene resin composition can be blended with various additives as necessary and kneaded with a kneading extruder, a Banbury mixer, or the like to obtain a molding material.

3. Physical Properties of Polyethylene Resin Composition of the Present Invention The polyethylene resin composition of the present invention must satisfy the MFR and density ranges described below for the entire composition.

5-1. MFR
The melt flow rate (MFR) of the polyethylene resin composition of the present invention is 0.1 to 1 g / 10 minutes, preferably 0.2 to 0.5 g / 10 minutes. If the MFR is less than 0.1 g / 10 min, the flowability of the polyethylene-based resin composition is poor, and the motor load of the extruder may become too high, or the spreadability may be inferior. If the MFR is greater than 1 g / 10 min, the polyethylene resin composition and the molded article may have poor mechanical strength such as impact strength, tear strength and tensile strength, and molding processability, which is not preferable.
In addition, MFR means the value when it measures on the conditions similar to the above-mentioned conditions (A-2).

5-2. Density The density of the polyethylene resin composition of the present invention is 0.950 to 0.965 g / cm ³ , preferably 0.950 to 0.960 g / cm ³ .
When the density of the polyethylene resin composition is lower than 0.950 g / cm ³ , the rigidity of the polyethylene resin composition and the molded article is low and stickiness tends to occur. In the case of body, not only various inconveniences in the use of products, but also inconveniences may occur in post-processing steps such as product winding process, surface printing / bonding, etc. When the product is a thick molded body such as a pipe or various containers, the product is too soft and may be deformed. Moreover, when the density of a polyethylene resin composition is higher than 0.965 g / cm < ³ >, the impact strength of a polyethylene-type resin composition and this molded object will fall, and transparency will also deteriorate.
In addition, a density says the value when it measures on the conditions similar to the above-mentioned conditions (A-3).

Moreover, it is preferable that the composition of the present invention further satisfies the following characteristics (i) to (iii).
Characteristic (i): It is preferable that the all notched creep test (FNCT) based on ISO DIS 16770 is 100 hours or more. If the FNCT is less than 100 hours, the resistance to environmental stress cracking is inferior, and there is a risk that the container will be destroyed by the stress cracking and the internal solution will leak.
Here, the all notched creep test (FNCT) based on ISO DIS 16770 is an evaluation of long-term mechanical properties, and the sample is a razor blade on the entire circumference of a 6 mm × 6 mm × 11 mm prism. Prepare a test piece with a 1 mm notch and a cross section of 4 mm × 4 mm, and give the specimen a tensile stress equivalent to 3.7 MPa in pure water at 80 ° C. This is a value obtained by measuring the time until completion.
The FNCT can be adjusted by the molecular weight, density, and blending amount of the ethylene polymer (A2) of the ethylene polymer resin (A), specifically, the molecular weight is increased, the density is increased. The FNCT time can be improved by reducing the density and increasing the amount of the compound.

Characteristic (ii): The peak top time in isothermal crystallization at 121.5 ° C. measured by a differential scanning calorimeter (DSC) is preferably 200 seconds or less. More preferably, it is 150 seconds or less, More preferably, it is 120 seconds or less. If this value exceeds 200 seconds, the molding speed may be delayed, and the molding cycle may be lengthened. When it is within the above range, the crystallization speed is high, the high-speed moldability is excellent, and the molding high cycle can be achieved in the container production.
This value can be adjusted by the density, molecular weight and blending amount of the ethylene polymer (A2) of the ethylene polymer resin (A). Outside the scope of the present invention, when the MFR of the ethylene-based polymer is high, the density is low, and the blending amount is small, 121.5 ° C. measured by a differential scanning calorimeter (DSC) of the polyethylene resin composition. The peak top time in isothermal crystallization at 1 is increased.

