JP2017179300A - Polyethylene resin composition, molded body thereof and container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyethylene resin composition excellent in hollow moldability, environmental stress crack resistance and impact resistance and capable of manufacturing a molded article excellent in appearance, and provide a molded body and a container consisting of the same.SOLUTION: There is provided a polyethylene resin composition containing a specific polyethylene component (A) of 10 to 40 mass%, a specific polyethylene component (B) of 10 to 80 mass% and a specific polyethylene component (C) of 10 to 80 mass% and satisfying properties (1) to (5). Property (1):MFR is 0.1 to 1 g/10 min. Property (2):HLMFR is 10 to 50 g/10 min. Property (3):HLMFR/MFR is 40 to 140. Property (4):density is 0.940 to 0.965 g/cm. Property (5):an inflection point of elongation viscosity caused by strain hardening is observed in a double logarithmic plot of elongation viscosity η(t) (unit:Pa sec.) and elongation time t (unit:sec.) measured at temperature of 170°C and elongation strain rate of 0.1 (unit:1/sec.).SELECTED DRAWING: None

Description

  The present invention relates to a polyethylene resin composition, and a molded body and a container comprising the same.

In polyethylene hollow molding, injection molding, inflation molding, and extrusion molding, materials having good molding processability and physical properties are generally required. Especially for hollow bottles that are generally used as cosmetic containers, detergents, shampoos and rinse containers, or food containers such as edible oils, a polyethylene resin excellent in moldability, physical characteristics and chemical characteristics. Is widely used.
Furthermore, in recent years, there has been a demand for lighter and thinner hollow bottles in order to reduce costs. In these hollow bottle applications, particularly excellent properties such as environmental stress crack resistance and impact strength are required. Yes. As polyethylene that satisfies such requirements, those having a relatively high molecular weight and a wide molecular weight distribution are suitable.

Polyethylene polymerized using a chromium-based catalyst has a relatively wide molecular weight distribution and a molecular structure having a long-chain branched structure, which makes it easy to hollow-mold, specifically, a high melt tension and swell ratio. In addition, since the pinch-off part of the hollow bottle is easily thickened uniformly, it is generally widely used as a hollow molding material.
In addition, polyethylene that has been two-stage polymerized using a titanium-based catalyst can impart excellent environmental stress crack resistance by selectively copolymerizing a comonomer with a high molecular weight component, and low Since the molecular weight and molecular weight distribution can be adjusted by controlling the molecular weight component, it is generally widely used as a high environmental stress cracking grade suitable for hollow molding.
And the polyethylene polymer composition which mixed the polyethylene polymerized in two steps using the titanium-type catalyst and the polyethylene polymerized using the chromium-type catalyst, and made use of the mutual advantage is disclosed (for example, patent document) 1-7).
However, as the weight of containers and the diversification of designs continue to increase, it is necessary to increase the density of polyethylene when attempting to secure the rigidity of the container while the container is thinned, that is, the amount of comonomer copolymerization is suppressed. Since there is a need and it is contrary to the maintenance of the environmental stress crack resistance, there is still a demand for a material that has an excellent balance between rigidity and environmental stress crack resistance and can cope with the thinning.

Therefore, a polyethylene resin composition composed of multiple components is disclosed which includes polyethylene using a metallocene catalyst and has improved rigidity and environmental stress crack resistance balance (see, for example, Patent Documents 8 to 13).
However, polyethylene using a metallocene-based catalyst has a relatively narrow molecular weight distribution and a molecular structure having a uniform comonomer distribution. Since the melt tension and the swell ratio are small, it is limited to the purpose of storing a specific content liquid or as a container having a specific shape.
Furthermore, as described in Patent Document 8, polyethylene using a metallocene-based catalyst has a low melting point and crystallization temperature corresponding to the same density, that is, it is easy to melt due to rigidity and is difficult to crystallize. The phenomenon that the speed is reduced is recognized, and there is a need to further increase the crystallization speed for high-speed molding.

