JP6743455B2 - Polyethylene resin composition, molded body and container thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyethylene resin composition, and a molded product and a container made of the same.

In polyethylene hollow molding, injection molding, inflation molding, and extrusion molding, materials having good molding processability and physical properties are generally required. In particular, hollow bottles that are commonly used as cosmetics containers, detergents, shampoo and rinse containers, or food containers such as edible oils have polyethylene resin excellent in moldability, physical properties and chemical properties. Is widely used.
Further, in recent years, in order to reduce costs, it has been required to reduce the weight and thickness of hollow bottles. In these hollow bottle applications, particularly excellent properties such as environmental stress crack resistance (ESCR) and impact strength are required. Is required. Polyethylene having a relatively high molecular weight and a wide molecular weight distribution is suitable as polyethylene satisfying such requirements.

Polyethylene polymerized using a chromium-based catalyst has a relatively wide molecular weight distribution and, due to its molecular structure with a long-chain branched structure, features that it is easily hollow-molded, specifically, has a large melt tension and swell ratio. Moreover, since it is easy to uniformly thicken the pinch-off part of the hollow bottle, it is widely used as a hollow molding material.
In addition, polyethylene that has been subjected to two-stage polymerization using a titanium-based catalyst is capable of imparting excellent environmental stress crack resistance by selectively copolymerizing a comonomer with a high molecular weight component, and low Since it is possible to control the molecular weight and the molecular weight distribution by controlling the molecular weight component, it is generally widely used as a high environmental stress cracking grade suitable for blow molding.
Then, a polyethylene polymer composition is disclosed in which polyethylene that has been subjected to two-step polymerization using a titanium-based catalyst and polyethylene that has been polymerized using a chromium-based catalyst are mixed to take advantage of each other (for example, Patent Document 1). 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 when attempting to secure the rigidity of the container while keeping the container thin, that is, to suppress the comonomer copolymerization amount. Since the necessity arises and it is contrary to the maintenance of the environmental stress crack resistance, there is still a demand for a material having an excellent balance between rigidity and environmental stress crack resistance and capable of coping with thinning.

Therefore, a multi-component polyethylene resin composition containing polyethylene using a metallocene-based catalyst and having improved balance between rigidity and resistance to environmental stress cracking is disclosed (see, for example, Patent Documents 8 to 13).
However, polyethylene using a metallocene-based catalyst has a relatively narrow molecular weight distribution, and because of its molecular structure having a uniform comonomer distribution, it is extremely excellent in environmental stress crack resistance, but is poor in hollow moldability, and specifically Since it has a feature that the melt tension and the swell ratio are small, it is used only for the purpose of storing a specific content liquid and as a container having a specific shape.
Further, as described in Patent Document 8, polyethylene using a metallocene-based catalyst has a low melting point or crystallization temperature with the same density, that is, it is easily melted with rigidity and is less likely to be crystallized, and thus is crystallized. The phenomenon that the speed becomes slow is recognized, and it is necessary to further increase the crystallization speed for high-speed molding.

Then, it contains polyethylene using a metallocene-based catalyst, and polyethylene mixed with a chromium-based catalyst is mixed, and by taking advantage of each other, it is excellent in balance of rigidity and environmental stress crack resistance and suitable for hollow moldability as well. The intended polyethylene polymer composition is disclosed (for example, patent documents 14-16).
However, Patent Document 14 discloses that by mixing polyethylene using a high molecular weight metallocene catalyst and polyethylene polymerized using a chromium catalyst, mechanical strength, moldability, and compatibility of each component are good and low gel. Although a composition having both excellent properties has been disclosed, the composition has an extremely high viscosity and is not suitable for high-speed moldability, and its use is limited to large hollow molding containers and the like.
Further, in Patent Documents 15 and 16, a composition having both mechanical strength and moldability is obtained by mixing a composition containing polyethylene using a high-molecular weight metallocene catalyst and polyethylene polymerized using a chromium catalyst. Although the composition is disclosed, the composition has not been sufficiently studied on the compatibility of each component, the molecular weight of polyethylene using a high molecular weight metallocene catalyst is too high, or contributes to the compatibility. Since the amount of polyethylene polymerized using a chromium-based catalyst is small, sufficient compatibility cannot be obtained and the appearance of the molded product is not always sufficient.

On the other hand, for the purpose of further increasing the environmental stress crack resistance of polyethylene using a metallocene catalyst, an increase in the molecular weight is extremely effective, while the compatibility with other polyethylene deteriorates, so polyethylene using a metallocene catalyst is used. In a polyethylene resin composition containing, it is important to design a resin that has both compatibility and environmental stress crack resistance.
In view of such circumstances, while having the hollow moldability required for conventional polyethylene resin compositions for containers, high rigidity, impact resistance, etc., the crystallization rate is high, and high-speed molding high cycle can be achieved. Furthermore, there is a demand for a polyethylene material that is particularly excellent in the appearance of molded products.

Therefore, the applicant has found a polyethylene material or the like having a high crystallization rate that can achieve further high-speed molding and high cycle while having hollow moldability, high rigidity, impact resistance, etc., and filed an application first. (Patent Documents 17 to 19). Patent Documents 17 to 19 are polymerized by using a metallocene-based catalyst containing Ti, Zr or Hf with respect to 60 to 90 mass% of specific polyethylene, and HLMFR and density have specific values, respectively, and long chain branching. Disclosed is a polyethylene resin composition for containers, which contains 10 to 40% by mass of a specific ethylene polymer having a structure and which satisfies specific properties.
Further, the applicant of the present invention discloses in Patent Document 20 a polyethylene resin composition containing a specific amount of a polyethylene-based resin satisfying specific characteristics and a specific ethylene/α-olefin copolymer, and a molded product made of the same. Disclosure.
However, the required performance required for products is increasing day by day, and further performance improvement is demanded in view of the problems of the above-mentioned conventional techniques.

JP-A-59-196345 JP-A-59-196346 JP, 60-036547, A JP, 2004-059650, A JP 2004-091739 A JP, 2004-168817, A JP, 2005-298811, A Japanese Patent Laid-Open No. 08-283476 JP-A-08-283477 JP, 2006-83370, A JP, 11-106574, A JP, 11-199719, A JP, 2009-7579, A JP, 2003-213053, A JP, 11-138618, A Japanese Patent Publication No. 2009-506163 JP, 2013-204015, A JP, 2014-208749, A JP, 2014-208750, A JP, 2014-208817, A

The object of the present invention is, in view of the above problems of the prior art, hollow moldability, environmental stress crack resistance, excellent impact resistance, thinner, can be molded with a light weight, crystallization speed is fast, It has excellent high-speed moldability, can be molded into a high cycle, has high melt tension, has excellent drawdown resistance, has good pinch-off characteristics, and is capable of hollow molding of complex shapes. It is an object of the present invention to provide a polyethylene resin composition which is expensive and has a particularly excellent appearance of a molded product, and a molded product made of the same.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have contained a specific amount of a specific polyethylene component (A), a specific polyethylene component (B) and a specific polyethylene component (C), and satisfied specific properties. The polyethylene resin composition has excellent hollow moldability, environmental stress crack resistance, and impact resistance, and can be molded with a thinner and lighter weight, has a high crystallization rate, has excellent high-speed moldability, and has a high molding cycle. It has a high melt tension, excellent drawdown resistance, good pinch-off characteristics, and is capable of hollow molding of complicated shapes. In addition, it has a high compatibility with resin components and is particularly excellent in the appearance of molded products. It was found that a polyethylene resin composition and a molded product made of the same can be obtained, and the present invention has been completed.

That is, according to the first aspect of the present invention, 10% by mass or more and 40% by mass or less of the following polyethylene component (A) polymerized by a metallocene-based catalyst, and the following polyethylene component (B) polymerized by a chromium-based catalyst: 5 mass% or more and 50 mass% or less, and 40 mass% or more and 85 mass% or less of the following polyethylene component (C) polymerized by a Ziegler-Natta catalyst are contained, and the following characteristics (1) to (5) and ( A polyethylene resin composition satisfying 9) is provided.
Polyethylene component (A); Characteristic (a1): Melt flow rate (HLMFR) at a temperature of 190° C. and a load of 21.6 kg is 0.57 g/10 minutes or more and less than 5 g/10 minutes, and characteristic (a2): density is 0.915 g / cm ³ or more 0.945 g / cm ³ der hereinafter is, characteristics (a3): dynamic melt viscosity eta _{H · 0.01} the frequency ω at a temperature 190 ° C. is measured when 0.01 rad / sec (unit: Pa · sec) 100,000 exceeded, polyethylene Ru der less than 800,000.
Polyethylene component (B); Characteristic (b1): HLMFR is 2 g/10 minutes or more and less than 20 g/10 minutes, and characteristic (b2): Density is more than 0.945 g/cm ^{3 and} 0.965 g/cm ³ or less. Characteristics (b3): elongation viscosity η(t) (unit: Pa·sec) and elongation time t (unit: sec) measured at a temperature of 170° C. and elongation strain rate of 0.1 (unit: 1/sec). Polyethylene where the inflection point of extensional viscosity due to strain hardening is observed in a log-log plot.
Polyethylene component (C); Characteristic (c1): Melt flow rate (MFR) at a temperature of 190° C. and a load of 2.16 Kg is 10 g/10 minutes or more and 200 g/10 minutes or less, and characteristic (c2): density is 0. 960 g / cm ³ or more 0.980 g / cm ³ or less polyethylene is.
Characteristic (1): MFR is 0.1 g/10 minutes or more and 1 g/10 minutes or less.
Characteristic (2): HLMFR is 10 g/10 minutes or more and 50 g/10 minutes or less.
Characteristic (3): The melt flow rate ratio (HLMFR/MFR), which is the ratio of HLMFR to MFR, is 50 or more and 130 or less.
Characteristics (4): density of 0.940 g / cm ³ or more 0.965 g / cm ³ or less.
Characteristic (5): Both elongation viscosity η(t) (unit: Pa·sec) and elongation time t (unit: sec) measured at a temperature of 170° C. and elongation strain rate of 0.1 (unit: 1/sec). In the logarithmic plot, the inflection point of elongational viscosity due to strain hardening is observed.
Characteristic (9): Dynamic melt viscosity η _H of polyethylene component (A) against dynamic melt viscosity η _W·0.01 of polyethylene resin composition measured at a frequency ω of 0.01 rad/sec at a temperature of 190° C. _{· 0.01} ratio eta _H-0.01 / eta _W-0.01 1 excess is less than 14.

According to a second aspect of the present invention, there is provided a polyethylene resin composition according to the first aspect, wherein the polyethylene component (B) satisfies the following characteristic (b4).
Characteristic (b4): The molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) is 10 or more and 50 or less.

According to a third aspect of the present invention, there is provided a polyethylene resin composition which further satisfies the following characteristic (6) in the first or second aspect.
Characteristic (6): The peak top time (T) and the melting point (Tm) in the isothermal crystallization at 121.5° C. measured by a differential scanning calorimeter (DSC) satisfy the following relational expression (1).
T [second]≦−76.80×Tm [° C.]+10,410 Relational expression (1)

According to a fourth aspect of the present invention, there is provided a polyethylene resin composition according to any one of the first to third aspects, which further satisfies the following characteristic (7).
Characteristic (7): Melt tension (MT) measured at 190° C. is 50 mN or more.

According to a fifth aspect of the present invention, there is provided a polyethylene resin composition according to any one of the first to fourth aspects, wherein the polyethylene component (A) satisfies the following characteristic (a4).
Characteristic (a4): The melt flow rate ratio (HLMFR/MFR), which is the ratio of HLMFR to MFR, is 10 or more and 35 or less.

According to a sixth aspect of the present invention, there is provided a polyethylene resin composition according to any one of the first to fifth aspects, wherein the polyethylene component (C) satisfies the following characteristics (c3) and (c4). To be done.
Characteristic (c3): Melt flow rate (MLMFR) at a temperature of 190° C. and a load of 11.1 Kg is 50 g/10 minutes or more and 2,000 g/10 minutes or less.
Characteristic (c4): The melt flow rate ratio (MLMFR/MFR), which is the ratio of MLMFR to MFR, is 3 or more and 15 or less .

Moreover, according to the 7th invention of this invention, the molded object produced using the polyethylene resin composition of any one of the 1st- 6th invention is provided.

Moreover, according to the 8th invention of this invention, the container produced using the polyethylene resin composition of any one of the 1st- 6th invention is provided.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in hollow formability, environmental stress cracking resistance, and impact resistance, can be formed in a thinner and lighter weight, has a high crystallization rate, is excellent in high-speed formability, and has a forming high cycle. Polyethylene, which has a high melt tension, excellent drawdown resistance, pinch-off characteristics, hollow molding of complex shapes, high compatibility of resin components, and excellent appearance of the molded product. There is an effect that a resin composition can be provided.
Further, according to the present invention, it is possible to provide a molded body and a container having excellent environmental stress crack resistance and impact resistance, excellent surface properties, and good appearance.

FIG. 1 is a typical plot diagram of extensional viscosity, and is a diagram illustrating a case where an inflection point of extensional viscosity is observed. FIG. 2 is a typical plot diagram of elongational viscosity, and is a diagram illustrating a case where an inflection point of elongational viscosity is not observed.

The polyethylene resin composition of the present invention contains 10% by mass or more and 40% by mass or less of the following polyethylene component (A), 5% by mass or more and 50% by mass or less of the following polyethylene component (B), and 40% by mass of the following polyethylene component (C). The content is from 85% by mass to 85% by mass and satisfies the following properties (1) to (5).
Polyethylene component (A); Property (a1): Melt flow rate (HLMFR) at a temperature of 190° C. and a load of 21.6 Kg is 0.2 g/10 min or more and less than 5 g/10 min, and property (a2): density is Polyethylene of 0.915 g/cm ³ or more and 0.945 g/cm ³ or less.
Polyethylene component (B); Characteristic (b1): HLMFR is 2 g/10 minutes or more and less than 20 g/10 minutes, and characteristic (b2): Density is more than 0.945 g/cm ^{3 and} 0.965 g/cm ³ or less. Characteristics (b3): elongation viscosity η(t) (unit: Pa·sec) and elongation time t (unit: sec) measured at a temperature of 170° C. and elongation strain rate of 0.1 (unit: 1/sec). Polyethylene where the inflection point of extensional viscosity due to strain hardening is observed in a log-log plot.
Polyethylene component (C); Characteristic (c1): Melt flow rate (MFR) at a temperature of 190° C. and a load of 2.16 Kg is 10 g/10 minutes or more and 200 g/10 minutes or less, and characteristic (c2): density is 0.960 g. /Cm ³ or more and 0.980 g/cm ³ or less polyethylene.
Characteristic (1): MFR is 0.1 g/10 minutes or more and 1 g/10 minutes or less.
Characteristic (2): HLMFR is 10 g/10 minutes or more and 50 g/10 minutes or less.
Characteristic (3): The melt flow rate ratio (HLMFR/MFR), which is the ratio of HLMFR to MFR, is 50 or more and 140 or less.
Characteristics (4): density of 0.940 g / cm ³ or more 0.965 g / cm ³ or less.
Characteristic (5): Both elongation viscosity η(t) (unit: Pa·sec) and elongation time t (unit: sec) measured at a temperature of 170° C. and elongation strain rate of 0.1 (unit: 1/sec). In the logarithmic plot, the inflection point of elongational viscosity due to strain hardening is observed.
Hereinafter, the present invention will be described in detail for each item.
In addition, in the present invention, polyethylene is a generic term for an ethylene homopolymer and a copolymer of ethylene and an olefin described later, and is also referred to as an ethylene polymer.

1. Polyethylene component (A)
Characteristic (a1)
As the polyethylene component (A) used in the present invention, those having an HLMFR of 0.2 g/10 minutes or more and less than 5 g/10 minutes are selected from the viewpoint of exerting the effect of the present invention. The HLMFR of the polyethylene component (A) is preferably in the range of 0.3 g/10 minutes or more and 1.0 g/10 minutes or less, more preferably 0.4 g/10 minutes or more and 0.7 g/10 minutes or less. If this HLMFR is less than 0.2 g/10 minutes, HLMFR cannot be achieved within the specified range in the final resin composition, the fluidity may be reduced, or the compatibility may be reduced, so that The appearance may be impaired. On the other hand, if the HLMFR is 5 g/10 minutes or more, the final resin composition may not be able to achieve the environmental stress crack resistance, and the long-term durability of the molded product may be reduced.
HLMFR can be measured according to JIS K6922-2:1997.
HLMFR can be adjusted mainly by the amount of hydrogen and the polymerization temperature during the polymerization of the polyethylene component (A).

Characteristic (a2)
As the polyethylene component (A) used in the present invention, those having a density of 0.915 g/cm ³ or more and 0.945 g/cm ³ or less are selected from the viewpoint of exerting the effect of the present invention. The density of polyethylene component (A) is preferably 0.920 g / cm ³ or more 0.935 g / cm ³ or less, still more preferably 0.924 g / cm ³ or more 0.930 g / cm ³ or less. If the density is less than 0.915 g/cm ³ , the density range in the final resin composition cannot be achieved, rigidity is insufficient, and the crystallization rate is reduced, which may result in a reduction in molding cycle. .. On the other hand, if the density exceeds 0.945 g/cm ³ , the environmental stress cracking resistance of the final resin composition may decrease.
The density can be measured according to JIS K6922-1, 2:1997.
The density can be adjusted mainly by the amount of α-olefin during the polymerization of the polyethylene component (A).