Characteristic (iii): tan δ measured at 150 ° C. and 100 rad / sec measured with a rheometer is 0.50 to 0.80.
The tan δ at 150 ° C. and 100 rad / sec as measured by a rheometer, which is the characteristic (iii) of the polyethylene resin composition of the present invention, is preferably 0.50 or more. If this value is less than 0.50, the elastic behavior will be strong at the time of molding, and the shape of the pinch-off part will deteriorate, or the strength of the pinch-off part fusion interface will decrease, resulting in impact resistance as a container. May decrease.
This value can be adjusted by the molecular weight and blending amount of the ethylene polymer (A2) of the ethylene polymer resin (A).
Here, tan δ measured with a rheometer is a dynamic viscoelastic property measurement test apparatus (ARES manufactured by Reometrics), using a press sheet adjusted by hot press, 150 ° C., angular velocity 100 rad / sec. The storage elastic modulus G ′ and the loss elastic modulus G ″ are measured and calculated (tan δ = G ″ / G ′).

Characteristic (IV): The melt tension (MT, 190 ° C.) is preferably 50 mN or more. If the melt tension is less than 50 mN, a so-called draw-down phenomenon in which the parison hangs down during hollow molding tends to occur, and in particular, it may be difficult to form a relatively large hollow molding.
According to the polyethylene resin composition of the present invention, since it is preferably a polyethylene material that also has the above characteristics (i) to (iii), it is excellent in environmental stress crack resistance and impact resistance, and is thinner and lighter. In addition to being able to be molded, the crystallization speed is fast, the high-speed moldability is excellent, and a high molding cycle is possible.

  Various resins can be mixed in the polyethylene resin composition of the present invention. Moreover, 1 type (s) or 2 or more types can be used together suitably for the polyethylene resin composition of this invention. Specifically, antioxidants (phenolic, phosphorus, sulfur, etc.), UV absorbers / UV inhibitors, light stabilizers / weathering agents, lubricants, antistatic agents, antifogging agents, antiblocking agents, Processing aids such as dispersants, colored pigments (organic or inorganic pigments), pearl pigments, polarizing pearl pigments, crosslinking agents, foaming agents, neutralizing agents, thermal stabilizers, crystal nucleating agents, inorganic or organic fillers / fillers [Calcium carbonate, talc, metal powder (aluminum, copper, iron, lead, etc.), silica, diatomaceous earth, alumina, gypsum, mica, clay, asbestos, graphite, carbon black, titanium oxide, etc.], flame retardants, etc. Is possible.

[II] Molded product and use of the polyethylene resin composition of the present invention The molded product of the polyethylene resin composition of the present invention is obtained by molding the polyethylene resin composition of the present invention described in [I] above. The molding method of the polyolefin resin and polyolefin resin composition such as injection molding, compression injection molding, rotational molding, extrusion molding, hollow molding, blow molding, etc., which are conventionally known Either can be referred to.

Among the above-mentioned molded articles of the polyethylene resin composition of the present invention, when molded by hollow molding (blow molding), it is excellent in molding processability and has a balance between environmental stress crack resistance and rigidity and transparency, The effect of the present invention that can produce a molded article excellent in impact strength is more exhibited, and in particular, it is preferable because of excellent effects of molding processability and high molding speed.
For example, the blow molded product of the polyethylene resin composition of the present invention is particularly suitable for uses such as containers for detergents, shampoos and rinses, or food containers such as edible oils.

  In the following, the present invention will be described in more detail with reference to examples and comparative examples, and the superiority of the present invention and the superiority in the structure of the present invention will be demonstrated, but the present invention is limited by these examples. It is not a thing.

1. Measurement method The measurement methods used in the examples and comparative examples are as follows. The following catalyst synthesis step and polymerization step were all performed under a purified nitrogen atmosphere, and the solvent used was dehydrated and purified with molecular sieve 4A.

The measurement methods used in the examples are as follows.
(1) Melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg:
Measured according to JIS K6922-2: 1997.
(2) Melt flow rate (MLMFR) at a temperature of 190 ° C. and a load of 11.1 kg:
Measured according to JIS K6922-2: 1997.
(3) Melt flow rate (HLMFR) at a temperature of 190 ° C. and a load of 21.6 kg:
Measured according to JIS K6922-2: 1997.

(4) Density:
It measured based on JIS K6922-1,2: 1997.
(5) Melt tension Melt tension (melt tension: MT) is a value determined by measuring stress when a molten ethylene polymer is stretched at a constant speed, and was measured under the following conditions.
[Measurement condition]
・ Model used: Capillograph 1B, manufactured by Toyo Seiki Seisakusho
・ Nozzle diameter: 2.095mm
・ Nozzle length: 8.0mm
Inflow angle: 180 ° (flat)
Extrusion speed: 15mm / min
・ Pickup speed: 6.5 m / min
・ Measurement temperature: 190 ℃

(6) Environmental stress crack resistance (FNCT)
A full notched creep test (FNCT) was performed according to ISO DIS 16770. A sample is prepared by preparing a test piece having a cross section of 4 mm × 4 mm in which a 1 mm notch is made with a razor blade around a 6 mm × 6 mm × 11 mm square pillar, and pure water at 80 ° C. In particular, a tensile stress corresponding to 3.7 MPa was applied to the specimen, and the time until the specimen broke was measured.
(7) Crystallization time:
The sample was allowed to stand at 190 ° C. for 5 minutes with a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer Co., Ltd.), then cooled to 121.5 ° C. at a rate of 120 ° C./min, and held. The peak top was detected and measured when crystallization was completed at an isothermal temperature of 121.5 ° C.

(8) Pinch-off moldability tan δ, which is an index of pinch-off moldability, was measured using a rheometer (ARES manufactured by Remetrics) using a sample adjusted by hot pressing, and linear viscoelasticity measurement at 150 ° C. and an angular velocity of 100 rad / sec ( Storage elastic modulus G ′ and loss elastic modulus G ″) were performed, and tan δ (= G ″ / G ′) was calculated. The measurement conditions are described below.
[Measurement condition]
・ Device: Ales manufactured by Rheometrics
・ Jig: 25mm diameter parallel plate, plate spacing approx. 1.7mm
・ Measurement temperature: 150 ℃
・ Distortion: 10%

[Method for measuring strain hardening degree of ethylene polymer]
The strain hardening degree (λmax) of the extensional viscosity was measured by the method described in the present specification using a rheometer. Prior to the preparation of the test piece, the polymer was dissolved and reprecipitated according to the following procedure.
300 ml of xylene was introduced into a 500 ml two-necked flask equipped with a cooling tube, and nitrogen bubbling was performed at room temperature for 30 minutes. 6.0 grams of polymer and 1.0 gram of 2,6-di-t-butylhydroxytoluene (BTH) were introduced. The mixture was stirred at 125 ° C. for 30 minutes under a nitrogen atmosphere to completely dissolve the polymer in xylene. The xylene solution in which the polymer was dissolved was poured into 2.5 L of ethanol to precipitate the polymer. The polymer recovered by filtration was dried with a vacuum dryer at 80 ° C.

2. Examples, Comparative Examples and Evaluation [Example 1]
(1) Production of ethylene polymer (A1) <Production of Ziegler catalyst>
As the solid catalyst component, a Ti-based catalyst obtained by a dissolution precipitation method was used. The manufacturing method is as follows.
The inside of a 1 liter three-necked flask equipped with a stirrer and a condenser was sufficiently purged with nitrogen, and then dried hexane 250 ml, anhydrous magnesium chloride 11.4 g previously pulverized in a 3 liter vibration mill for 1 hour and n -110 ml of butanol was added and heated at 68 ° C for 2 hours to obtain a uniform solution (1a).
After cooling this solution (1a) to room temperature, 8 g of methylpolysiloxane having a kinematic viscosity at 25 ° C. of 25 cSt was added and stirred for 1 hour to obtain a uniform solution (1b).
Next, after the solution (1b) was cooled with water, 50 ml of titanium tetrachloride and 50 ml of dry hexane were dropped into the solution using a dropping funnel over 1 hour to obtain a solution (1c). The solution (1c) was uniform, and the complex of the reaction product was not precipitated.
The solution (1c) was heated at 68 ° C. for 2 hours while refluxing. About 30 minutes after the start of heating, precipitation of the reaction product complex (1d) was observed. This was collected, washed 6 times with 250 ml of dry hexane, and further dried with nitrogen gas to recover 19 g of the reaction product complex (1d).
When the reaction product complex (1d) was analyzed, it contained Mg 14.5% by mass, n-butanol 44.9% by mass and Ti 0.3% by mass, and the specific surface area was 17 m ² / g. .