Characteristic (a3)
The polyethylene component (A) used in the present invention preferably satisfies the following characteristic (a3).
Characteristic (a3): Dynamic melt viscosity η _H·0.01 (unit: Pa·sec) measured at a frequency ω of 0.01 rad/sec at a temperature of 190° C. exceeds 100,000 and less than 1,000,000. ..
In the characteristic (a3), the polyethylene component (A) used in the present invention has a dynamic melt viscosity η _H·0.01 (unit: Pa·sec) of 1,000 rad/sec at a frequency ω of 1,000, It is preferably less than 000, more preferably less than 800,000, even more preferably less than 600,000. On the other hand, the lower limit is not particularly limited, but it is preferably 100,000 or more, and more preferably 200,000 or more, because an appropriate molecular weight is required in order to maintain high environmental stress crack resistance in the final resin composition. Preferably, it is more preferably 300,000 or more. When the dynamic melt viscosity is less than 1,000,000, the viscosity of the polyethylene component (A) is suppressed to be low, and the viscosity ratio between the low molecular weight component polyethylene component (C) and the high molecular weight component polyethylene component (A). Can be suppressed to be small, and a composition having excellent compatibility can be obtained. Therefore, it is easy to improve the appearance of the molded product and suppress deterioration of physical properties such as impact resistance.
The dynamic melt viscosity was measured by blending 2000 ppm of an antioxidant (IRGANOX B225 manufactured by BASF Japan Ltd.) into a sample, melt-kneading the mixture and molding it into a sheet having a thickness of 1.0 mm by a hot press, and using a rheometer (Ares manufactured by Rheometrics). Use the parallel plate to bring the sample into close contact with the plate and melt it, then relax the stress at a temperature of 210 to 220°C, and cool the sample to a temperature of 190°C while adjusting the plate interval so that there is no gap between the plates. Then, the measurement can be performed at a frequency ω of 0.01 rad/sec by performing the measurement in a plate interval of about 1.0 mm and a strain of 0.2 to 1%.
The dynamic melt viscosity of the polyethylene component (A) can be generally controlled by the molecular weight, the molecular weight distribution, the long chain branched structure and the like. Therefore, in order to obtain the polyethylene component (A) having a dynamic melt viscosity in a specific range, a polyethylene having a specific molecular weight and molecular weight distribution and an appropriate long-chain branched structure is used, and a specific catalyst is also used. Can be suitably obtained by polymerizing with.

Characteristic (a4)
The polyethylene component (A) used in the present invention preferably satisfies the following characteristic (a4).
Characteristic (a4): The melt flow rate ratio (HLMFR/MFR), which is the ratio of HLMFR to MFR, is 10 or more and 35 or less.
According to the characteristic (a4), HLMFR/MFR is preferably 30 or less, more preferably 25 or less, while preferably 15 or more, more preferably 20 or more.
HLMFR/MFR has a strong correlation with the molecular weight distribution, and when HLMFR/MFR has a large value, the molecular weight distribution is wide, and when HLMFR/MFR has a small value, the molecular weight distribution is narrow. It is suggested that when the HLMFR/MFR exceeds 35, the influence of the long-chain branched structure appears strongly, and when the HLMFR/MFR is 35 or less, the compatibility of each component tends to be good. That is, the compatibility with the polyethylene component (C) is likely to be good, the surface properties of the molded product are likely to be smooth, the appearance is excellent, and deterioration of physical properties such as impact resistance of the molded product is easily suppressed. On the other hand, the lower limit is not particularly limited, but is preferably 10 or more because impact resistance and ESCR are required.
MFR can be measured according to JIS K6922-2:1997.
Moreover, the control method of HLMFR/MFR can be mainly performed according to the control method of molecular weight distribution.

Characteristic (a5)
Furthermore, the polyethylene component (A) used in the present invention preferably has a long chain branched structure. When the polyethylene component (A) has a long-chain branched structure, it becomes easy to observe an inflection point of extensional viscosity due to strain hardening in the polyethylene resin composition. That is, when the polyethylene component (A) of the present invention has a long-chain branched structure, the polyethylene resin composition of the present invention has an elongation measured at a temperature of 170° C. and an elongation strain rate of 0.1 (unit: 1/second). In the logarithmic plot of the viscosity η(t) (unit: Pa·sec) and the elongation time t (unit: sec), it becomes easy to observe the inflection point of the elongation viscosity due to strain hardening. By observing the inflection point, the crystallization rate of the polyethylene resin composition can be extremely effectively increased, and the molding cycle can be improved.

The relationship between the long-chain branched structure of the polyethylene component (A) and HLMFR/MFR is considered as follows. In general, when polyethylene has a long-chain branched structure, components having a long relaxation time due to the entanglement of long-chain branches increase. As a result, even if the molecular weight and molecular weight distribution are the same, the viscosity in the low shear rate region increases, so that η ₀ (zero shear viscosity) shows a large value, MFR becomes small, and HLMFR/MFR increases. .. That is, a large value of HLMFR/MFR can be regarded as one of the indicators suggesting an increase in the entanglement of long chain branches. Therefore, the inflection point of extensional viscosity was observed in the polyethylene resin composition, and the HLMFR/MFR in the polyethylene component (A) was 10 or more and 35 or less, which means that the polyethylene component (A) had a specific long chain It is suggested to have a branched structure.

In the present specification, the presence or absence of an inflection point of elongational viscosity due to strain hardening can be observed in the measurement of strain hardening degree.
Regarding the method for measuring the strain hardening degree, the same value can be obtained in principle by any method as long as the uniaxial elongation viscosity can be measured. Details are given.
In measuring polyethylene according to the present invention, the following may be mentioned as preferable measuring methods and measuring instruments.

Measuring method:
-Device: Ares manufactured by Rheometrics
・Jig: Extensive Viscosity Fixture manufactured by TA Instruments
・Measurement temperature: 170℃
-Strain rate: 0.1/sec-Preparation of test piece: Press molding is performed to prepare a sheet having a size of 18 mm x 10 mm and a thickness of 0.7 mm.

Calculation method:
The elongation viscosity at 170° C. and a strain rate of 0.1/second is plotted in a logarithmic graph with time t (second) on the horizontal axis and elongation viscosity η(t) (Pa·second) on the vertical axis. On the logarithmic log graph, the maximum extensional viscosity before strain is 4.0 after strain hardening is η _Max (t1) (t1 is the time at which the maximum extensional viscosity is shown), and the extensional viscosity before strain hardening The value calculated as η _Max (t1)/η _Linear (t1) is defined as the strain hardening degree (λmax), where η _Linear (t) is the approximate straight line. The presence or 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 with the passage of time.
1 and 2 are typical plots of extensional viscosity. FIG. 1 shows a case where an inflection point of extensional viscosity is observed, and η _Max (t1) and η _Linear (t1) are shown in the figure. FIG. 2 shows the case where no inflection point of extensional viscosity is observed.

In order for the polyethylene component (A) to have a long-chain branched structure, it is preferable to apply a suitable polymerization catalyst for polymerization, and it is preferable to select from the polymerization catalysts described below.

Characteristic (a6)
The polyethylene component (A) used in the present invention preferably satisfies the following characteristic (a6).
Characteristic (a6): Dynamic melt viscosity η ^* (Pa·second) measured at a frequency ω of 100 rad/sec to 0.01 rad/sec at a temperature of 190° C. is approximated by the following relational expression (2). The zero shear viscosity η ₀ (Pa·sec) is 100,000 or more and 1,000,000 or less.
η ^* /η ₀ =1/{1+(τ ₀ ω) ⁿ } Relational expression (2)
(In the relational expression (2), τ ₀ is a parameter indicating the relaxation time, and n is a parameter indicating the shear rate dependence of the melt viscosity in the high shear rate region.)
In the characteristic (a6), the polyethylene component (A) used in the present invention preferably has a zero shear viscosity η ₀ (unit: Pa·sec) of 1,000,000 or less, but less than 800,000 is more preferable. Preferably, less than 600,000 is even more preferable. On the other hand, the lower limit is not particularly limited, but is preferably 100,000 or more for the reason that an appropriate molecular weight is required for maintaining high environmental stress crack resistance in the final resin composition. It is more preferably 200,000 or more, still more preferably 400,000 or more. When the zero shear viscosity is 1,000,000 or less, the viscosity of the polyethylene component (A) is suppressed to be low, and the viscosity ratio of the low molecular weight component polyethylene component (C) and the high molecular weight component polyethylene component (A). Is preferable, and a composition having excellent compatibility can be obtained, which is preferable. Therefore, it is easy to improve the appearance of the molded product and suppress deterioration of physical properties such as impact resistance.

The zero shear viscosity η ₀ (unit: Pa·sec) is defined as the shear viscosity at zero shear flow, and in the present specification, the relaxation time τ ₀ (sec) is used together with ANTEC'94 (The Society of Plastics Engineers, 1994). ), page 1814 (S. Lai et al.), a value obtained by approximating the dynamic melt viscosity η ^* (unit: Pa·sec) by a cross viscosity formula (the following relational expression (2)). Here, the dynamic melt viscosity η ^* is in the range of a plate spacing of 1.0 mm, a strain of 0.2 to 1% using a parallel plate at 190° C., and a frequency ω of 100 to 0.01 (unit: rad/sec). Is a value obtained when measured with a rheometer (Ares manufactured by Rheometrics, Inc.), and approximation of the result to the following relational expression (2) is performed by a regression method using a commercially available computer program. Can be calculated.
η ^* /η ₀ =1/{1+(τ ₀ ω) ⁿ } Relational expression (2)
In the above relational expression (2), n is a parameter indicating the shear rate dependence of melt viscosity in the high shear rate region, and τ ₀ is a parameter indicating the relaxation time.

In general, polyethylenes having different molecular weights, in other words, when melt-mixing polyethylenes having different viscosities, the one having a smaller viscosity ratio is more likely to be mixed, and the one having a high viscosity has a high viscosity. It is known that the component becomes unevenly distributed and becomes a gel due to poor dispersion, which causes poor appearance. For example, more detailed studies have been conducted on Newtonian fluids, and when mixing liquids with different viscosity ratios, the conditions for dispersing highly viscous liquids: the number of capillaries depends on the kneading mode and the viscosity ratio of the two. It has been reported that they can be arranged (HP Grace: Chem. Eng. Commun., 14, 225 (1982)). It has also been reported that when the same strain is applied to a system in which liquids having different viscosity ratios are mixed, the strain rate of the high-viscosity liquid becomes smaller in a system having a larger viscosity ratio, which causes a dispersion failure. (A. Biswas et al.: SPE-ANTEC, 336 (1994)).
On the other hand, since polyethylene resin and the like are non-Newtonian fluids, the above knowledge cannot be simply applied because the viscosity depends on the shear rate, but it is considered that the above knowledge can be referred to. From the above, in the dispersion of polyethylene having a large viscosity ratio, it is considered that the viscosity of the region of low strain rate of the high viscosity component is an important factor, and the viscosity of the region of low strain rate of the resin is within the range of the present invention. It is speculated that the polyethylene component (A) will be highly dispersed in the polyethylene resin composition.
Further, the value of the zero shear viscosity η ₀ of the polyethylene component (A) can be generally adjusted by the molecular weight, the molecular weight distribution and the long chain branching. Therefore, in order to obtain the zero-shear viscosity η ₀ within a specific range, a long-chain branched structure having a specific molecular weight and a specific molecular weight distribution and being appropriately controlled may be used. It can be preferably produced by using the above catalyst.

From the above, it is considered that the compatibility may be poor in the resin composition containing the component having the long-chain branched structure. However, even if it has a long chain branching structure, the length and/or number of long chain branches can be controlled by using a component having a specific melt flow rate ratio (HLMFR/MFR) and a specific viscosity characteristic. It is presumed that is controlled, in the resin composition, while the compatibility is improved, the effect of having a long-chain branched structure is also exerted, and the effect of the present invention as described above can be exerted. Was found.

The polyethylene component (A) having a long-chain branched structure used in the present invention is not particularly limited as a production method, but preferably, as a polymerization catalyst, a specific metallocene catalyst, that is, a catalyst having a specific structure metallocene complex. Can be used to polymerize.
The polyethylene component (A) having a long-chain branched structure can be obtained by producing polyethylene (macromonomer) having a terminal vinyl group by chain transfer to ethylene and copolymerizing the macromonomer with ethylene.
Among the metallocene catalysts, a catalyst having a metallocene complex having a specific structure is preferable, and a metallocene complex having a cyclopentadienyl ring and a heterocyclic aromatic group, or a metallocene complex having a cyclopentadienyl ring and a fluorenyl ring is particularly preferable. preferable.

It is important that the polyethylene component (A) is polymerized by a metallocene catalyst containing Ti, Zr or Hf. Examples of the metallocene catalyst include a combination of a cocatalyst and a complex called a metallocene complex in which a ligand having a cyclopentadiene skeleton is coordinated with a transition metal. As a specific metallocene catalyst, a metallocene complex 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 cocatalyst include a combination of an organometallic compound of Group 1 to 3 elements of the periodic table such as aluminoxane, and a supported type in which these complex catalysts are supported on a carrier such as silica.

The metallocene catalyst used in the present invention contains the following catalyst component (i) and catalyst component (ii), and is a catalyst which is combined with the catalyst component (iii) as required.
Catalyst component (i): Metallocene complex Catalyst component (ii): Compound that reacts with catalyst component (i) to form a cationic metallocene compound Catalyst component (iii): Fine particle carrier

(1) Catalyst component (i)
As the catalyst component (i), a metallocene compound of a transition metal of Group 4 of the periodic table is used. Specifically, the 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 general formula (I)
^{_{Q 1 (C 5 H 4-}} c R 1 c) (C 5 H 4-d R 2 d) MXY general formula (II)
^{_{Q 2 (C 5 H 4-}} e R 3 e) ZMXY general formula (III)
^{_{(C 5 H 5-f R}} 3 f) ZMXY general formula (IV)
^{_{(C 5 H 5-f R}} 3 f) MXYW formula (V)
^{_{Q 3 (C 5 H 5-}} g R 4 g) (C 5 H 5-h R 5 h) MXY formula (VI)
^{_{Q 4 Q 5 (C 5 H}} 3-i R 6 i) (C 5 H 3-j R 7 j) MXY formula (VII)

Here, Q ¹ , Q ⁴ , and Q ⁵ are bonding groups that bridge the two conjugated five-membered ring ligands, and Q ² is a bonding group that bridges the conjugated five-membered ring ligand and the Z group, Q ³ is a bonding group bridging R ⁴ and R ⁵ , M is a transition metal of Groups 3 to 12 of the periodic table, and X, Y and W are each independently hydrogen, halogen, and a carbon number of 1 to 20. Hydrocarbon group, C1-C20 oxygen-containing hydrocarbon group, C1-C20 nitrogen-containing hydrocarbon group, C1-C20 phosphorus-containing hydrocarbon group, or C1-C20 silicon-containing hydrocarbon Z is a ligand containing oxygen, 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. Show. M is preferably a Group 4 transition metal such as Ti, Zr or Hf.

R ^{1 to} R ⁷ 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, and silicon. It represents a hydrocarbon group containing, a hydrocarbon group containing phosphorus, a hydrocarbon group containing nitrogen, or a hydrocarbon group containing boron. Among these, at least one of R ^{1 to} R ⁵ is preferably 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 hydrocarbon groups. It may have a hydrogen group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, but in that case, a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing hydrocarbon group are preferable. In addition, adjacent two R ¹ , two R ² , two R ³ , two R ⁴ , two R ⁵ , two R ⁶ , or two R ⁷ are respectively bonded. And may form a ring having 4 to 10 carbon atoms. a, b, c, d, e, f, g, h, i and j are 0≦a≦5, 0≦b≦5, 0≦c≦4, 0≦d≦4, 0≦e≦, respectively. It is an integer that satisfies 4, 0≦f≦5, 0≦g≦5, 0≦h≦5, 0≦i≦3, and 0≦j≦3.

Bonding group Q ¹ , Q ⁴ , Q ⁵ bridging ^two conjugated five-membered ring ligands, bonding group Q ² bridging the conjugated five-membered ring ligand and Z group, and R Specific examples of Q ³ which bridges 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 cross-linking groups such as silylene group, methyl ethyl silylene group, methylphenyl silylene group, methyl-t-butyl silylene group, disilylene group, tetramethyldisilylene group, germanium-containing cross-linking group, alkylphosphine, amine and the like. .. 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, but Zr is Hf. Alternatively, a compound substituted with Ti can be used as well. Further, 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.

Compound of General Formula (I) Biscyclopentadienyl zirconium 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-furylcyclopentadienyl) Zirconium dichloride, bis(2-furylindenyl)zirconium dichloride, bis(2-furyl-4,5-benzoindenyl)zirconium dichloride.