Next, 4.5 g of the reaction product complex (1d) was taken in a 1-liter three-necked flask equipped with a stirrer and a condenser under a nitrogen atmosphere, and 250 ml of dry hexane and 25 ml of titanium tetrachloride were added thereto. The mixture was heat-treated at 68 ° C. for 2 hours under reflux, cooled to room temperature, washed 6 times with 250 ml of dry hexane, and dried with nitrogen gas to recover 4.6 g of the solid catalyst component (1e).
When this solid catalyst component (1e) was analyzed, it contained 12.5% by mass of Mg, 17.0% by mass of n-butanol and 9.0% by mass of Ti, and the specific surface area was 29 m ² / g. . When this solid catalyst component (1e) was observed with an SEM, the particle size was uniform and the shape was close to a sphere.

<Manufacture of polymer>
The solid catalyst component (1e) 0.79 g / hr obtained in the production of the catalyst from the catalyst supply line and the triisobutylaluminum (TIBAL) were organically added to the liquid-filled loop type first stage reactor having an internal volume of 145 liters. While supplying continuously from a metal compound supply line at a rate of 0.2 mmol / hr and discharging the polymerization contents at a required rate, dehydration-purified isobutane 160 (l / hr), hydrogen 32 (G / hr), ethylene 10 (kg / hr) was supplied at a rate, and the first stage polymerization was continuously performed under the conditions of a total pressure of 4.2 MPa and an average residence time of 0.8 hours.
A part of the polymerization product in the first-stage reactor was collected, and the polymer was collected and measured for physical properties. As a result, the MFR was 106 g / 10 min, and the density (D) was 0.9710 kg / m ³ .

The entire amount of the slurry-like polymerization product produced in the first stage reactor is directly introduced into the second stage reactor having an internal volume of 290 liters, and the contents of the polymerizer are discharged at the required speed without adding a catalyst. At 95 ° C., dehydrated and purified isobutane 160 (l / hr), hydrogen 21 (g / hr) and ethylene 9.5 (kg / hr) were supplied at a total pressure of 4.2 MPa and an average residence time of 0 The second stage polymerization was carried out continuously under the condition of .8Hr.
The polymerization product discharged from the second stage reactor was introduced into a flushing tank, the polymerization product was continuously withdrawn, and unreacted gas was removed from the degassing line.
As a result of evaluating the physical properties of the obtained polymer, the MFR was 99.0 and the density (D) was 0.9708 kg / m ^3. This polymer was an ethylene polymer (A1), and the results are shown in Table 1. did.

(2) Production of ethylene polymer (A2) <Production of polymer using metallocene catalyst>
Metallocene catalyst described in Example 10 of JP-T-2002-535339, dimethylsilylenebis {1,1 ′-{2- [2- (5-trimethylsilyl) furyl] -4,5-dimethyl-cyclopentadi An ethylene polymer (A2) was produced by using the following method using an enil}} zirconium dichloride.