Compound of the general formula (II) dimethylsilylenebis(1,1'-cyclopentadienyl)zirconium dichloride, dimethylsilylenebis[1,1'-(2-methylindenyl)]zirconium dichloride, dimethylsilylenebis[1, 1'-(2-Methyl-4-phenyl-indenyl)]zirconium dichloride, ethylenebis[1,1'-(2-methyl-4,5-benzoindenyl)]zirconium dichloride, dimethylsilylenebis[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 dichloride, dimethylsilylenebis[1,1′-(2-ethyl-4-phenyl-4H-azurenyl)]zirconium dichloride, ethylenebis[ 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, dimethyl silylene bis {1,1'-{2-[2-(5-trimethylsilyl)furyl]-4,5-dimethyl-cyclopentadienyl}} zirconium dichloride, dimethyl silylene bis {1,1 '-[2-(2-Furyl)indenyl]} zirconium dichloride, dimethylsilylene bis{1,1'-[2-(2-furyl)-4-phenyl-indenyl]} zirconium dichloride, dimethylsilylene bis{1, 1'-[2-(2-(5-methyl)furyl)-4-phenyl-indenyl]}zirconium dichloride, dimethylsilylene bis{1,1'-[2-(2-(5-methyl)furyl)- 4-(4-Isopropyl)phenyl-indenyl]}zirconium dichloride, dimethylsilylene bis{1,1′-[2-(2-(5-methyl)furyl)-4-(4-t-butyl)phenyl-indenyl ] Zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) [9-(2,7-t-butyl)fluorenyl] zirconium dichloride, diphenylmethylene (cyclo) Pentadienyl)[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-[eta] ⁵ -cyclopentadienyl)-1,2-ethanediyl zirconium dichloride, (methylamido)-(tetramethyl-[eta] ⁵ -cyclopentadienyl) -1,2-ethanediyl-zirconium dichloride, (ethylamido)(tetramethyl-[eta] ⁵ -cyclopentadienyl)-methylenezirconium dichloride, (t-butylamido)dimethyl-(tetramethyl-[eta] 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) Phosphido)dimethyl(tetramethyl-[eta] ⁵ -cyclopentadienyl)silane zirconium dibenzyl.

Compound of the 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.

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

Compounds 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.

Examples of the compound (i) of the general formula (VII) containing a secondary carbon:
_{(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- (Me 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} 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- Adama Methyl)-5-Me} ₂ ZrCl ₂ , rac-(Me ₂ Si) ₂ {η ⁵ -C ₅ H-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 Si) 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, a.

(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} (n-C 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, a.

(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(nC 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-(dimethylsilyl)-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- ( dimethyl silyl _{) -5-Me} 2 Zr (} CH 2 C 6 H 5) 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- ( _{butyldimethylsilyl) -5-Me} 2 ZrMe 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( dimethyl _{silyl) -5-Me} 2 Zr (} n-C 4 H 9) 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{butyldimethylsilyl) -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- (Trimethyl Silyl)-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- ( diphenyl _{silyl) 2} 2 Zr (CH 2 C 6 H 5} ) 2, rac- (Me 2 Si) 2 {η 5 -C 5 H-3- ( _{butyldiphenylsilyl) -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- ( _{butyldiphenylsilyl) -5-Me} 2 Zr (} CH 2 _{C 6 H 5) 2, 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- ( _{butyldiphenylsilyl) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, (Me 2 Si) ₂ {η ⁵ -C ₅ H-3,5-(phenylmethylsilyl) ₂ } ₂ ZrCl ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5-(phenylmethylsilyl) ₂ } ₂ ZrMe ₂ , (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5-(phenylmethylsilyl) ₂ } ₂ Zr(nC 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- ( phenylmethyl Silyl)-5-Me} ₂ ZrCl ₂ , rac-(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3-(phenylmethylsilyl)-5-Me} ₂ ZrMe ₂ , rac-(Me ₂ Si). ₂ {η ⁵ -C ₅ H-3-(phenylmethylsilyl)-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- ( phenylmethyl silyl) -5-Me } ₂ ZrCl ₂ , meso-(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3-(phenylmethylsilyl)-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 Shi _{Lil) -5-Me} 2 Zr (} CH 2 C 6 H 5) 2, a.

Preferred among these are compounds of a combination of secondary carbons and primary carbon, more _{preferred, 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 , 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-(dimethylsilyl)-5-Me} ₂ ZrMe ₂ .
Compounds obtained by replacing the silylene group of the compounds of these specific examples with a germylene group are also exemplified as suitable compounds.
As a specific example of the metallocene complex, Japanese Patent Application Laid-Open No. 7-188335 and Journal of American Chemical Society, 1996, Vol. It is also possible to use a transition metal compound having a ligand containing one or more elements other than carbon in the 5-membered ring or the 6-membered ring disclosed in 118,2291.
An example of the metallocene complex having a heterocyclic hydrocarbon group as a substituent is disclosed in Japanese Patent No. 3674509.

Among the catalyst components (i) described above, the preferred metallocene complex for producing the polyethylene component (A) is preferably a metallocene complex represented by the general formula (I) or the general formula (II), and However, a metallocene complex having a cyclopentadienyl ring and a heterocyclic aromatic group is preferable, and a metallocene complex having an indenyl ring skeleton is more preferable. A metallocene complex represented by the general formula (II) is preferable, and a metallocene complex represented by the general formula (II) is preferable from the viewpoint of being capable of producing a high molecular weight polymer and having excellent copolymerizability in the copolymerization of ethylene with another α-olefin. The metallocene complex represented by and having an indenyl ring skeleton is most preferable. The ability to produce high molecular weight compounds has the advantage that polymers of various molecular weights can be designed by the method of adjusting the molecular weights of various polymers as described below.
Further, the following compounds are preferred among the metallocene complexes represented by the general formula (II) from the viewpoint that polyethylene having a high molecular weight and long chain branching can be produced.

As one example of a preferred embodiment, the compound group is a bridged metallocene complex containing at least one heterocyclic aromatic group in the compound as R ^{1 to} R ² . Preferred heterocyclic aromatic groups include the group consisting of furyl groups, benzofuryl groups, thienyl groups, benzothienyl groups. These substituents may further have a substituent such as a silicon-containing group. Among the substituents selected from the group consisting of furyl group, benzofuryl group, thienyl group and benzothienyl group, furyl group and benzofuryl group are more preferable. Furthermore, it is preferable that these substituents are introduced at the 2-position of the substituted cyclopentadienyl group or the substituted indenyl group, and at least one other substituted cyclopentadienyl group having no condensed ring structure can be used. It is particularly preferable that the compound has.

By using these compounds as a metallocene complex, and further by employing specific polymerization conditions, the polyethylene component (A) preferable in the present invention can be easily produced.

These metallocene complexes are preferably used as a supported catalyst as described below. In the first group of compounds, due to the interaction between the so-called heteroatoms contained in the furyl group and thienyl group and the solid acid on the carrier, heterogeneity occurs in the active site structure, and long chain branching easily occurs. I think it was. Also, in the second compound group, it is considered that the space around the active site is changed by using the supported catalyst, so that the long chain branching is easily generated.

(2) Catalyst component (ii)
In the method for producing a polyethylene component (A) according to the present invention, a cationic metallocene compound is formed as an essential component of an olefin polymerization catalyst by reacting with a metallocene compound of the catalyst component (i) in addition to the catalyst component (i). It is characterized in that it contains a compound (catalyst component (ii)) to be added, and optionally a fine particle carrier (catalyst component (iii)).

An organoaluminum oxy compound is mentioned as one of the catalyst components (ii).
The organoaluminum oxy compound has an Al-O-Al bond in the molecule, and the number of bonds is usually 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 organic aluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene and other aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons can be used, aliphatic hydrocarbons or Preference is given to using aromatic hydrocarbons.

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

The alkyl group of trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. Is particularly preferable.
The above organoaluminum compounds may be used as a mixture of two or more kinds.

The reaction ratio of water and the organoaluminum compound (water/Al molar ratio) is preferably 0.25/1 to 1.2/1, particularly preferably 0.5/1 to 1/1, and the reaction temperature is , Usually in the range of −70 to 100° C., preferably −20 to 20° C. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only mere water but also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like, and components capable of generating water in the reaction system can be used.
Incidentally, among the above-mentioned organoaluminum oxy compounds, those obtained by reacting alkylaluminum with water are usually called aluminoxane, and particularly methylaluminoxane (including those substantially consisting of methylaluminoxane (MAO)). Is suitable as an organic aluminum oxy compound.
Of course, as the organoaluminum oxy compound, it is also possible to use a combination of two or more of the above-mentioned organoaluminum oxy compounds, and a solution obtained by dissolving or dispersing the organoaluminum oxy compound in the above-mentioned inert hydrocarbon solvent. You may use what was said.

Further, other specific examples of the catalyst component (ii) include borane compounds and borate compounds.
More specifically, the borane compound is represented by triphenylborane, tri(o-tolyl)borane, tri(p-tolyl)borane, tri(m-tolyl)borane, tri(o-fluorophenyl)borane, tris( p-fluorophenyl)borane, tris(m-fluorophenyl)borane, tris(2,5-difluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-trifluoromethylphenyl)borane, tris (3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl), tris( Examples thereof include perfluoroanthryl)borane and tris(perfluorobinaphthyl)borane.

Among these, tris(3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluoro) Biphenyl)borane, tris(perfluoroanthryl)borane, tris(perfluorobinaphthyl)borane are more preferable, and tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris( Perfluoronaphthyl)borane and tris(perfluorobiphenyl)borane are exemplified as preferable compounds.

Further, when specifically expressing the borate compound, the first example is a compound represented by the following general formula (IX).
^{[L 1 -H] + [BR} b R c X b X c] - general formula (IX)

In general formula (IX), L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is Bronsted acid such as ammonium, anilinium, or phosphonium.
Examples of ammonium include trialkyl-substituted ammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium and tri(n-butyl)ammonium, and dialkylammonium such as di(n-propyl)ammonium and dicyclohexylammonium.

Examples of the anilinium include N,N-dimethylanilinium, N,N-diethylanilinium, and N,N-dialkylanilinium such as N,N-2,4,6-pentamethylanilinium.
Further, examples of the phosphonium include triarylphosphonium, tributylphosphonium, tributylphosphonium, tri(methylphenyl)phosphonium, tri(dimethylphenyl)phosphonium, and the like, and trialkylphosphonium.

Further, in the general formula (IX), R ^b and R ^c are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, which are mutually linked by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, which may be linked, an alkyl group represented by a methyl group, an ethyl group, a propyl group, an isopropyl group, or a halogen such as fluorine, chlorine, bromine, or iodine is preferable. ..
Further, X ^b and X ^c are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, and a substituted carbon group containing 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by halogen atoms. It is a hydrogen group.

Specific examples of the compound represented by the general formula (IX) include tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tributylammonium tetra(3,5- Ditrifluoromethylphenyl)borate, tributylammonium tetra(2,6-difluorophenyl)borate, tributylammonium tetra(perfluoronaphthyl)borate, dimethylanilinium tetra(pentafluorophenyl)borate, dimethylanilinium tetra(2,6- Ditrifluoromethylphenyl)borate, dimethylanilinium tetra(3,5-ditrifluoromethylphenyl)borate, dimethylanilinium tetra(2,6-difluorophenyl)borate, dimethylanilinium tetra(perfluoronaphthyl)borate, triphenyl Phosphonium tetra(pentafluorophenyl)borate, triphenylphosphonium tetra(2,6-ditrifluoromethylphenyl)borate, triphenylphosphonium tetra(3,5-ditrifluoromethylphenyl)borate, triphenylphosphonium tetra(2,6- Difluorophenyl)borate, triphenylphosphonium tetra(perfluoronaphthyl)borate, trimethylammonium tetra(2,6-ditrifluoromethylphenyl)borate, triethylammonium tetra(pentafluorophenyl)borate, triethylammonium tetra(2,6-ditri) Fluoromethylphenyl)borate, triethylammonium tetra(perfluoronaphthyl)borate, tripropylammonium tetra(pentafluorophenyl)borate, tripropylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tripropylammonium tetra(perfluoro) Examples thereof include naphthyl)borate, di(1-propyl)ammonium tetra(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

Among these, tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tributylammonium tetra(3,5-ditrifluoromethylphenyl)borate, tributylammonium tetra(perfluoro) Naphthyl)borate, dimethylanilinium tetra(pentafluorophenyl)borate, dimethylanilinium tetra(2,6-ditrifluoromethylphenyl)borate, dimethylanilinium tetra(3,5-ditrifluoromethylphenyl)borate, dimethylanilinium Tetra(perfluoronaphthyl)borate is preferred.

A second example of the borate compound is represented by the following general formula (X).
^{[L 2] + [BR b} R c X b X c] - general formula (X)

In the general formula (X), L ² is carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, Examples thereof include sodium cation and proton. R ^b , R ^c , X ^b and X ^c are the same as defined in the general formula (IX).

Specific examples of the compound include trityl tetraphenyl borate, trityl tetra(o-tolyl)borate, trityl tetra(p-tolyl)borate, trityl tetra(m-tolyl)borate, trityl tetra(o-fluorophenyl)borate, Trityl tetra(p-fluorophenyl)borate, trityl tetra(m-fluorophenyl)borate, trityl tetra(3,5-difluorophenyl)borate, trityl tetra(pentafluorophenyl)borate, trityl tetra(2,6-ditrifluoro) Methylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, tropinium tetraphenylborate, tropinium tetra(o-tolyl)borate, tropinium tetra(p- Tolyl)borate, tropinium tetra(m-tolyl)borate, tropinium tetra(o-fluorophenyl)borate, tropinium tetra(p-fluorophenyl)borate, tropinium tetra(m-fluorophenyl)borate, tropinium tetra (3,5-difluorophenyl)borate, tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, tropinium tetra(3,5-ditrifluoromethylphenyl)borate, Tropi tetra (perfluoro-naphthyl) _{borate, NaBPh 4, NaB (o-} CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 -Ph) 4, NaB (o- _{F-Ph) 4, NaB (} p-F-Ph) 4, NaB (m-F-Ph) 4, NaB (3,5-F 2 -Ph) 4, NaB (C 6 F 5) 4, NaB ( _{2,6- (CF 3) 2 -Ph)} 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, H + BPh 4 · 2 diethyl ether, ^{H +} _{B (3,5-F 2 -Ph)} 4 · 2 diethyl ^{_{ether, H + B (C 6 F}} 5) 4 - · 2 diethyl _{^{ether, H + B (2,6- (CF}} 3) 2 -Ph) 4 · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ^{_{ether, H + B (C 10 H}} 7) 4 · 2 Diethyl ether can be illustrated.

Among these, trityl tetra(pentafluorophenyl)borate, trityl tetra(2,6-ditrifluoromethylphenyl)borate, trityl tetra(3,5-ditrifluoromethylphenyl)borate, trityl tetra(perfluoronaphthyl)borate, Tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, tropinium tetra(3,5-ditofluoromethylphenyl)borate, tropinium tetra(perfluoronaphthyl)borate, _{NaB (C 6 F 5) 4} , NaB (2,6- (CF 3) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, ^{_{H + B (C 6 F 5}} ) 4 - · 2 diethyl _{^{ether, H + B (2,6- (CF}} 3) 2 -Ph) 4 · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) _{2 -Ph) 4} · ₂ diethyl ^{_{ether, H + B (C 10 H}} 7) 4 · 2 diethyl ether.

More preferably, among these, trityl tetra(pentafluorophenyl)borate, trityl tetra(2,6-ditrifluoromethylphenyl)borate, tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoro) methylphenyl) _{borate, NaB (C 6 F 5)} 4, NaB (2,6- (CF 3) 2 -Ph) 4, H + B (C 6 F 5) 4 - · 2 diethyl ^{ether, H} + B ( _{2,6- (CF 3) 2 -Ph)} 4 · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ^{_{ether, H + B (C 10 H}} 7) 4 -2 diethyl ether is mentioned.

A particularly preferred catalyst component (ii) is an organoaluminum oxy compound.
By using these compounds as the catalyst component (ii), and further by adopting specific polymerization conditions, the preferred polyethylene component (A) in the present invention can be easily produced.

(3) Catalyst component (iii)
Examples of the fine particle carrier which is the catalyst component (iii) include an inorganic carrier, a particulate polymer carrier, or 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.

In addition, examples of the metal oxide include single oxides or complex oxides of elements of Groups 1 to 14 of the periodic table, for example, SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , TiO ₂ , _{ZrO 2, Fe 2 O 3,} Al 2 O 3 · MgO, Al 2 O 3 · CaO, Al 2 O 3 · SiO 2, Al 2 O 3 · MgO · CaO, Al 2 O 3 · MgO · SiO 2, Al Examples thereof include various natural or synthetic single oxides or composite oxides such as ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂ O ₃ .NiO, and SiO ₂ .MgO.
Here, the above formula does not represent a molecular formula but represents only the composition, and the structure and catalyst component ratio of the composite oxide used in the present invention are not particularly limited.
Further, the metal oxide used in the present invention may absorb a small amount of water and may contain a small amount of impurities.

As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable.
The metal carbonate is preferably an alkali metal or alkaline earth metal carbonate, and specific examples thereof include magnesium carbonate, calcium carbonate, barium carbonate and the like.
Examples of the carbonaceous material include carbon black and activated carbon.
Any of the above inorganic carriers can be preferably used in the present invention, but it is particularly preferable to use a metal oxide, silica, alumina or the like.