<Preparation of supported catalyst>
Toluene solution of methylalumoxane (Albemarle, Al concentration 2.93 mol / L) 8.5 ml (25 mmol) and dimethylsilylenebis {1,1 ′-{2- [2- (5-trimethylsilyl) furyl] ] -4,5-dimethyl-cyclopentadienyl}} zirconium dichloride (85 mg) was added, and the mixture was stirred at room temperature for 30 minutes under light shielding to obtain a catalyst component solution.
Next, the catalyst component solution was added to 5.0 g of SiO ₂ (manufactured by GRACE, 2212, average particle size 12 μ) calcined at 600 ° C. for 8 hours under a nitrogen atmosphere, and stirred at 40 ° C. for 1 hour. Thereafter, vacuum drying was performed while maintaining 40 ° C. to obtain a solid catalyst.

<Ethylene polymerization>
To an autoclave with an internal volume of 1.5 L purged with nitrogen, 1 mmol of triisobutylaluminum, 2 ml of a 2% hexane solution of STADIS 450 and 1 ml of 1-hexene were added, and 800 ml of isobutane was introduced. The internal temperature of the autoclave was raised to 80 ° C., 16 ml of hydrogen was added, and ethylene was introduced so that the ethylene partial pressure was 1.4 MPa. Next, 30 mg of the catalyst was introduced into the autoclave to initiate polymerization. During the polymerization, ethylene was added so as to maintain 80 ° C. and ethylene partial pressure of 1.4 MPa. Further, in order to keep the hydrogen concentration during the polymerization constant, the hydrogen concentration in the gas phase part of the autoclave was measured, and the polymerization was continued while appropriately adding hydrogen. Furthermore, 1-hexene was continuously supplied at a ratio of 1 wt% of the added ethylene. After 3 hours, the reaction was stopped by purging the internal pressure of the autoclave and isobutane.
As a result, 176 g of polymer was recovered. The average hydrogen / ethylene molar ratio of the gas phase portion during polymerization was 0.08%. The physical property values of the obtained polymer are shown in Table 1.

(3) Production of ethylene polymer (A) <Production of polyethylene resin composition (A)>
The polyethylene (A1) and the ethylene-based polymer (A2) were melted and mixed at the ratio shown in Table 1 to produce a polyethylene resin composition (A).
The physical properties and evaluation results of the resin composition are shown in Table 1. The resulting composition has a high balance between density and FNCT, excellent balance between rigidity and environmental stress cracking resistance, excellent fluidity and high melt tension, and excellent hollow moldability, and a short crystallization time. Excellent molding high cycle performance.

(4) Production of ethylene polymer (B) [Preparation of metallocene catalyst B]
Under a nitrogen atmosphere, 5 grams of silica calcined at 600 ° C. for 5 hours was placed in a 200 ml two-necked flask and dried under reduced pressure with a vacuum pump for 1 hour while heating in a 150 ° C. oil bath. In a separately prepared 100 ml two-necked flask, under a nitrogen atmosphere, 52.5 mg of rac-ethylenebisindenylzirconium dichloride (manufactured by Strem Chemicals, Inc.) was added as a metallocene complex, and dissolved in 13.4 ml of dehydrated toluene. Further, 8.6 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle was added at room temperature and stirred for 30 minutes. While heating and stirring the 200 ml two-necked flask containing the vacuum-dried silica in an oil bath at 40 ° C., the whole toluene solution of the reaction product of the complex and methylaluminoxane was added. After stirring at 40 ° C. for 1 hour, a separately prepared 10 mg dehydrated toluene solution of 201 mg of N, N-dimethylanilinium tetrakispentafluorophenylborate was added and reacted for another 30 minutes. The solvent was distilled off under reduced pressure to obtain a solid catalyst B.
[Production of ethylene / 1-hexene copolymer]
Using the solid catalyst B, an ethylene / 1-hexene copolymer was produced. That is, 800 mL of isobutane, 22 mL of 1-hexene and 0.20 mmol of triethylaluminum were added to a 2 L autoclave equipped with an induction stirrer, the temperature was raised to 75 ° C., 130 mL of H2 was added, and ethylene was further introduced to adjust the ethylene partial pressure to 1. The pressure was kept at 4 MPa. Next, 54 mg of the above solid catalyst B was injected with nitrogen, polymerization was continued for 120 minutes while maintaining an ethylene partial pressure of 1.4 MPa and a temperature of 75 ° C., and then ethanol was added to stop the polymerization. During the polymerization reaction, H ₂ and 1-hexene were additionally supplied at a supply rate proportional to the ethylene consumption rate. As a result, the H ₂ / C ₂ (hydrogen / ethylene) molar ratios in the autoclave gas phase at 10 minutes after the start of polymerization and at the end of the polymerization were 0.21% and 0.35%, respectively, and 1-hexene was additionally supplied. The amount was 28 mL. The ethylene polymer (B) thus obtained was 205 g, and its MFR and density were 0.3 g / 10 min and 0.923 g / cm ³ , respectively. The ethylene polymer (B) is summarized in Table 1.

(5) Production of polyethylene resin composition A polyethylene resin composition (A) and an ethylene polymer (B) were melt-mixed at a mixing ratio shown in Table 1 to produce a polyethylene resin composition.
The physical properties and evaluation results of the resin composition are shown in Table 1. The resulting composition has an excellent balance between rigidity and environmental stress crack resistance, and has excellent flowability and high melt tension, so that it has excellent hollow moldability, and has a short crystallization time for density, and high molding cycle performance. It was excellent.

[Comparative Example 1]
In Example 1, instead of the ethylene polymer (B), a high-pressure radical process low-density polyethylene (LF240 manufactured by Nippon Polyethylene Co., Ltd .; MFR 0.7 g / 10 min, density 0.924 g / cm ³ ) was used. A polyethylene resin composition was produced in the same manner as in Example 1.
The physical properties and evaluation results of the resin composition are shown in Table 1. The resulting composition resulted in a poor balance between rigidity and environmental stress crack resistance.

[Example 2]
(1) As the ethylene polymer (A1), the one obtained in Example 1 (1) was used.
(2) Production of ethylene polymer (A2) <Production of polymer using metallocene catalyst>
Metallocene complex according to Synthesis Example 1 of JP 2011-132409 _{JP, rac- (Me 2 Si) 2} {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2 (rac- An ethylene polymer (A2) was produced by the following method using DMP-Me).

<Preparation of supported catalyst>
According to Example 1 of Unexamined-Japanese-Patent No. 2011-132409, the solid catalyst was obtained.

<Ethylene polymerization>
In the polymerization of ethylene in Example 1, instead of using the solid catalyst obtained in Example 1, a polymer was obtained by the following method using the solid catalyst.
To an autoclave with an internal volume of 2 L purged with nitrogen, 0.4 mmol of triethylaluminum and 11 ml of 1-hexene were added, and 1000 ml of hexane was introduced. The internal temperature of the autoclave was raised to 80 ° C., 18 ml of hydrogen was added, and ethylene was introduced so that the ethylene partial pressure was 1.5 MPa. Next, 120 mg of a solid catalyst was introduced into the autoclave to initiate polymerization. During the polymerization, ethylene and hydrogen were added to maintain 0.17% at 80 ° C., ethylene partial pressure of 1.5 MPa, and the hydrogen concentration in the gas phase as an average value, and polymerization was performed for 2 hours.
As a result, 218 g of polymer was recovered as an ethylene polymer (A2). The physical property values of the obtained polymer are shown in Table 1.

(3) Production of ethylene polymer resin (A) The ethylene polymers (A1) and (A2) were melt-mixed at the ratio shown in Table 1 to produce a polyethylene resin composition (A).
The physical properties and evaluation results of the resin composition are shown in Table 1. Although the obtained composition was inferior in melt tension, it was excellent in the balance between density and resistance to environmental stress cracking.

(4) As the ethylene polymer (B), the one obtained in Example 1 (4) was used.
(5) Production of polyethylene resin composition The polyethylene resin composition (A) and the ethylene-based polymer (B) were melt-mixed at the ratio shown in Table 1 to produce a polyethylene resin composition.
The physical properties and evaluation results of the resin composition are shown in Table 1. The resulting composition has a high balance between density and FNCT, excellent balance between rigidity and environmental stress crack resistance, excellent fluidity and high melt tension, excellent hollow moldability, and crystallization suitable for density. The time was short and the molding high cycle property was excellent.