These inorganic carriers are usually calcined at 200 to 800° C., preferably 400 to 600° C. in air or in an inert gas such as nitrogen or argon so that the amount of surface hydroxyl groups is 0.8 to 1.5 mmol/g. It is preferable to adjust it to the following.
The properties of these inorganic carriers are not particularly limited, but usually, the average particle size is 5 to 200 μm, preferably 10 to 150 μm, the average pore size is 20 to 1000 Å, preferably 50 to 500 Å, and the specific surface area is 150 to 1000 m. ² /g, preferably 200 to 700 m ² /g, pore volume 0.3 to 2.5 cm ³ /g, preferably 0.5 to 2.0 cm ³ /g, apparent specific gravity 0.10 to 0 It is preferable to use an inorganic carrier having a density of 0.50 g/cm ³ .

The above-mentioned inorganic carrier can of course be used as it is, but as a pretreatment, these carriers are treated with trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, It can be used after being brought into contact with an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

Further particularly preferred catalyst components (iii) include SiO ₂ , Al ₂ O ₃ and Al ₂ O ₃ .SiO ₂ .
By using these compounds as the catalyst component (iii), and further by employing specific polymerization conditions, the preferred polyethylene component (A) in the present invention can be easily produced.

(4) Contact method, etc. The metallocene-based catalyst according to the present invention is a method for contacting each component when obtaining a catalyst component (i), a catalyst component (ii), and, if necessary, a catalyst component (iii). Is not particularly limited, and for example, the following method can be arbitrarily adopted.

Contact method (1): The catalyst component (i) and the catalyst component (ii) are brought into contact with each other, and then the catalyst component (iii) is brought into contact therewith.
Contact method (2): The catalyst component (i) and the catalyst component (iii) are brought into contact with each other, and then the catalyst component (ii) is brought into contact therewith.
Contact method (3): The catalyst component (ii) and the catalyst component (iii) are brought into contact with each other, and then the catalyst component (i) is brought into contact therewith.

Among these contacting methods, the contacting methods (1) and (3) are preferable, and the contacting method (1) is most preferable. In any contacting method, generally, in an inert atmosphere such as nitrogen or argon, aromatic hydrocarbons (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, and ethylbenzene, heptane, hexane, decane, dodecane are generally used. A method is used in which each component is brought into contact with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane.
This contact is usually -100°C to 200°C, preferably -50°C to 100°C, more preferably 0°C to 50°C, for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, and more preferably It is desirable to carry out 30 minutes to 12 hours.

When the catalyst component (i) or the catalyst component (ii) and the catalyst component (iii) are brought into contact with each other, as described above, an aromatic hydrocarbon solvent in which a certain component is soluble or sparingly soluble, and a certain component Any insoluble or sparingly soluble aliphatic or alicyclic hydrocarbon solvent can be used.

When the contact reaction between the components is carried out stepwise, it may be used as it is as a solvent for the contact reaction in the latter step without removing the solvent used in the former step. In addition, after the first-stage catalytic reaction using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, and other aliphatic hydrocarbons). Hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon) and recover the desired product as a solid, or once the soluble solvent is partially or entirely removed by a means such as drying to obtain the desired product. After removing the product as a solid, the subsequent catalytic reaction of the desired product can also be carried out using any of the inert hydrocarbon solvents described above. In the present invention, the catalytic reaction of each component may be carried out multiple times.

In the present invention, the use ratios of the catalyst component (i), the catalyst component (ii), and the catalyst component (iii) are not particularly limited, but the following ranges are preferable.

When an organoaluminum oxy compound is used as the catalyst component (ii), the atomic ratio (Al/M) of aluminum of the organo aluminum oxy compound to the transition metal (M) in the catalyst component (i) is usually 1 to 100, 000, preferably 5 to 1,000, more preferably 50 to 200, and when a borane compound or a borate compound is used, the atomic ratio of boron to the transition metal (M) in the metallocene compound (B/ It is desirable to select M) in the range of usually 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10.
Furthermore, when a mixture of an organoaluminum oxy compound, a borane compound and a borate compound is used as the catalyst component (ii), each compound in the mixture is used in the same manner as described above for the transition metal (M). It is desirable to select in proportion.

The amount of the catalyst component (iii) used is 1 g per 0.0001 to 5 mmol of the transition metal in the catalyst component (i), preferably 0.001 to 0.5 mmol, and more preferably 0.01 to 0.1 mmol. Is.

The catalyst component (i), the catalyst component (ii), and the catalyst component (iii) are brought into contact with each other by any of the contact methods (1) to (3), and then the solvent is removed. The olefin polymerization catalyst can be obtained as a solid catalyst. It is desirable to remove the solvent under normal pressure or reduced pressure at 0 to 200° C., preferably 20 to 150° C. for 1 minute to 50 hours, preferably 10 minutes to 10 hours.

The metallocene catalyst can also be obtained by the following method.
Contact method (4): The catalyst component (i) and the catalyst component (iii) are brought into contact with each other to remove the solvent, and this is used as a solid catalyst component, and under the polymerization conditions, an organoaluminum oxy compound, a borane compound, a borate compound or these Contact with a mixture of.
Contact method (5): An organoaluminum oxy compound, a borane compound, a borate compound or a mixture thereof is brought into contact with the catalyst component (iii) to remove the solvent, and this is used as a solid catalyst component. Contact with i).
Also in the case of the contact methods (4) and (5), the same component ratios, contact conditions and solvent removal conditions as described above can be used.

Further, a layered silicate may be used as a component that also serves as the catalyst component (ii) and the catalyst component (iii), which are essential components of the method for producing the polyethylene component (A) according to the present invention.
The layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding force.
Most of the layered silicates are naturally produced mainly as the main components of clay minerals, but these layered silicates are not limited to those of natural origin, and may be synthetic products.

Among these, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, and teniolite, vermiculite, and mica are preferable.

In general, natural products are often non-ion-exchangeable (non-swellable). It is preferable to perform a treatment for imparting. Among such treatments, the following chemical treatments are particularly preferable.
Here, as the chemical treatment, both surface treatment for removing impurities adhering to the surface and treatment for affecting the crystal structure and chemical composition of the layered silicate can be used.
Specifically, (a) acid treatment using hydrochloric acid, sulfuric acid, etc., (b) alkali treatment using NaOH, KOH, NH _3, etc., (c) selected from Groups 2 to 14 of the periodic table Salt treatment with a salt consisting of at least one anion selected from the group consisting of a cation containing at least one atom and an anion derived from a halogen atom or an inorganic acid, (d) alcohol, hydrocarbon Examples include treatment with compounds, formamide, aniline, and other organic substances. These treatments may be performed alone or two or more treatments may be combined.

The particle properties of the layered silicate can be controlled by pulverization, granulation, sizing, fractionation, etc. at any point before, during, or after all the steps. The method can be any purposeful. In particular, if the granulation method is described, for example, spray granulation method, tumbling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation method. Method, emulsion granulation method, submerged granulation method and the like. Particularly preferable granulation methods are the spray granulation method, the rolling granulation method, and the compression granulation method among the above.

The above-mentioned layered silicate can be used as it is, but these layered silicates are trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, It can be used in combination with an organic aluminum compound such as diisobutylaluminum hydride or an organic aluminum oxy compound containing an Al-O-Al bond.

In the metallocene-based catalyst according to the present invention, in order to support the catalyst component (i) on the layered silicate, the catalyst component (i) and the layered silicate are brought into contact with each other, or the catalyst component (i) and the organoaluminum compound. The layered silicates may be in contact with each other.
The method of contacting each component is not particularly limited, and for example, the following method can be arbitrarily adopted.
Contact method (6): The catalyst component (i) is contacted with the organoaluminum compound, and then contacted with the layered silicate support.
Contact method (7): The catalyst component (i) is contacted with the layered silicate support, and then contacted with the organoaluminum compound.
Contact method (8): After bringing the organoaluminum compound into contact with the layered silicate support, the catalyst component (i) is contacted.

Of these contact methods, contact methods (6) and (8) are preferred. In any contacting method, usually in an inert atmosphere such as nitrogen or argon, aromatic hydrocarbons (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, and ethylbenzene, heptane, hexane, decane, dodecane are generally used. A method in which each component is brought into contact with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as cyclohexane and the like.

The use ratio of the catalyst component (i), the organoaluminum compound, and the layered silicate carrier is not particularly limited, but the following range is preferable.
The supported amount of the catalyst component (i) is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, and more preferably 0.01 to 0.1 mmol, per 1 g of the layered silicate support.
The amount of Al supported when an organoaluminum compound is used is preferably 0.01 to 100 mol, preferably 0.1 to 50 mol, and more preferably 0.2 to 10 mol.

As the method for supporting and removing the solvent, the same conditions as those for the above inorganic carrier can be used.
When a layered silicate is used as a component that also serves as both the catalyst component (ii) and the catalyst component (iii), the polymerization activity is high and the productivity of the ethylene polymer having a long chain branch is improved.
The olefin polymerization catalyst thus obtained may be used after preliminarily polymerizing the monomer, if necessary.

As an example of producing a metallocene-based catalyst, for example, it can be produced by considering "catalyst" and "blending ratio and conditions of raw materials" described in JP-T-2002-535339 and JP-A-2004-189869. it can. The index of the polymer can be controlled by various polymerization conditions, for example, the method described in JP-A-2-269705 and JP-A-3-21607.

The polyethylene component (A) is a homopolymer of ethylene or an α-olefin having 3 to 12 carbon atoms and ethylene, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 -It is obtained by copolymerization with octene and the like. Further, copolymerization with a diene for the purpose of modification is also possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene and dicyclopentadiene. The comonomer content during the polymerization can be arbitrarily selected. For example, in the case of copolymerizing ethylene with an α-olefin having 3 to 12 carbon atoms, an ethylene/α-olefin copolymer is used. The α-olefin content therein is 0 to 40 mol %, preferably 0 to 30 mol %.
The ethylene used for each polyethylene component used in the polyethylene resin composition of the present invention may be ethylene produced from crude oil derived from usual fossil raw materials, or may be ethylene derived from plants. .. Examples of plant-derived ethylene and polyethylene include ethylene and polymers thereof described in JP 2010-511634 A. Plant-derived ethylene and its polymers have carbon-neutral properties (does not use fossil raw materials and do not lead to an increase in carbon dioxide in the atmosphere), and it is possible to provide environmentally friendly products.

The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but by adding hydrogen to the polymerization reaction system, the molecular weight can be adjusted more effectively. You can
In addition, it can be carried out without any trouble even if a component for the purpose of removing water, that is, a scavenger is added to the polymerization system.
Examples of the scavenger include organoaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, the organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, diethylzinc, organozinc compounds such as dibutylzinc, and diethyl. Organomagnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable.
The present invention can also be applied without problems to a multi-stage polymerization system of two or more stages in which the polymerization conditions such as hydrogen concentration, amount of monomers, polymerization pressure, and polymerization temperature are different from each other.

The polyethylene component (A) can be produced by a production process such as a gas phase polymerization method, a solution polymerization method and a slurry polymerization method, and preferably the slurry polymerization method. Among the polymerization conditions for the polyethylene component (A), the polymerization temperature can be selected from the range of 0 to 200°C. In the slurry polymerization, the 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 a hydrocarbon such as hexane, heptane, or isobutane, an aromatic hydrocarbon such as benzene, toluene, or xylene, or an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, with oxygen or water removed. It can be produced by carrying out slurry polymerization of ethylene and α-olefin in the presence of a selected inert hydrocarbon solvent.

If the polyethylene component (A) satisfies the range specified in the present invention, the polyethylene component (A) is continuously polymerized in a single polymerization vessel, a plurality of reactors connected in series or in parallel, and a plurality of ethylene polymers are separately polymerized. It may be a mixture after being mixed.

2. Polyethylene component (B)
Characteristic (b1)
As the polyethylene component (B) used in the present invention, those having an HLMFR of 2 g/10 minutes or more and less than 20 g/10 minutes are selected from the viewpoint of exerting the effect of the present invention. The HLMFR of the polyethylene component (B) is preferably 3 g/10 minutes or more and 15 g/10 minutes or less, more preferably 4 g/10 minutes or more and 12 g/10 minutes or less, particularly preferably 4 g/10 minutes or more and 10 g/10. It is in the range of minutes or less.
If this HLMFR is less than 2 g/10 minutes, the molecular weight may increase and flowability and moldability may not be secured. Further, in the final resin composition, the HLMFR cannot be achieved within the specified range, the fluidity may be lowered, and the polyethylene component (B) becomes the component having the highest viscosity in the low strain rate range, and the polyethylene component (B ) Is poorly dispersed, which may impair the appearance of the molded product.
On the other hand, if the HLMFR is 20 g/10 minutes or more, the impact resistance may not be ensured due to the increase in the amount of low molecular weight components, and the low strain rate of the polyethylene component (A) and the polyethylene component (B). There is a risk that the difference in viscosity in the region becomes small and the effect of promoting the dispersion of the polyethylene component (A) is reduced.
HLMFR can be measured as described above.
HLMFR can be adjusted mainly by the amount of hydrogen and the polymerization temperature during the polymerization of the polyethylene component (B).

Characteristic (b2)
The polyethylene component (B) used in the present invention is selected from those having a density of more than 0.945 g/cm ^{3 and} 0.965 g/cm ³ or less from the viewpoint of exerting the effect of the present invention. Density polyethylene component (B) is preferably 0.950 g / cm ³ or more 0.963 g / cm ³ or less, still more preferably 0.955 g / cm ³ or more 0.961 g / cm ³ or less.
When the density of the polyethylene component (B) is 0.945 g/cm ³ or less, the density range in the final resin composition cannot be achieved, the rigidity is insufficient, and the crystallization rate decreases, resulting in a molding cycle. May decrease. In addition, the rigidity of the container is poor and the container is likely to be deformed at a high temperature, which may cause the container to deform due to the influence of the internal pressure of the container and cause leakage.
On the other hand, if the density exceeds 0.965 g/cm ³ , the impact resistance performance of the final resin composition may decrease, and the impact resistance of the container may deteriorate.
The density can be measured as described above.
The density can be adjusted mainly by the amount of α-olefin during the polymerization of the polyethylene component (B).

Characteristic (b3)
The polyethylene component (B) used in the present invention has an elongational viscosity η(t) (unit: unity/second) measured at a temperature of 170° C. and an elongation strain rate of 0.1 (unit: 1/sec) from the viewpoint of exerting the effect of the present invention. : Pa·sec) and elongation time t (unit: second) in a logarithmic plot, a polyethylene is selected in which an inflection point of elongational viscosity due to strain hardening is observed.
The presence or absence of the inflection point of elongational viscosity due to strain hardening can be observed in the measurement of the strain hardening degree, and can be measured by the same method as the method for measuring the strain hardening degree of the polyethylene component (A) described above. it can.
In order for the polyethylene component (B) to have a long-chain branched structure, it is preferable to apply an appropriate polymerization catalyst for polymerization, and it is preferable to use a chromium-based catalyst as described below.

Characteristic (b4)
The polyethylene component (B) used in the present invention preferably satisfies the following characteristic (b4).
Characteristic (b4): The molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) is 10 or more and 50 or less.
In the polyethylene component (B) used in the present invention, the molecular weight distribution (Mw/Mn) is more preferably 15 or more and 30 or less.
The molecular weight distribution (Mw/Mn) measured by GPC relates to the improvement of various physical properties and moldability of the polymer, and also to the improvement of the appearance of the molded product.
When the molecular weight distribution (Mw/Mn) of the polyethylene component (B) used in the present invention is within the above range, more excellent blow molding processability can be exhibited. Further, when the molecular weight distribution (Mw/Mn) is 10 or more, the compatibility with the polyethylene component (A) and the polyethylene component (C) is better and the product appearance is excellent, and the resin pressure during extrusion molding is high. Is preferable, the phenomenon of flow instability such as sharkskin is less likely to occur, and defective appearance is easily suppressed, which is preferable. On the other hand, when the molecular weight distribution (Mw/Mn) is 50 or less, deterioration of the pinch-off shape of the molded product can be easily suppressed, and the impact strength as a hollow molded product can be easily improved.
The molecular weight distribution can be set within a predetermined range by employing a catalyst capable of controlling the molecular weight distribution and suitable polymerization conditions. In the case of a bimodal or multimodal polymer, it can be controlled by adjusting the molecular weight of each component.