[Comparative Example 2]
In Example 2, instead of the ethylene polymer (B), a high-pressure radical method low-density polyethylene (LF240 manufactured by Nippon Polyethylene Co., Ltd .; MFR 0.7 g / 10 min, density 0.924 g / cm ³ ) was used. A polyethylene resin composition was produced in the same manner as in Example 2.
The physical properties and evaluation results of the resin composition are shown in Table 1. The resulting composition resulted in a poor balance between rigidity and environmental stress crack resistance.

Example 3
<Production of ethylene polymer (A1)>
Similar to the polymerization of Example 2 (2), except that the solid catalyst used in Example 2 (2) was ethylene homopolymerized, and the hydrogen concentration during the polymerization was set to give the composition shown in Table 1. Went to. The evaluation results of the obtained polymer composition are shown in Table 1.
<Production of ethylene-based polymer (A2)>
Example 2 (2) was carried out except that 1-hexene and hydrogen concentration conditions were set so as to obtain the composition shown in Table 1. The evaluation results of the obtained polymer composition are shown in Table 1.

<Production of polyethylene resin composition (A)>
The said ethylene polymer (A1) and the ethylene polymer (A2) were melt-mixed in the ratio shown in Table 1, and the polyethylene resin composition (A) was manufactured.
The physical properties and evaluation results of the resin composition are shown in Table 1. Although the obtained composition was inferior in melt tension, it was excellent in the balance between density and resistance to environmental stress cracking.

<Production of ethylene polymer (B)>
The ethylene polymer (B) used was the one obtained in Example 1 (4).
<Manufacture of polyethylene resin composition>
The polyethylene resin composition (A) and the ethylene-based polymer (B) were melt-mixed at a ratio shown in Table 1 to produce a polyethylene resin composition.
The physical properties and evaluation results of the resin composition are shown in Table 1. The resulting composition has a high balance between density and FNCT, excellent balance between rigidity and environmental stress crack resistance, excellent fluidity and high melt tension, excellent hollow moldability, and crystallization suitable for density. The time was short and the molding high cycle property was excellent.

[Comparative Example 3]
In Example 3, instead of the ethylene-based polymer (B), a high-pressure radical process low-density polyethylene (LF240 manufactured by Nippon Polyethylene Co., Ltd .; MFR 0.7 g / 10 min, density 0.924 g / cm ³ ) was used. A polyethylene resin composition was produced in the same manner as in Example 1.
The physical properties and evaluation results of the resin composition are shown in Table 1. The resulting composition resulted in a poor balance between rigidity and environmental stress crack resistance.

As is clear from the above, the polyethylene resin composition of the present invention is excellent in molding process characteristics, and at the same time, excellent in the balance between environmental stress crack resistance and rigidity, and further excellent in transparency and impact resistance. In addition, a molded product obtained by injection molding, compression injection molding, rotational molding, extrusion molding or hollow molding of the polyethylene-based resin composition also has a balance between resistance to environmental stress cracking and rigidity, transparency, Since the impact property is excellent, it is possible to provide a thin molded product economically advantageously.
Therefore, the industrial value of the polyethylene resin composition of the present invention, which can economically advantageously provide a molded product having such desirable characteristics, is extremely large.

Claims (9)

41 to 99% by weight of ethylene polymer resin (A) satisfying the following condition (A-1) and ethylene polymer (B) satisfying the following conditions (B-1) to (B-6) 1 to 59% by weight, a melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 1 g / 10 minutes, and a density is 0.950 to 0.965 g / cm ³ . A polyethylene-based resin composition characterized by that.
(A-1) Ethylene polymer satisfying 50 to 90% by weight of ethylene polymer (A1) and the following conditions (A2-1) and (A2-2) based on the whole ethylene polymer resin (A) It consists of 10 to 50% by weight of the polymer (A2).
(A2-1) The melt flow rate (HLMFR _A2 ) at a temperature of 190 ° C. and a load of 21.6 kg is 0.1 g / 10 min or more and less than 5 g / 10 min.
(A2-2) The density (density _A2) is 0.915 to 0.945 g / cm ³ (B-1) MFR (MFR _B ) is 0.01 to 5.0 g / 10 minutes.
(B-2) The density (density _{B 1} ) is 0.900 to 0.960 g / cm ³ .
(B-3) The ratio ([Mw / Mn] _B ) between the weight average molecular weight and the number average molecular weight measured by gel permeation chromatography (GPC) is 2.0 to 6.0.
(B-4) The strain hardening degree ([λmax (2.0)] _B ) measured at a temperature of 170 ° C. and an elongation strain rate of 2 (unit: 1 / second) is 1.2 to 10.0.
(B-5) Strain hardening degree ([λmax (2.0)] _B ) measured at a temperature of 170 ° C. and an elongation strain rate of 2 (unit 1 / second), and an elongation strain rate of 0.1 (unit 1 / unit). strain hardening degree in the case of a second) the ratio of _{([λmax (0.1)] B} ) ([λmax (2.0)] B /[λmax(0.1)] B) is 1.2 to 10.0.
(B-6) A polymer produced by a polymerization reaction of ethylene using a catalyst containing a transition metal. The polyethylene-based resin composition according to claim 1, wherein the ethylene-based polymer (B) further satisfies the following condition (B-7).
(B-7) The content (WC) of a component having a molecular weight of 1 million or more measured by a GPC measurement device in which a differential refractometer, a viscosity detector, and a light scattering detector are combined is 0.01 to 10%, and The branching index (g _{C ′} ) at the molecular weight of 1,000,000 is 0.30 to 0.70.   The polyethylene-based polymer according to claim 1 or 2, wherein the ethylene-based polymer (B) is an ethylene / α-olefin copolymer produced by copolymerization of ethylene and α-olefin by a metallocene catalyst. Resin composition.   The ethylene-based polymer (B) is an ethylene / α-olefin copolymer produced by vapor phase or slurry copolymerization of ethylene and an α-olefin. The polyethylene-based resin composition according to Item. The polyethylene-based resin according to any one of claims 1 to 4, wherein the ethylene-based polymer resin (A) further satisfies the following conditions (A-2) and (A-3). Composition.
(A-2) MFR (MFR _A ) is 0.1 to 1 g / 10 minutes, and HLMFR (HLMFR _A ) is 10 to 50 g / 10 minutes.
(A-3) The density (density _{A 1} ) is 0.950 to 0.965 g / cm ³ . The polyethylene-based resin composition according to any one of claims 1 to 5, wherein the ethylene-based polymer resin (A) further satisfies the following condition (A-4).
(A-4) Melt flow rate ratio (HLMFR _A / MFR _A ) is 60-140.   Ethylene / α-olefin produced by copolymerization of ethylene and α-olefin using a metallocene catalyst containing at least ethylene-based polymer (A2) of ethylene-based polymer resin (A) containing Ti, Zr or Hf It is a copolymer, The polyethylene-type resin composition of any one of Claims 1-6 characterized by the above-mentioned. Furthermore, the following characteristics (i)-(iii) are satisfied, The polyethylene-type resin composition of any one of Claims 1-7 characterized by the above-mentioned.
Characteristic (i): All notched creep test (FNCT) based on ISO DIS 16770 is 100 hours or more.
Characteristic (ii): The peak top time in isothermal crystallization at 121.5 ° C. measured by a differential scanning calorimeter (DSC) is 200 seconds or less.
Characteristic (iii): tan δ at 150 ° C. and 100 rad / sec measured with a rheometer is 0.50 to 0.80 or more. A molded article obtained by hollow-molding the polyethylene-based resin composition according to any one of claims 1 to 8.

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