The molecular weight and molecular weight distribution can be measured by gel permeation chromatography (GPC) under the following conditions.
[Measurement condition]
Model used: Alliance GPCV2000 manufactured by Nippon Waters Co., Ltd. Measuring temperature: 145°C
Solvent: Orthodichlorobenzene (ODCB)
Column: Showa Denko Shodex HT-806M x 2 + same HT-G
Flow rate: 1.0 mL/min Injection volume: 0.3 mL

[Sample preparation]
In a 4 mL vial, 3 mg of the sample and 3 mL of orthodichlorobenzene (containing 0.1 mg/mL of 1,2,4-trimethylphenol) were weighed and covered with a resin screw cap and a Teflon (registered trademark) septum. Then, it melt|dissolves for 2 hours using the Senshu Scientific Co., Ltd. model SSC-9300 high temperature shaker set to the temperature of 150 degreeC. After completion of the dissolution, visually confirm that there are no insoluble components.
[Creation of calibration curve]
Four 4 mL glass bottles were prepared, and 0.2 mg each of the monodisperse polystyrene standard sample or n-alkane of the combination of (1) to (4) below was weighed in each, followed by orthodichlorobenzene (0.1 mg/mL). 3 mL of 1,2,4-trimethylphenol) was weighed and covered with a resin screw cap and a Teflon (registered trademark) septum, and then the temperature was set to 150° C. by Senshu Scientific Co., Ltd. SSC-9300 type. Dissolve for 2 hours using a high temperature shaker.
(1) Shodex S-1460, same S-66.0, n-eicosan (2) Shodex S-1950, same S-152, n-tetracontane (3) Shodex S-3900, same S-565, same S -5.05
(4) Shodex S-7500, same S-1010, same S-28.5
The vial containing the sample solution is set in the device, the measurement is performed under the above-mentioned conditions, and the chromatogram (data set of retention time and response of the differential refractometer detector) is recorded at a sampling interval of 1 second. The retention time (peak apex) of each polystyrene standard sample is read from the obtained chromatogram and plotted against the logarithmic value of the molecular weight. Here, the molecular weights of n-eicosane and n-tetracontane are 600 and 1200, respectively. The nonlinear least squares method is applied to this plot, and the obtained quartic curve is used as the calibration curve.

[Calculation of molecular weight]
The measurement is performed under the above conditions, and the chromatogram is recorded at the sampling interval of 1 second.
From this chromatogram, Sadao Mori "Size Exclusion Chromatography" (Kyoritsu Shuppan), Chapter 4, p. 51 to 60, the differential molecular weight distribution curve and the average molecular weight values (Mn, Mw and Mz) are calculated. However, in order to correct the molecular weight dependence of dn/dc, the height H from the baseline in the chromatogram is corrected by the following formula. The recording of the chromatogram (data acquisition) and the calculation of the average molecular weight are performed using a program (made by Visual Basic 6.0 made by Microsoft) on a PC on which OS Windows (registered trademark) XP made by Microsoft is installed.
H'=H/[1.032+189.2/M(PE)]
The following formula is used to convert the molecular weight of polystyrene to polyethylene.
M(PE)=0.468×M(PS)

The polyethylene component (B) used in the present invention is preferably an ethylene polymer polymerized with a chromium catalyst.
A preferable example of the chromium-based catalyst is a chromium-based catalyst in which at least a part of chromium atoms becomes hexavalent by supporting a chromium compound on an inorganic oxide carrier and firing and activating it in a non-reducing atmosphere. It is known and is known as a catalyst. An overview of this catalyst can be found in M.M. P. McDaniel, Advances in Catalysis, Volime 33, p. 47, 1985, Academic Press Inc. , M.; P. McDaniel, Handbook of Heterogeneous Catalysis, 2400, 1997, VCH, M.; B. Welch et al., Handbook of Polyolefins: Synthesis and Properties, p. 21, 1993, Marcel Dekker et al.

The inorganic oxide carrier is preferably an oxide of a metal of Group 2, 4, 13 or 14 of the periodic table. Specific examples include magnesia, titania, zirconia, alumina, silica, thoria, silica-titania, silica-zirconia, silica-alumina, and mixtures thereof. Of these, silica, silica-titania, silica-zirconia, and silica-alumina are preferable. In the case of silica-titania, silica-zirconia, and silica-alumina, titanium, zirconium, or aluminum atom as a metal component other than silica is 0.2 to 10% by mass, preferably 0.5 to 7% by mass, more preferably 1 to The thing containing 5 mass% is used.
The preparation method, physical properties and characteristics of the carrier suitable for these chromium-based catalysts are described in C.I. E. Marsden, Preparation of Catalysts, Volume V, p. 215, 1991, Elsevier Science Publishers, C.I. E. Marsden, Plastics, Rubber and Composites Processing and Applications, Volume 21, page 193, 1994.

Inorganic oxide so that the specific surface area of the carrier of the chromium-based catalyst before calcination activation is 250 to 1000 m ² /g, preferably 300 to 900 m ² /g, and more preferably 400 to 800 m ² /g It is preferable to choose a carrier. When the specific surface area is less than 250 m ² /g, it is considered that this is related to the narrow molecular weight distribution and the increase in long chain branching, but both durability and impact resistance may decrease. A carrier having a specific surface area of more than 1000 m ² /g may be difficult to manufacture.

The pore volume of the inorganic oxide support, as in the case of common chromium-based catalyst carrier used, 0.5~3.0cm ³ / g, preferably 1.0~2.0cm ³ / g , And more preferably in the range of 1.2 to 1.8 cm ³ /g. If the pore volume is less than 0.5, the pores become small due to the polymerized polymer during the polymerization, and the monomer may not be able to diffuse, which may reduce the activity. A carrier having a pore volume of more than 3.0 cm ³ /g may be difficult to manufacture.
The average particle size of the inorganic oxide carrier is in the range of 10 to 200 μm, preferably 20 to 150 μm, and more preferably 30 to 100 μm, like the carrier used for general chromium-based catalysts.

A chromium compound is supported on the inorganic oxide carrier. The chromium compound may be any compound as long as it is a compound in which at least a part of the chromium atoms becomes hexavalent when activated by firing in a non-reducing atmosphere after being supported, and chromium oxide, a halide of chromium, an oxyhalide, a chromate salt. , Dichromates, nitrates, carboxylates, sulfates, chromium-1,3-diketo compounds, chromates and the like. Specifically, chromium trioxide, chromium trichloride, chromyl chloride, potassium chromate, ammonium chromate, potassium dichromate, chromium nitrate, chromium sulfate, chromium acetate, tris(2-ethylhexanoate) chromium, chromium acetyl. Acetonate, bis(tert-butyl)chromate, etc. may be mentioned. Of these, chromium trioxide, chromium acetate, and chromium acetylacetonate are preferable. Even when a chromium compound having an organic group such as chromium acetate or chromium acetylacetonate is used, the organic group portion is burned by the firing activation in the non-reducing atmosphere described later, and finally chromium trioxide is used. It is known that it reacts with the hydroxyl groups on the surface of the inorganic oxide carrier in the same manner as described above, and at least some of the chromium atoms become hexavalent and are immobilized in the structure of chromate ester (V. J. Ruddick). Et al., J. Phys. Chem., Volume 100, page 11062, 1996, SM Augustine et al., J. Catal., Volume 161, 641, page 1996).

The supporting of the chromium compound on the inorganic oxide carrier can be carried out by a known method such as impregnation, solvent removal, sublimation, etc., and an appropriate method may be used depending on the kind of the chromium compound used. The amount of the chromium compound supported is 0.2 to 2.0% by mass, preferably 0.3 to 1.7% by mass, and more preferably 0.5 to 1.5% by mass, as chromium atoms, with respect to the carrier. is there.

After supporting the chromium compound, it is fired to be activated. The calcination activation can be performed in a non-reducing atmosphere substantially free of water, such as oxygen or air. At this time, an inert gas may coexist. Preferably, it is carried out in a fluidized state by using molecular sieves or the like in which air is sufficiently dried. The firing activation is carried out at 350 to 900° C., preferably 420 to 850° C., more preferably 450 to 800° C., for 30 minutes to 48 hours, preferably 1 hour to 36 hours, more preferably 2 hours to 24 hours. By this firing activation, at least a part of the chromium atoms of the chromium compound supported on the inorganic oxide carrier is oxidized to be hexavalent and is chemically fixed on the carrier. If the temperature is lower than 350°C, the polymerization activity may be lost. On the other hand, if firing activation is performed at a temperature higher than 900° C., sintering may occur and the activity may decrease.

By using the chromium-based catalyst thus obtained, an ethylene-based polymer suitable for the polyethylene component (B) can be produced.
The MLMFR and MFR are mainly adjusted by the polymerization temperature, and the density is mainly adjusted by the amount of α-olefin, and can be applied to the ethylene polymer according to the present invention. That is, by increasing the polymerization temperature, the molecular weight can be decreased and consequently the HLMFR can be increased, and by decreasing the polymerization temperature, the molecular weight can be increased and consequently the HLMFR can be decreased.

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

As the ethylene polymer, any method such as slurry polymerization, liquid phase polymerization method such as solution polymerization or gas phase polymerization method can be adopted, but slurry polymerization method is particularly preferable, and a pipe loop type reactor is preferable. Either the slurry polymerization method used or the slurry polymerization method using an autoclave type reactor can be used. Among them, the slurry polymerization method using a pipe loop type reactor is preferable (for details of the pipe loop type reactor and the slurry polymerization using the same, see “Polyethylene Technology Manual”, 148, 2001, edited by Kazuo Matsuura and Naotaka Mikami. It is listed in the Industrial Research Board).

The liquid phase polymerization method is usually carried out in a hydrocarbon solvent. As the hydrocarbon solvent, propane, n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene and the like may be used alone or as a mixture. The gas phase polymerization method can employ a commonly known polymerization method such as a fluidized bed and a stirring bed in the presence of an inert gas, and a so-called condensing mode in which a medium for removing heat of polymerization can coexist in some cases. ..
The polymerization temperature in the liquid phase polymerization method is generally 0 to 300°C, practically 20 to 200°C, preferably 50 to 180°C, and more preferably 70 to 150°C. The catalyst concentration and ethylene concentration in the reactor can be any concentration sufficient to drive the polymerization. For example, the catalyst concentration can range from about 0.0001 to about 5 wt% based on the weight of the reactor contents for liquid phase polymerization. Similarly, the ethylene concentration can range from about 1% to about 10% based on the weight of the reactor contents for liquid phase polymerization.

As the polymerization method, not only single-stage polymerization in which polyethylene is produced using one reactor, but also multi-stage polymerization can be performed by connecting at least two reactors in order to improve the production amount. In the case of multi-stage polymerization, a two-stage polymerization in which two reactors are connected and the reaction mixture obtained by polymerizing in the first stage reactor is continuously fed to the second stage reactor is preferable.

3. Polyethylene component (C)
Characteristic (c1)
The polyethylene component (C) used in the present invention has a melt flow rate (MFR) of 10 g/10 minutes or more and 200 g/10 minutes or less at a temperature of 190° C. and a load of 2.16 Kg from the viewpoint of exerting the effect of the present invention. Select. The MFR of the polyethylene component (C) is preferably in the range of 11 g/10 minutes or more and 198 g/10 minutes or less, more preferably 11 g/10 minutes or more and 195 g/10 minutes or less.
If this MFR is less than 10 g/10 minutes, the molecular weight increases, and fluidity and moldability may not be ensured. In addition, in the final resin composition, HLMFR cannot be achieved within the specified range, and the fluidity is lowered, so that a flow instability phenomenon such as sharkskin and melt fracture easily occurs, so that the molded product The appearance may be impaired.
On the other hand, if the MFR exceeds 200 g/10 minutes, impact resistance may not be ensured due to the influence of an increase in the amount of low molecular weight components. In addition, impact resistance cannot be achieved in the final resin composition, and the drop impact resistance of the molded product may be reduced.
MFR can be measured in the same manner as described above.
The MFR can be adjusted mainly by the amount of hydrogen during the polymerization of the polyethylene component (C) and the polymerization temperature.

Characteristic (c2)
Polyethylene component used in the present invention (C), from the viewpoint of providing the effect of the invention, to select one density of less 0.960 g / cm ³ or more 0.980 g / cm ^3. The density of the polyethylene component (C) is preferably 0.961 g/cm ³ or more and 0.975 g/cm ³ or less, more preferably 0.963 g/cm ³ or more and 0.970 g/cm ³ or less.
When the density is less than 0.960 g/cm ³ , the density range in the final resin composition cannot be achieved, the rigidity is insufficient, and the crystallization rate is decreased, which may result in a decrease in molding cycle. .. In addition, the rigidity of the container is poor and the container is likely to be deformed at a high temperature, which may cause the container to deform due to the influence of the internal pressure of the container and cause leakage.
On the other hand, if the density exceeds 0.980 g/cm ³ , the impact resistance performance of the final resin composition may decrease, and the drop impact resistance of the container may deteriorate.
The density can be measured as described above.
The density can be adjusted mainly by the amount of α-olefin during the polymerization of the polyethylene component (C).

Characteristic (c3) and characteristic (c4)
It is preferable that the polyethylene component (C) further satisfies the following characteristics (c3) and (c4).
Characteristic (c3): Melt flow rate (MLMFR) at a temperature of 190° C. and a load of 11.1 Kg is 50 g/10 minutes or more and 2,000 g/10 minutes or less.
The MLMFR of the polyethylene component (C) is more preferably 70 g/10 minutes or more and 1,700 g/10 minutes or less.
If this MLMFR is less than 50 g/10 minutes, the molecular weight increases, and fluidity and moldability may not be secured. In addition, in the final resin composition, HLMFR cannot be achieved within the specified range and the fluidity is lowered, so that a flow instability phenomenon such as shark skin or melt fracture occurs, and the appearance of the smoothed molded article is reduced. There is a risk of damage.
On the other hand, if the MLMFR exceeds 2000 g/10 minutes, impact resistance may not be ensured due to the influence of an increase in the amount of low molecular weight components. Further, in the final resin composition, the impact resistance cannot be achieved, and the drop impact resistance of the molded product may decrease.
Characteristic (c4): The melt flow rate ratio (MLMFR/MFR), which is the ratio of MLMFR to MFR, is 3 or more and 15 or less.
When the MLMFR/MFR of the polyethylene component (C) is within the range, the balance between fluidity and impact resistance is improved. The MLMFR/MFR of the polyethylene component (C) is more preferably 5 or more and 10 or less.

The polyethylene component (C) used in the present invention is an ethylene homopolymer or an ethylene-α-olefin copolymer, and can be polymerized using various polymerization catalysts as long as the above characteristics can be satisfied. The polyethylene component (C) used in the present invention can be produced by polymerizing using a Ziegler-Natta catalyst or a metallocene catalyst, and is preferably a Ziegler-Natta catalyst-derived polyethylene. The polyethylene component (A) or polyethylene It can be produced according to the polymerization method of the component (B). As the Ziegler-Natta catalyst, a conventionally known catalyst can be appropriately selected and used.

4. Polyethylene resin composition The polyethylene resin composition of the present invention contains the polyethylene component (A) in an amount of 10% by mass to 40% by mass, the polyethylene component (B) in an amount of 5% by mass to 50% by mass, and the polyethylene component ( A polyethylene resin composition containing 40% by mass or more and 85% by mass or less of C). Preferably, the composition contains 15% by mass or more and 35% by mass or less of the polyethylene component (A), 10% by mass or more and 40% by mass or less of the polyethylene component (B), and 45% by mass or more and 75% by mass or less of the polyethylene component (C). It is a thing. More preferably, the content of the polyethylene component (A) is 20% by mass or more and 30% by mass or less, the content of the polyethylene component (B) is 10% by mass or more and 30% by mass or less, and the polyethylene component (C) is 50% by mass or more and 70% by mass or less. It is a composition.
It is important that the polyethylene resin composition of the present invention satisfies the following properties (1) to (5).
Characteristic (1): MFR is 0.1 g/10 minutes or more and 1 g/10 minutes or less.
Characteristic (2): HLMFR is 10 g/10 minutes or more and 50 g/10 minutes or less.
Characteristic (3): The melt flow rate ratio (HLMFR/MFR), which is the ratio of HLMFR to MFR, is 50 or more and 140 or less.
Characteristics (4): density of 0.940 g / cm ³ or more 0.965 g / cm ³ or less.
Characteristic (5): Both elongation viscosity η(t) (unit: Pa·sec) and elongation time t (unit: sec) measured at a temperature of 170° C. and elongation strain rate of 0.1 (unit: 1/sec). In the logarithmic plot, the inflection point of elongational viscosity due to strain hardening is observed.
The characteristics (1) to (5) can be measured in the same manner as described above.

Characteristic (1)
The polyethylene resin composition of the present invention has an MFR of 0.1 g/10 minutes or more and 1 g/10 minutes or less. The MFR is preferably 0.15 g/10 minutes or more and 0.8 g/10 minutes or less, more preferably 0.2 g/10 minutes or more and 0.6 g/10 minutes or less, particularly preferably 0.25 g/10 minutes. The range is 0.50 g/10 minutes or less.
If the MFR is less than 0.1 g/10 minutes, the fluidity may decrease, which may increase the amount of heat generated by the extruder motor during molding and the amount of heat generated by the resin during shearing, or the fluidity of sharkskin, melt fracture, etc. Since the stability phenomenon is likely to occur, the appearance of the molded product may be impaired.
On the other hand, when the MFR exceeds 1 g/10 minutes, impact resistance and environmental stress crack resistance cannot be achieved, and drop impact resistance and long-term durability of the molded product may be deteriorated.
The MFR of the polyethylene resin composition can be adjusted by the respective amounts of hydrogen and temperature during polymerization of the polyethylene component (A), the polyethylene component (B) and the polyethylene component (C), and the blending amount of each component.

Characteristic (2)
The polyethylene resin composition of the present invention has an HLMFR of 10 g/10 minutes or more and 50 g/10 minutes or less. The HLMFR is preferably 12 g/10 minutes or more and 48 g/10 minutes or less, more preferably 15 g/10 minutes or more and 45 g/10 minutes or less.
If this HLMFR is less than 10 g/10 min, the fluidity may decrease, which may increase the amount of heat generated by the extruder motor during molding or the amount of heat generated by the resin during shearing. Is likely to occur, which may impair the appearance of the molded product.
On the other hand, when the HLMFR exceeds 50 g/10 minutes, impact resistance and environmental stress crack resistance cannot be achieved, and drop impact resistance and long-term durability of the molded product may be reduced.
The HLMFR of the polyethylene resin composition can be adjusted by the respective hydrogen amounts and temperatures during the polymerization of the polyethylene component (A), the polyethylene component (B) and the polyethylene component (C), and the blending amount of each component.

Characteristic (3)
The polyethylene resin composition of the present invention has a melt flow rate ratio (HLMFR/MFR), which is a ratio of HLMFR to MFR, of 50 or more and 140 or less. The melt flow rate ratio is preferably 51 or more and 130 or less, more preferably 52 or more and 120 or less.
HLMFR/MFR has a strong correlation with the molecular weight distribution, and when HLMFR/MFR has a large value, the molecular weight distribution becomes wide, and when HLMFR/MFR has a small value, the molecular weight distribution becomes narrow. When HLMFR/MFR exceeds 140, the compatibility of each component may be deteriorated, pinch-off moldability may be deteriorated, and impact resistance may be deteriorated. There is a possibility that a stable phenomenon is likely to occur and ESCR may be lowered.
The HLMFR/MFR can be controlled mainly according to the method of controlling the molecular weight distribution.

Characteristic (4)
Polyethylene resin composition of the present invention, density of 0.940 g / cm ³ or more 0.965 g / cm ³ or less. The density is preferably 0.942 g / cm ³ or more 0.963 g / cm ³ or less, more preferably 0.945 g / cm ³ or more 0.960 g / cm ³ or less.
If the density is less than 0.940 g/cm ³ , the rigidity may be insufficient and the crystallization rate may be decreased, resulting in a decrease in molding cycle. On the other hand, when the density exceeds 0.965 g/cm ³ , the environmental stress crack resistance performance may decrease.
The density can be adjusted mainly by the amount of the α-olefin during the polymerization of the polyethylene component (A), the polyethylene component (B) and the polyethylene component (C), and can be adjusted by the blending amount of each component. it can.

Characteristic (5)
The polyethylene resin composition of the present invention has an elongation viscosity η(t) (unit: Pa·sec) and an elongation time t (unit:) measured at a temperature of 170° C. and an elongation strain rate of 0.1 (unit: 1/sec). 2) is a polyethylene resin composition in which an inflection point of elongational viscosity due to strain hardening is observed in a logarithmic plot of (second).
The presence or absence of the inflection point of elongational viscosity due to strain hardening can be observed in the measurement of the strain hardening degree, and can be measured by the same method as the method for measuring the strain hardening degree of the polyethylene component (A) described above. it can.
In order that the polyethylene resin composition has a long-chain branched structure, it is preferable to use a predetermined amount of the polyethylene component (B) having a long-chain branched structure, and the polyethylene component (A) having a long-chain branched structure and a long-chain branched structure. A predetermined amount of the polyethylene component (B) having a chain branch structure is preferably used together.

Characteristic (6)
It is preferable that the polyethylene resin composition of the present invention further satisfies the following characteristic (6) from the viewpoint of molding high cycle.
Characteristic (6): The peak top time (T) and the melting point (Tm) in the isothermal crystallization at 121.5° C. measured by a differential scanning calorimeter (DSC) satisfy the following relational expression (1).
T [second]≦−76.80×Tm [° C.]+10,410 Relational expression (1)
The peak top time (T) in isothermal crystallization at 121.5° C. was 121.5 at a rate of 120° C./min after leaving the sample at 190° C. for 5 minutes with a differential scanning calorimeter (DSC). It is possible to obtain the crystallization time by cooling to and holding the temperature, and detecting and measuring the peak top at the time when crystallization is completed under the isothermal condition of 121.5° C.
The melting point (Tm) can be measured by a differential scanning calorimeter (DSC). A press sheet having a thickness of 0.2 mm is cut into a circle, and about 5 mg of the sample is packed in an aluminum pan and placed under a nitrogen atmosphere. After raising the temperature to 200° C., holding at the same temperature for 5 minutes, cooling to 30° C. at 10° C./minute, holding at the same temperature for 5 minutes, then raising to 200° C. at 10° C./minute, After holding the temperature for 5 minutes, the temperature is lowered to 30° C. at 10° C./minute, and the temperature at which the change in the amount of heat due to melting becomes maximum can be obtained as the melting point (Tm).
In order for the polyethylene resin composition of the present invention to satisfy the characteristic (6), the polyethylene component (A), the polyethylene component (B) and the polyethylene component (C) having specific physical properties should be mixed in a predetermined mixing ratio. Is preferred.

Characteristic (7)
It is preferable that the polyethylene resin composition of the present invention further satisfies the following characteristic (7) from the viewpoint of hollow moldability such as drawdown resistance.
Characteristic (7): Melt tension (MT) measured at 190° C. is 50 mN or more. The melt tension is more preferably 60 mN or more, still more preferably 65 mN or more. Further, those having a high melt tension corresponding to HLMFR and satisfying the following relational expression (3) are preferable, and those satisfying the following relational expression (4) are more preferable.
MT>−22.45×ln(HLMFR)+137.82 Relational expression (3)
MT>−22.45×ln(HLMFR)+157.82 Relational expression (4)
Here, MT (mN) is a melt tension, and HLMFR (g/10 minutes) is a melt flow rate at a temperature of 190° C. and a load of 21.6 Kg.
In the present invention, when the horizontal axis represents HLMFR and the vertical axis represents melt tension, and the example data of the present invention is plotted, the relational expression (3) is a mathematical expression for distinguishing the preferable range of the present invention from the prior art. Then, the relational expression (4) is a mathematical expression for defining a more preferable range of the present invention.
The melt tension is determined by measuring the stress when the melted ethylene-based polymer is stretched at a constant rate, and can be measured under the following conditions.
[Measurement condition]
Model used: Capillograph 1B, manufactured by Toyo Seiki Seisakusho Ltd.
Nozzle diameter: 2.095 mm
Nozzle length: 8.0 mm
Inflow angle: 180° (flat)
Extrusion speed: 15 mm/min Pulling speed: 6.5 m/min Measuring temperature: 190°C
In order for the polyethylene resin composition of the present invention to satisfy the characteristic (7), the polyethylene component (A), the polyethylene component (B) and the polyethylene component (C) having specific physical properties should be mixed in a predetermined mixing ratio. Is preferred.

Characteristic (8)
The polyethylene resin composition of the present invention preferably satisfies the following characteristic (8) from the viewpoint of good dispersion of the polyethylene component (A). When the polyethylene component (A) can be highly dispersed in the polyethylene component (B) and the polyethylene component (C), the surface property of the molded article becomes smooth and the appearance becomes particularly excellent.
Characteristic (8): Dynamic melt viscosity η _W·0.01 (unit: Pa·sec) measured at a frequency ω of 0.01 rad/sec at a temperature of 190° C. is _more than 20,000 and less than 100,000.
The dynamic melt viscosity η _W·0.01 was determined by using a sample formed into a sheet having a thickness of 2.0 mm by hot pressing, using a rheometer (Ares made by Rheometrics), and using a parallel plate at a temperature of 190° C. The dynamic melt viscosity (unit: Pa·sec) measured at 1.7 mm, strain of 10%, and frequency ω of 0.01 rad/sec was calculated as the dynamic melt viscosity at low strain rate (ηW·0.01). ).
[Measurement condition]
Device: Ares manufactured by Rheometrics
Jig: Diameter 25mm parallel plate, plate spacing 1.7mm
Measurement temperature: 190℃
Frequency range: 0.01-100 (unit: rad/sec)
Distortion: 10%
In order for the polyethylene resin composition of the present invention to satisfy the characteristic (8), the polyethylene component (A), the polyethylene component (B) and the polyethylene component (C) having specific physical properties should be mixed in a predetermined mixing ratio. Is preferred.

Characteristic (9)
It is preferable that the polyethylene resin composition of the present invention further satisfies the following characteristic (9) from the viewpoint of good dispersion of the polyethylene component (A).
Characteristic (9): Dynamic melt viscosity η _H of polyethylene component (A) against dynamic melt viscosity η _W·0.01 of polyethylene resin composition measured at a frequency ω of 0.01 rad/sec at a temperature of 190° C. _{· 0.01} ratio eta _H-0.01 / eta _W-0.01 1 exceeded, less than 14, more preferably 1 exceeded, less than 10, even more preferably 1 excess, less than 8.
In order for the polyethylene resin composition of the present invention to satisfy the characteristic (9), the polyethylene component (A), the polyethylene component (B) and the polyethylene component (C) having specific physical properties should be mixed in a predetermined mixing ratio. Is preferred.

Characteristic (10)
It is preferable that the polyethylene resin composition of the present invention further satisfies the following characteristic (10) from the viewpoint of particularly excellent balance of rigidity (density) and long-term durability such as environmental stress crack resistance.
Characteristic (10): The time and density (D) of a full notched creep test (FNCT) performed according to ISO DIS 16770 satisfy the following relational expression (5).
log(FNCT[hr])≧−257.5×D[g/cm ³ ]+247.9 Relational expression (5)
Here, FNCT (time) is the breaking time of the creep test with all notches shown below, and D is the density (g/cm ³ ). The longer the full notched creep test (FNCT), the better the long-term durability such as environmental stress crack resistance.
In the present invention, when density (g/cm ³ ) is plotted on the horizontal axis and FNCT (time) is plotted on the vertical axis, and the example data of the present invention is plotted, the relational expression (5) shows that the preferable range of the present invention is This is a mathematical expression to distinguish it from technology.
All notched creep tests can be performed in accordance with ISO DIS 16770. For the sample, prepare a test piece having a cross section of 4 mm × 4 mm in which a notch of 1 mm is attached with a razor blade around the entire circumference of a prism of 6 mm × 6 mm × 11 mm, and pure water at 80°C is prepared. Among them, a tensile stress corresponding to 3.7 MPa is applied to the sample, the time until the sample breaks is measured, and this is taken as the FNCT break time.
The polyethylene resin composition of the present invention preferably satisfies the above relational expression (5) and has an FNCT (hour) of more than 20 hours, more preferably 180 hours or more, and further more 600 hours. The above is preferable.
In order for the polyethylene resin composition of the present invention to satisfy the characteristic (10), the polyethylene component (A), the polyethylene component (B) and the polyethylene component (C) having specific physical properties are mixed in a predetermined mixing ratio. Preferably.

According to the polyethylene resin composition of the present invention, since it is a polyethylene material having the above properties (1) to (5), it is excellent in hollow moldability, environmental stress crack resistance and impact resistance, and is thinner and lighter. It is possible to mold with high crystallization rate, excellent high-speed moldability, molding high cycle is possible, good pinch-off characteristics, high compatibility of resin components, It is possible to obtain a molded product having a particularly excellent appearance.
Furthermore, preferably, a polyethylene resin composition having one or more of the above characteristics (6) to (10) in addition to the above characteristics (1) to (5) will exhibit the above effects even better.

The above effect will be further described below.
By mixing and using the specific polyethylene component (A), the specific polyethylene component (B), and the specific polyethylene component (C), the effect of the component having a long-chain branched structure can significantly increase the crystallization rate. The speed can be effectively increased, the same effect as adding a so-called crystal nucleating agent can be exhibited, the crystallization time can be shortened, and high-speed molding high cycle as a polyethylene resin composition for containers can be achieved.
Further, by using the specific polyethylene component (A) together with the specific polyethylene component (B) and the specific polyethylene component (C), an ethylene polymer composition using a conventional chromium-based catalyst, It is possible to further improve the environmental stress crack resistance as compared with an ethylene polymer composition using a Ziegler catalyst and an ethylene polymer composition in which they are mixed.

Generally, polyethylene is processed into an industrial product by a molding method such as film molding, blow molding, foam molding, etc., which goes through a molten state. At this time, the extensional flow characteristics represented by the extensional viscosity and strain hardening degree described above are used. It is well known that has a great influence on the ease of molding.
That is, polyethylene having a narrow molecular weight distribution and no long chain branching has poor meltability because of its low melt strength, while polyethylene having an ultrahigh molecular weight component or long chain branching component is strain-hardened (strain-hardened) during melt elongation. Hardening), that is, polyethylene having a characteristic that the elongational viscosity sharply increases on the high strain side, and which exhibits this characteristic remarkably, is said to have excellent moldability. The polyethylene resin having such extension flow characteristics can prevent uneven thickness and blowout of the product in film molding or hollow molding, enable high-speed molding, and increase the closed cell ratio in foam molding. It is effective and has the advantages of improved strength, improved designability, reduced weight, improved molding cycle, improved heat insulation, etc. on the other hand, but on the other hand, if the extensional flow characteristics of polyethylene are too strong, the Due to the strength anisotropy presumed to be due to the orientation, the impact strength of the molded body may be lowered, and other disadvantages may occur.
On the other hand, the long chain branching structure, which is the main controlling factor of the elongational viscosity characteristic, is devised in order to improve the molding processability and to overcome the inconvenience in the mechanical property of the molded body caused by the elongational flow characteristic of polyethylene. In order to solve this problem, the polyethylene resin composition was earnestly studied. According to the present invention, as described above, the polyethylene component (B), which is a medium molecular weight component and in which an inflection point of elongational viscosity due to strain hardening is observed, satisfying the specific physical property balance is a high molecular weight component. And a polyethylene component (A) having specific physical properties, which is used as a compatibilizing agent for low molecular weight components, as a low melt flow component, that is, a high molecular weight component of the composition, and a polyethylene component (C) having specific physical properties. By using it as a high melt flow component of the product, that is, a low molecular weight component and a high density component, it contributes to rigidity, environmental stress crack resistance and impact resistance improvement, as well as molding processing characteristics, especially drawdown resistance and pinch-off. It is also excellent in hollow moldability such as moldability, can be molded with thinner and lighter weight, has high melt tension, excellent drawdown resistance, and is capable of hollow molding of complex shapes. It is considered that it is also excellent in improving the crystallization rate.

Since the polyethylene component (B) satisfying the specific physical property balance is used as a compatibilizing agent for the high molecular weight component and the low molecular weight component, the compatibility of each resin component in the resin composition is excellent and The polyethylene resin composition has a particularly excellent appearance. Further, since the polyethylene component (B) satisfying the specific physical property balance has a wide molecular weight distribution and a high extensional viscosity, it is easy to suppress poor appearance due to a flow instability phenomenon such as sharkskin and is particularly excellent in the appearance of the molded product. It is estimated to be.
In particular, when the polyethylene component (A) has an appropriate long-chain branched structure, the melt flow rate ratio becomes specific, whereby the polyethylene component (A) is converted into the polyethylene component (B) and the polyethylene component (C). The compatibility is good because a high degree of dispersion is possible. Therefore, in the molded product, the surface properties become smooth and the appearance becomes particularly excellent.
Since the polyethylene resin composition of the present invention is a polyethylene resin composition having the above physical properties, it is also excellent in moldability, high fluidity, odor, food safety, rigidity, heat resistance and the like.

5. Method for producing polyethylene resin composition The polyethylene resin composition of the present invention is also required by melt-mixing the polyethylene component (A) with the polyethylene component (B) and the polyethylene component (C) in a predetermined mixing ratio. According to the above, it can be produced by adding other components and melt-mixing.
The polyethylene resin composition of the present invention comprises the following substances in addition to the essential polyethylene component (A) other than the polyethylene component (B) and the polyethylene component (C) as long as the object of the present invention is not impaired. It can be blended as an optional component.
For example, various ethylene-based polymers such as high-density polyethylene, low-density polyethylene, high-pressure polyethylene, polar monomer graft-modified polyethylene, ethylene wax, ultrahigh molecular weight polyethylene, ethylene elastomer, and modified products thereof can be used. Addition of high-density polyethylene is preferable for improving rigidity, heat resistance, impact strength and the like. Addition of low-density polyethylene is preferable for improving flexibility, impact strength, easy adhesion, transparency, low temperature strength and the like. Addition of high-pressure polyethylene is preferred to improve flexibility, easy adhesion, transparency, low temperature strength, moldability and the like. The addition of polar monomer graft-modified polyethylene such as maleic acid modified polyethylene, ethylene/acrylic acid derivative copolymer, ethylene/vinyl acetate copolymer, etc., has flexibility, easy adhesion, colorability, affinity for various materials, gas barrier property, etc. It is preferable to improve. Addition of an ethylene wax is preferable for improving colorability, affinity for various materials, molding processability, and the like. The addition of ultra-high molecular weight polyethylene is preferable for improving mechanical strength, wear resistance and the like. Addition of an ethylene-based elastomer is preferable for improving flexibility, mechanical strength, impact strength and the like.
In addition to the above polymers, various resins can be used. Specifically, various nylon resins, various polyamides, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), various polyesters, polycarbonate resins, EVOH, EVA, PMMA, PMA, various engineering plastics, polylactic acid, celluloses, Examples thereof include natural rubbers, polyurethanes, vinyl chloride, fluorine resins such as Teflon (registered trademark), and inorganic polymers such as silicone resins.

According to a conventional method, the polyethylene resin composition of the present invention can be pelletized by mechanical melt mixing with a pelletizer, a homogenizer or the like, and then molded by various molding machines to obtain a desired molded product.
In addition, the polyethylene resin composition obtained by the above method, in addition to other olefin polymers, rubbers, etc., antioxidants, ultraviolet absorbers, light stabilizers, lubricants, antistatic agents, Known additives such as a clouding agent, an antiblocking agent, a processing aid, a color pigment, a crosslinking agent, a foaming agent, an inorganic or organic filler, and a flame retardant can be added.
As additives, for example, antioxidants (phenol-based, phosphorus-based, sulfur-based), lubricants, antistatic agents, light stabilizers, ultraviolet absorbers and the like can be used alone or in combination of two or more as appropriate. As the filler, calcium carbonate, talc, metal powder (aluminum, copper, iron, lead, etc.), silica stone, diatomaceous earth, alumina, gypsum, mica, clay, asbestos, graphite, carbon black, titanium oxide, etc. can be used. Among them, it is preferable to use calcium carbonate, talc, mica and the like. In any case, the polyethylene resin composition may be mixed with various additives as necessary and kneaded with a kneading extruder, a Banbury mixer or the like to obtain a molding material.

In the present invention, it is also an effective method to use a nucleating agent in order to further accelerate the crystallization rate of the polyethylene resin composition.
As the nucleating agent, a generally known one can be used, and a general organic or inorganic nucleating agent can be used. For example, dibenzylidene sorbitol or a derivative thereof, an organic phosphoric acid compound or a metal salt thereof, an aromatic sulfonate or a metal salt thereof, an organic carboxylic acid or a metal salt thereof, a partial metal salt of rosin acid, inorganic fine particles such as talc, imides , Amides, quinacridonequinones, or mixtures thereof.
Among them, a dibenzylidene sorbitol derivative, an organic phosphoric acid metal salt, an organic carboxylic acid metal salt and the like are preferable because they are excellent in transparency.
Specific examples of the dibenzylidene sorbitol derivative include 1,3:2,4-bis(o-3,4-dimethylbenzylidene)sorbitol and 1,3:2,4-bis(o-2,4-dimethylbenzylidene). Sorbitol, 1,3:2,4-bis(o-4-ethylbenzylidene)sorbitol, 1,3:2,4-bis(o-4-chlorobenzylidene)sorbitol, 1,3:2,4-dibenzylidene Examples thereof include sorbitol, and specific examples of the metal salt of benzoic acid include aluminum hydroxy-di(t-butylbenzoate).

When the nucleating agent is blended in the polyethylene resin composition of the present invention, the blending amount of the nucleating agent is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the composition. Parts by mass, more preferably 0.01 to 1 part by mass, particularly preferably 0.01 to 0.5 parts by mass. When the amount of the nucleating agent is less than 0.01 parts by mass, the effect of improving the high-speed moldability is not sufficient, while when it exceeds 5 parts by mass, there is a problem in that the nucleating agent tends to aggregate and become hard.

6. Molded Product and Container The molded product of the present invention is a molded product produced using the polyethylene resin composition of the present invention.
The container of the present invention is a container made using the polyethylene resin composition of the present invention.
A molded body can be produced by various molding methods using the polyethylene resin composition of the present invention as a raw material. Preferably, it is mainly molded by a hollow molding method or the like, and various molded products such as hollow containers are preferably obtained.

Since the polyethylene resin composition of the present invention satisfies the above characteristics, the molded article of the present invention using the same is excellent in environmental stress crack resistance, impact resistance, odor, food safety, rigidity, In addition to being excellent in heat resistance, the compatibility of the resin component is high, the surface properties of the molded product are excellent, and the appearance is particularly good. In addition, it can be formed thinner and lighter, has a high crystallization rate, is excellent in high-speed formability, can be formed into a high cycle, and has good pinch-off characteristics.
Therefore, it is suitable for applications such as containers that require such properties, and in particular, it is required to have a good appearance, such as cosmetic containers, detergents, shampoo and rinse containers, or food containers such as edible oil. It can be suitably used for the purpose.

In particular, the container which is a molded product using the polyethylene resin composition of the present invention is capable of high-speed molding and high cycle, has excellent product properties, and is economically advantageous, such as detergent, shampoo and rinse. It is suitable as a container.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.

1. Measuring method The measuring method used in the examples is as follows.
(1) Melt flow rate (MFR) at a temperature of 190° C. and a load of 2.16 kg:
It was 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:
It was 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:
It was measured according to JIS K6922-2:1997.
(4) Density:
It was measured according to JIS K6922-1, 2:1997.

(5) Melt tension:
The melt tension (MT) was determined by measuring the stress when the melted ethylene-based polymer was stretched at a constant rate, and was measured under the following conditions.
[Measurement condition]
Model used: Capillograph 1B, manufactured by Toyo Seiki Seisakusho Ltd.
Nozzle diameter: 2.095 mm
Nozzle length: 8.0 mm
Inflow angle: 180° (flat)
Extrusion speed: 15 mm/min Pulling speed: 6.5 m/min Measuring temperature: 190°C

(6) Environmental stress crack resistance (FNCT):
All notched creep tests were performed according to ISO DIS 16770. For the sample, prepare a test piece having a cross section of 4 mm × 4 mm in which a notch of 1 mm is attached with a razor blade around the entire circumference of a prism of 6 mm × 6 mm × 11 mm, and pure water at 80°C is prepared. Among them, a tensile stress corresponding to 3.7 MPa was applied to the specimen, and the time until the specimen broke was measured and used as the fracture time of FNCT.

(7) Tensile impact strength:
A 1.5 mm compression molded sheet is prepared according to JIS K6922-2, and a test piece punched out with an S-type dumbbell is prepared according to ASTM D1822, and the measurement is performed at 23° C. and 50% RH. went.

(8) Crystallization time (crystallization speed):
The sample was left at 190° C. for 5 minutes with a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer Co., Ltd.), and then cooled to 121.5° C. at a rate of 120° C./minute to retain the sample. The peak top was detected and measured at the time when the crystallization was completed under the isothermal condition of 121.5° C., and the measurement was taken as the crystallization time.

(9) Melting point:
The melting point and the crystallization temperature were measured with a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer). That is, about 5 mg of a sample obtained by cutting a 0.2 mm-thick press sheet into a circle was packed in an aluminum pan, heated to 200° C. under a nitrogen atmosphere, kept at the same temperature for 5 minutes, and kept at 10° C./minute for 30 minutes. After cooling to ℃, hold at the same temperature for 5 minutes, then raise to 200 ℃ at 10 ℃ / min, hold at the same temperature for 5 minutes, then cool to 30 ℃ at 10 ℃ / min to melt The temperature at which the change in the amount of heat accompanied was the maximum was defined as the melting point (Tm).

(10) Presence or absence of long-chain branched structure:
Using a test piece that was press-molded to form a sheet of 18 mm×10 mm and a thickness of 0.7 mm, a rheometer (Ares manufactured by Rheometrics) was used to measure extensional viscosity at 170° C. and a strain rate of 0.1/sec. Then, the presence or absence of a long-chain branched structure was confirmed by the presence or absence of strain hardening (whether or not the extension viscosity rises).
[Measurement condition]
Device: Ares manufactured by Rheometrics
Jig: Extensive Viscosity Fixture manufactured by TA Instruments
Measurement temperature: 170℃
Strain rate: 0.1/sec Preparation of test piece: Press molding was performed to prepare a sheet having a size of 18 mm×10 mm and a thickness of 0.7 mm.
[Calculation method]
The elongation viscosity at 170° C. and a strain rate of 0.1/second was plotted in a logarithmic graph with time t (unit: second) on the horizontal axis and elongation viscosity η(t) (unit: Pa·second) on the vertical axis. On the logarithmic log graph, the maximum extensional viscosity after strain hardening until the strain amount becomes 4.0 is η _Max (t1) (t1 is the time when the maximum extensional viscosity is obtained), and the extensional viscosity before strain hardening is set. The value calculated as η _Max (t1)/η _Linear (t1) is defined as the strain hardening degree (λmax), where η _Linear (t) is the approximate straight line. The presence or absence of strain hardening was judged by whether or not the elongational viscosity had an inflection point at which the upwardly convex curve changed to a downwardly convex curve over time.
1 and 2 are typical plots of extensional viscosity. FIG. 1 shows a case where an inflection point of extensional viscosity is observed, and η _Max (t1) and η _Linear (t1) are shown in the figure. FIG. 2 shows the case where no inflection point of extensional viscosity is observed.

(11) Measurement of molecular weight and molecular weight distribution by gel permeation chromatography (GPC):
It was measured by gel permeation chromatography (GPC) under the following conditions.
[Measurement condition]
Model used: Alliance GPCV2000 manufactured by Nippon Waters Co., Ltd. Measuring temperature: 145°C
Solvent: Orthodichlorobenzene (ODCB)
Column: Showa Denko Shodex HT-806M x 2 + same HT-G
Flow rate: 1.0 mL/min Injection volume: 0.3 mL

[Sample preparation]
In a 4 mL vial, 3 mg of the sample and 3 mL of orthodichlorobenzene (containing 0.1 mg/mL of 1,2,4-trimethylphenol) were weighed and covered with a resin screw cap and a Teflon (registered trademark) septum. After that, dissolution was performed for 2 hours using a SSC-9300 type high-temperature shaker manufactured by Senshu Scientific Co., which was set at a temperature of 150°C. After the dissolution was completed, it was visually confirmed that there were no insoluble components.
[Creation of calibration curve]
Four 4 mL glass bottles were prepared, and 0.2 mg each of the monodisperse polystyrene standard sample or n-alkane of the combination of (1) to (4) below was weighed in each, followed by orthodichlorobenzene (0.1 mg/mL). 3 mL of 1,2,4-trimethylphenol) was weighed and covered with a resin screw cap and a Teflon (registered trademark) septum, and then the temperature was set to 150° C. by Senshu Scientific SSC-9300 type high temperature. Dissolution was carried out for 2 hours using a shaker.
(1) Shodex S-1460, same S-66.0, n-eicosan (2) Shodex S-1950, same S-152, n-tetracontane (3) Shodex S-3900, same S-565, same S -5.05
(4) Shodex S-7500, same S-1010, same S-28.5
The vial containing the sample solution was set in the apparatus, the measurement was performed under the above-mentioned conditions, and the chromatogram (data set of retention time and response of the differential refractometer detector) was recorded at a sampling interval of 1 s. The retention time (peak apex) of each polystyrene standard sample was read from the obtained chromatogram and plotted against the logarithmic value of the molecular weight. Here, the molecular weights of n-eicosane and n-tetracontane were set to 600 and 1200, respectively. The nonlinear least squares method was applied to this plot, and the obtained quartic curve was used as the calibration curve.

[Calculation of molecular weight]
The measurement was performed under the above-mentioned conditions, and the chromatogram was recorded at a sampling interval of 1 s. this
Chromatogram Sadao Mori "Size Exclusion Chromatography" (Kyoritsu Shuppan) Chapter 4 p. 51 to 60, the differential molecular weight distribution curve and the average molecular weight values (Mn, Mw and Mz) were calculated. However, in order to correct the molecular weight dependence of dn/dc, the height H from the baseline in the chromatogram was corrected by the following formula. Recording of the chromatogram (data acquisition) and calculation of the average molecular weight were performed using an in-house program (created with Visual Basic 6.0 by Microsoft) on a PC on which OS Windows (registered trademark) XP by Microsoft was installed.
H'=H/[1.032+189.2/M(PE)]
The following formula was used to convert the molecular weight of polystyrene to polyethylene.
M(PE)=0.468×M(PS)

(12) Dynamic melt viscosity (η _H·0.01 ):
A sample was blended with 2000 ppm of an antioxidant (IRGANOX B225 manufactured by BASF Japan), melt-kneaded, and molded into a sheet with a thickness of 1.0 mm by hot pressing, and a rheometer (Ares manufactured by Rheometrics) was used, and a parallel plate was used. After the sample is brought into close contact with the plate and melted, the stress is relaxed at a temperature of 210 to 220° C., and the sample is cooled to a temperature of 190° C. while adjusting the plate interval so that there is no gap between the plates. The measurement was performed in the range of 0.0 mm and strain of 0.2 to 1%. The dynamic melt viscosity (unit: Pa·sec) measured at a frequency ω of 0.01 rad/sec was defined as the dynamic melt viscosity at low strain rate (η _H·0.01 ).
[Measurement condition]
Device: Ares manufactured by Rheometrics
Jig: Diameter 25mm parallel plate, plate spacing about 1.0mm
Measurement temperature: 190℃
Frequency range: 0.01-100 (unit: rad/sec)
Strain range: 0.2-1%

(13) Dynamic melt viscosity (η _W·0.01 ) of polyethylene resin composition:
Using a sample molded into a sheet having a thickness of 2.0 mm by hot pressing, a rheometer (Ares manufactured by Rheometrics) was used and a parallel plate was used at a temperature of 190° C. with a plate interval of 1.7 mm, strain of 10%, and frequency ω. The dynamic melt viscosity (unit: Pa·sec) measured at 0.01 rad/sec was defined as the dynamic melt viscosity at low strain rate (η _W·0.01 ).
[Measurement condition]
Device: Ares manufactured by Rheometrics
Jig: Diameter 25mm parallel plate, plate spacing 1.7mm
Measurement temperature: 190℃
Frequency range: 0.01-100 (unit: rad/sec)
Distortion: 10%

(14) Surface texture:
The area ratio of fish eyes was measured by the following method for evaluating miscibility, and this was used to evaluate the surface properties.
[Mixability evaluation method]
The sample to be measured is compression processed at a temperature of 180° C. and a pressure of 100 kgf/cm ² in the first step by a mold having a thickness of 0.35 mm and two press molding machines for compression processing and cooling. In the second step, it is cooled at a temperature of 30° C. and a pressure of 50 kgf/cm ² to form a press sheet having a thickness of 0.4 mm. This press sheet was cut into test pieces of 50×50×0.4 mm.
Next, the test piece was stretched by a biaxial stretching device. A biaxial stretching device SS-60 type manufactured by Shibayama Scientific Instruments Co., Ltd. was used as a biaxial stretching device, and the test piece was stretched twice at a temperature of 150° C. and a stretching speed of 60 mm/min. The stretching procedure was such that a 1 cm portion on each side of the test piece was chucked by a four-point chuck unit of a biaxial stretching device, and the central portion of the press sheet which was not chucked was set to be a square of 30×30 mm. Then, the test piece was heated to a temperature of 130 to 170° C., biaxially stretched until the distance between the diagonally opposite chucks became 60 mm, and a sheet in which the central portion without chucking was stretched about twice was obtained. Created.
The surface of a square area of 30×30 mm located almost in the center of the biaxially stretched sheet was imaged using a reflective 3D microscope. The magnification of the 3D microscope is 10 times, and the range of the imaged sheet (one visual field) is 10×10 mm. In order to increase the reliability of the measurement, one measurement was performed four times in a square area of 30×30 mm located in the center of the sheet so that the respective visual fields of view did not overlap. The photographed image was binarized into a fish eye portion and a non-fish eye portion (uniform matrix portion). The condition of the binarization process was set by the measurer, and the condition was used for all measurements.
The binarized image was read by a scanner and digitized to obtain image data.
The resolution of the scanner is 600 dpi or more, preferably 900 dpi or more. A scanner GT-F670 (manufactured by EPSON, resolution: 4800 dpi) was used as the scanner.
The analysis of image data is realized by a personal computer and a software program executed on the personal computer, and the image data is processed by the personal computer so that the area of each particle, the perimeter, the ratio of the major axis to the minor axis, the particle size, and the circularity are calculated. The characteristic parameters such as are calculated. For the calculation of the characteristic parameters in this case, generally commercially available image processing software or the like can be used, and WinROOF or the like manufactured by Mitani Corporation is used as the commercially available image analysis software.
The image data defines a threshold value for the color arrangement of the black portion and the white portion of the image, and is binarized and processed at an appropriate level. The condition of the binarization process was set by the measurer, and the condition was used for all measurements.
In image analysis, the area, circumference length, maximum length, maximum length vertical length (length in the direction perpendicular to the maximum length), etc. of each particle are calculated by known means, and various parameters of the particle are calculated for each particle. Can be calculated, and the calculated parameters include the equivalent circle diameter of the particle (diameter of the circle of the area equal to the area of the image of the particle), circularity (perimeter of the circle of the area equal to the area of the image of the particle). And the ratio of the perimeter of the image), the aspect ratio (the ratio between the maximum length of the image of the particles and the maximum vertical length).
The equivalent circle diameter is equivalent circle diameter=(area value of particle image/π) ^1/2 ×2, and circularity is circularity=(perimeter of circle having area value of particle image)/( The perimeter of the particle image) and the aspect ratio are calculated by (maximum length of particle image)/(maximum length of particle image vertical length).
In the present invention, as the measurement of fish eyes, the area ratio of fish eyes in the image was determined. The area ratio of the fish eyes of one sample was calculated by averaging the measured values obtained in each of four visual fields taken on one test piece.
And, when the area ratio of fish eyes occupying in the image is 0.2% or less, it is "1", when it exceeds 0.2 to 0.5%, it is "2", and when it exceeds 0.5 to 3.0%. The case was evaluated as "3", the case of more than 3.0 to 5.0% as "4", and the case of more than 5% as "5". The evaluation results are shown in Table 1.

(15) Overall evaluation:
Suitability such as hollow moldability as a polyethylene resin composition was evaluated, and in all of the following items, good ones were evaluated as “◯”, and other products were evaluated as “x”.
That is, the following pinch-off characteristics, drawdown resistance, crystallization time and extensional viscosity were measured, and environmental stress crack resistance was also added for evaluation.
1) Pinch-off characteristics: For measurement of tan δ at 150° C. and 100 rad/sec measured by a rheometer, a sample prepared by hot press is used, and a rheometer (Ares manufactured by Rheometrics) is used at 150° C. and an angular velocity of 100 rad/sec. The storage elastic modulus G′ and the loss elastic modulus G″ were measured, and tan δ(=G″/G′) was calculated. The conditions for measurement are described below. Those having a tan δ of 0.50 to 0.80 were regarded as having good pinch-off characteristics.
[Measurement condition]
Device: Ares manufactured by Rheometrics
Jig: Diameter 25mm parallel plate, plate spacing 1.7mm
Measurement temperature: 150°C
Distortion: 10%
2) Drawdown resistance: A melt tension (MT) of 50 mN or more was considered good.
3) Crystallization rate: The one in which the isothermal crystallization time of DSC satisfied the relational expression (1) was regarded as good.
T [second]≦−76.80×Tm [° C.]+1,0410 Relational expression (1)
(T [sec]: peak top time in isothermal crystallization at 121.5° C. measured by differential scanning calorimeter (DSC), Tm [° C.]: melting point)
4) The one in which the rise of extensional viscosity was confirmed was regarded as good.
5) Environmental stress crack resistance: FNCT (hour) is over 20 hours.

2. Examples and Comparative Examples <Synthesis of metallocene catalyst>
³ g of silica having an average particle size of 11 μm (average particle size of 11 μm, surface area of 313 m ² /g, pore volume of 1.6 cm ³ /g) was charged in a cylindrical flask equipped with an induction stirrer, which was sufficiently replaced with nitrogen, Toluene (75 ml) was added and the mixture was heated to 75° C. in an oil bath. In a separate flask, 8.0 ml of a toluene solution of methylaluminoxane (manufactured by Albemarle, 3.0 mol-Al/L) was collected. Dimethylsilylenebis[1,1'-{2-(2-(5-methyl)furyl)-4-(p-isopropylphenyl)-indenyl}]zirconium dichloride (63.4 mg, 75 μmol) in toluene solution (15 ml) Was added to a toluene solution of methylalumoxane at room temperature, the temperature was raised to 75° C., and the mixture was stirred for 1 hour. Next, this toluene solution was added to a toluene slurry of silica heated to 75° C. with stirring and held for 1 hour. Then, 175 ml of n-hexane was added with stirring at 23° C., and after 10 minutes, stirring was stopped and the mixture was allowed to stand. After allowing the catalyst to settle sufficiently, the supernatant was removed and 200 ml of n-hexane was added. After stirring once, the mixture was allowed to stand again and the supernatant was removed. This operation was repeated 3 times to remove the components liberated in n-hexane. Further, the solvent was distilled off under reduced pressure while heating at 40°C. After the degree of vacuum was 0.8 mmHg or less, vacuum drying was continued for another 15 minutes to obtain a metallocene catalyst (i).
<Production of anti-fouling ingredients>
3 g of n-octylated polyethyleneimine derived from polyethyleneimine (molecular weight 10,000) (in which 0.5 n-octyl groups were introduced per monomer unit of polyethyleneimine) and phosphoric ester in 100 mL of xylene 1 g of the compound phytic acid was mixed and stirred at room temperature to form a salt. Then, 6 g of dioctyl sulfosuccinic acid ester magnesium salt was mixed to obtain an anti-fouling component.

<Production of polyethylene component (A1)>
A polyethylene component (A1) was produced by carrying out ethylene/1-hexene copolymerization with the above metallocene catalyst. That is, 115 L/h of dehydrated and purified isobutane, 0.13 mol/h of triisobutylaluminum and 6 ml/h of anti-fouling component B were fed to a loop type slurry reactor having an inner volume of 290 L, and the temperature in the reactor was 80°C. As ethylene, 1-hexene and hydrogen were supplied while intermittently discharging from the reactor so as to keep the pressure at 4.2 MPaG, the molar ratio of 1-hexene to ethylene in the liquid during the polymerization (C6/ C2) was adjusted to 0.010 and the molar ratio of hydrogen to ethylene (H2/C2) was adjusted to 3.4×10 ⁻⁴ . Next, a hexane slurry of catalyst A diluted to 0.3 g/L with hexane was supplied to the reactor at 3 L/h to start polymerization, and ethylene was supplied so that the ethylene concentration in the reactor became 10 vol %. did. The produced polyethylene was intermittently discharged together with isobutane, flushed, and then sent to a product silo.
The polyethylene component (A1) obtained at this time had an HLMFR of 0.57 g/10 min, a density of 0.9242 g/cm ³ and an HLMFR/MFR of 23. The polyethylene component (A1) had a long chain branched structure because it showed a relatively large HLMFR/MFR in view of the molecular weight distribution.
<Production of polyethylene component (A2)>
A polyethylene component (A2) having the physical properties shown in Table 1 was produced according to the above-mentioned production of the polyethylene component (A1).

<Polyethylene component (B1)>
A polyethylene grade polymerized by a commercially available chromium-based catalyst (Novatech HD:HB410R manufactured by Nippon Polyethylene Co., Ltd.) was used. The HLMFR of the polymer was 4.6 g/10 minutes, the density was 0.9560 g/cm ³ , Mw was 292,000, and Mw/Mn was 17.4.
<Polyethylene component (B2)>
An ethylene polymer polymerized with a chromium-based catalyst manufactured according to the example of JP 2013-203983 A was used. The HLMFR of the polymer was 8.0 g/10 minutes, the density was 0.9603 g/cm ³ , Mw was 274,000, and Mw/Mn was 28.6.
<Polyethylene component (B3)>
A polyethylene grade polymerized by a commercially available chromium-based catalyst (Novatech HD: HB439RP manufactured by Nippon Polyethylene Co., Ltd.) was used. The HLMFR of the polymer was 54.2 g/10 minutes, the density was 0.9614 g/cm ³ , Mw was 130,000, and Mw/Mn was 8.5.

<Polyethylene component (C1)>
An ethylene polymer polymerized with a Ziegler-based catalyst manufactured according to the example of JP-A-2013-200415 was used. The polymer had MFR of 192 g/10 minutes, density of 0.9694 g/cm ³ , Mw of 37,000, and Mw/Mn of 7.7.
<Polyethylene component (C2)>
An ethylene polymer polymerized with a Ziegler type catalyst was used. The polymer had an MFR of 50 g/10 minutes, a density of 0.9660 g/cm ³ , an Mw of 49,000 and an Mw/Mn of 6.8.
<Polyethylene component (C3)>
An ethylene polymer polymerized with a Ziegler type catalyst was used. The MFR of the polymer was 11 g/10 minutes, the density was 0.9632 g/cm ³ , Mw was 73,000, and Mw/Mn was 6.5.
<Polyethylene component (C4)>
An ethylene polymer polymerized with a Ziegler type catalyst was used. The polymer had MFR of 33 g/10 minutes, density of 0.9644 g/cm ³ , Mw of 63,000, and Mw/Mn of 6.5.
<Polyethylene component (C5)>
An ethylene polymer polymerized with a Ziegler type catalyst was used. The polymer had an MFR of 17 g/10 minutes, a density of 0.9640 g/cm ³ , an Mw of 63,000, and an Mw/Mn of 6.5.

[Example 1]
<Production of polyethylene resin composition>
The above-mentioned polyethylene component (A) (A1), polyethylene component (B) polyethylene component (B1) and polyethylene component (C) polyethylene component (C1) were melted at the ratios shown in Table 1 under the following kneading conditions. The polyethylene resin composition was manufactured by mixing.
[Kneading conditions]
Equipment used: Labo Plastomill roller mixer manufactured by Toyo Seiki Seisakusho Ltd. (mixer model: R100/Blade shape: roller model R100B)
Additive blend: 2,000 ppm of IRGANOX B225 manufactured by BASF Japan and 1,000 ppm of calcium stearate manufactured by Tanan Chemical Co., Ltd. Filling amount: 70 g/batch
Kneading temperature: 190℃
Blade rotation speed: 40 rpm
Preheating time: 5 minutes Kneading time: 2 minutes

Table 1 shows the physical properties and evaluation results of the polyethylene resin composition. The obtained composition has extremely good compatibility of each component, has a short crystallization time, is excellent in molding high cycle property, and is also excellent in hollow moldability due to appropriate fluidity and high melt tension, and has a high density. It had excellent mechanical properties such as environmental stress crack resistance balance and impact resistance.

[Examples 2 to 6]
A polyethylene resin composition was produced in the same manner as in Example 1 except that the conditions were set so that the composition shown in Table 1 was obtained. The physical properties and evaluation results of the obtained polyethylene resin composition are shown in Table 1. The obtained polyethylene resin composition has extremely good compatibility of each component, high melt tension, short crystallization time, excellent molding high cycle property, and environmental stress crack resistance, impact resistance, etc. It had excellent mechanical properties.

[Comparative Example 1]
A polyethylene resin composition was produced in the same manner as in Example 1 except that the conditions were set so that the composition shown in Table 1 was obtained. The physical properties and evaluation results of the obtained polyethylene resin composition are shown in Table 1. The obtained polyethylene resin composition is a two-component composition, which has a low melt tension, poor drawdown resistance required for blow molding, and cannot be expected to have a high molding cycle due to its slow crystallization rate. Mixing was not good.

[Comparative Example 2]
A polyethylene resin composition was produced in the same manner as in Example 1 except that the conditions were set so that the composition shown in Table 1 was obtained. The physical properties and evaluation results of the obtained polyethylene resin composition are shown in Table 1. The obtained polyethylene resin composition is a two-component composition, which has a low melt tension, poor drawdown resistance required for blow molding, and cannot be expected to have a high molding cycle due to its slow crystallization rate. Mixing was not good.

[Comparative Example 3]
A polyethylene resin composition was produced in the same manner as in Example 1 except that the conditions were set so that the composition shown in Table 1 was obtained. The physical properties and evaluation results of the obtained polyethylene resin composition are shown in Table 1. The polyethylene resin composition obtained had a large HLMFR of the polyethylene component (B), had a low melt tension of the composition, and was not well mixed.

[Comparative Example 4]
A polyethylene resin composition was produced in the same manner as in Example 1 except that the conditions were set so that the composition shown in Table 1 was obtained. The physical properties and evaluation results of the obtained polyethylene resin composition are shown in Table 1. The evaluation results of the obtained polyethylene resin composition are shown in Table 1. The obtained polyethylene resin composition is a two-component composition and has a good balance of rigidity and physical properties of ESCR, but has a low melt tension of the composition and poor drawdown resistance required for blow molding, Since the crystallization rate was slow, it was not possible to expect a high cycle of molding, and the balance between hollow moldability and mixing was not good.

[Comparative Example 5]
A polyethylene resin composition was produced in the same manner as in Example 1 except that the conditions were set so that the composition shown in Table 1 was obtained. The physical properties and evaluation results of the obtained polyethylene resin composition are shown in Table 1. The evaluation results of the obtained polyethylene resin composition are shown in Table 1. The obtained polyethylene resin composition was a two-component composition, and although the hollow moldability and the mixing balance were good, the physical properties balance between rigidity and ESCR was not good.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in hollow moldability, environmental stress cracking resistance, and impact resistance, and can be molded in a thinner and lighter weight, has a high crystallization rate, is excellent in high-speed moldability, and has a molding high cycle It is possible to provide a polyethylene resin composition having excellent pinch-off characteristics, high compatibility with resin components, and particularly excellent appearance of a molded article, and a molded article comprising the same.
Furthermore, the polyethylene resin composition of the present invention is excellent in high fluidity during molding, and the molded product of the present invention is also excellent in odor, food safety, rigidity, heat resistance and the like.
Therefore, the polyethylene resin composition of the present invention and the molded article thereof are suitable for applications such as containers requiring such characteristics, and particularly cosmetic containers, detergents, shampoos and rinse containers having excellent appearance, or edible oil, etc. Can be suitably used for applications such as food containers.
Furthermore, the container using the polyethylene resin composition of the present invention is capable of high-speed molding and high cycle, has excellent product characteristics, and is economically advantageous, such as cosmetic containers, detergents, shampoos and rinses. It is suitable as a container.
Further, since the polyethylene resin composition of the present invention has excellent performance as described above, it can be suitably used for kerosene cans, chemical containers and the like that require such characteristics in addition to the above-mentioned containers. Because it can, it is very useful in industry.

Claims (8)

10 mass% to 40 mass% of the following polyethylene component (A) polymerized with a metallocene catalyst, 5 mass% to 50 mass% of the following polyethylene component (B) polymerized with a chromium catalyst, and Ziegler A polyethylene resin composition containing 40% by mass or more and 85% by mass or less of the following polyethylene component (C) polymerized by a Natta catalyst and satisfying the following characteristics (1) to (5) and (9) .
Polyethylene component (A); Characteristic (a1): Melt flow rate (HLMFR) at a temperature of 190° C. and a load of 21.6 kg is 0.57 g/10 minutes or more and less than 5 g/10 minutes, and characteristic (a2): density is 0.915 g / cm ³ or more 0.945 g / cm ³ der hereinafter is, characteristics (a3): dynamic melt viscosity eta _{H · 0.01} the frequency ω at a temperature 190 ° C. is measured when 0.01 rad / sec (unit: Pa · sec) 100,000 exceeded, polyethylene Ru der less than 800,000.
Polyethylene component (B); Characteristic (b1): HLMFR is 2 g/10 minutes or more and less than 20 g/10 minutes, and characteristic (b2): Density is more than 0.945 g/cm ^{3 and} 0.965 g/cm ³ or less. Characteristics (b3): elongation viscosity η(t) (unit: Pa·sec) and elongation time t (unit: sec) measured at a temperature of 170° C. and elongation strain rate of 0.1 (unit: 1/sec). Polyethylene where the inflection point of extensional viscosity due to strain hardening is observed in a log-log plot.
Polyethylene component (C); Characteristic (c1): Melt flow rate (MFR) at a temperature of 190° C. and a load of 2.16 Kg is 10 g/10 minutes or more and 200 g/10 minutes or less, and characteristic (c2): density is 0. 960 g / cm ³ or more 0.980 g / cm ³ or less polyethylene is.
Characteristic (1): MFR is 0.1 g/10 minutes or more and 1 g/10 minutes or less.
Characteristic (2): HLMFR is 10 g/10 minutes or more and 50 g/10 minutes or less.
Characteristic (3): The melt flow rate ratio (HLMFR/MFR), which is the ratio of HLMFR to MFR, is 50 or more and 130 or less.
Characteristics (4): density of 0.940 g / cm ³ or more 0.965 g / cm ³ or less.
Characteristic (5): Both elongation viscosity η(t) (unit: Pa·sec) and elongation time t (unit: sec) measured at a temperature of 170° C. and elongation strain rate of 0.1 (unit: 1/sec). In the logarithmic plot, the inflection point of elongational viscosity due to strain hardening is observed.
Characteristic (9): Dynamic melt viscosity η _H of polyethylene component (A) against dynamic melt viscosity η _W·0.01 of polyethylene resin composition measured at a frequency ω of 0.01 rad/sec at a temperature of 190° C. _{· 0.01} ratio eta _H-0.01 / eta _W-0.01 1 excess is less than 14. The polyethylene resin composition according to claim 1, wherein the polyethylene component (B) satisfies the following characteristic (b4).
Characteristic (b4): The molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) is 10 or more and 50 or less. Furthermore, the polyethylene resin composition according to claim 1 or 2, which satisfies the following characteristic (6).
Characteristic (6): The peak top time (T) and the melting point (Tm) in the isothermal crystallization at 121.5° C. measured by a differential scanning calorimeter (DSC) satisfy the following relational expression (1).
T [second]≦−76.80×Tm [° C.]+10,410 Relational expression (1) Furthermore, the polyethylene resin composition according to any one of claims 1 to 3, which satisfies the following characteristic (7).
Characteristic (7): Melt tension (MT) measured at 190° C. is 50 mN or more. Polyethylene component (A) is a polyethylene resin composition according to any one of claims 1 to 4, satisfying the following properties (a4).
Characteristic (a4): The melt flow rate ratio (HLMFR/MFR), which is the ratio of HLMFR to MFR, is 10 or more and 35 or less. Polyethylene component (C) is represented by the following characteristics (c3) and (c4) a polyethylene resin composition according to any one of claims 1 to 5 satisfying.
Characteristic (c3): Melt flow rate (MLMFR) at a temperature of 190° C. and a load of 11.1 Kg is 50 g/10 minutes or more and 2,000 g/10 minutes or less.
Characteristic (c4): The melt flow rate ratio (MLMFR/MFR), which is the ratio of MLMFR to MFR, is 3 or more and 15 or less. Moldings produced using the polyethylene resin composition according to any one of claims 1-6. Container created using polyethylene resin composition according to any one of claims 1-6.