And, including polyethylene using a metallocene catalyst, and further mixing polyethylene polymerized using a chrome catalyst, taking advantage of each other, it is excellent in balance between rigidity and environmental stress crack resistance and suitable for hollow moldability. The intended polyethylene polymer composition is disclosed (for example, Patent Documents 14 to 16).
However, Patent Document 14 discloses that a low gel is obtained by mixing a polyethylene using a high molecular weight metallocene catalyst and a polyethylene polymerized using a chromium catalyst, and having good mechanical strength and moldability and compatibility of each component. However, the composition has a very high viscosity and is not suitable for high-speed moldability, and its application is limited to a large hollow molded container.
In Patent Documents 15 and 16, a composition having both mechanical strength and formability 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 has been disclosed, the compatibility of each component has not been sufficiently studied, and the molecular weight of polyethylene using a high molecular weight metallocene catalyst is too high or contributes to compatibility. Since the blended 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 enhancing the environmental stress crack resistance of polyethylene using a metallocene-based catalyst, an increase in molecular weight is extremely effective, while compatibility with other polyethylenes deteriorates, so polyethylene using a metallocene-based catalyst In the polyethylene resin composition containing, a resin design that achieves compatibility and resistance to environmental stress cracking is important.
In view of such circumstances, while having the hollow moldability, high rigidity, impact resistance, etc. required for the conventional polyethylene resin composition for containers, the crystallization speed is fast, 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 a molded product.

Therefore, the present applicant has found a polyethylene material having a high crystallization speed 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).
In Patent Documents 17 to 19, polymerized using a metallocene-based catalyst containing Ti, Zr or Hf with respect to 60 to 90% by mass of specific polyethylene, HLMFR and density are specific values, respectively, and long chain branching A polyethylene resin composition for containers which contains 10 to 40% by mass of a specific ethylene polymer having a structure and satisfies specific characteristics is disclosed.
In addition, in Japanese Patent Application Laid-Open No. 2004-228867, the present applicant has disclosed 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 comprising the same. Disclosure.
However, the required performance required for products is increasing day by day, and further performance improvement is demanded in the problems of the prior art.

JP 59-196345 A JP 59-196346 A Japanese Unexamined Patent Publication No. 60-036547 JP 2004-059650 A JP 2004091739 A JP 2004-168817 A JP 2005-29881 A JP 08-283476 A Japanese Patent Laid-Open No. 08-283477 JP 2006-83370 A JP-A-11-106574 JP 11-199719 A JP 2009-7579 A JP 2003-213053 A Japanese Patent Laid-Open No. 11-138618 Special table 2009-506163 JP2013-204015A JP 2014-208749 A JP 2014-208750 A JP 2014-208817 A

  In view of the above-mentioned problems of the prior art, the object of the present invention is excellent in hollow moldability, environmental stress crack resistance, impact resistance, thinner and lighter, with high melt tension and high draw resistance. Providing a polyethylene resin composition and a molded body made of the same that have excellent down properties, good pinch-off characteristics, can be hollow-molded with complex shapes, have high compatibility with resin components, and are particularly excellent in the appearance of the molded body There is to do.

  As a result of intensive studies to solve the above problems, the inventors of the present invention contain specific amounts of specific polyethylene component (A), polyethylene component (B) and polyethylene component (C), and satisfy specific characteristics. The polyethylene resin composition has excellent hollow moldability, environmental stress crack resistance and impact resistance, can be molded thinner and lighter, has high melt tension, excellent drawdown resistance, and good pinch-off characteristics. Thus, it is found that a polyethylene resin composition and a molded body comprising the same can be obtained, and a hollow resin having a complicated shape can be obtained, and the compatibility of the resin components is high and the appearance of the molded body is excellent. It came to.

In the polyethylene resin composition of the present invention, the following polyethylene component (A) is 10% by mass to 40% by mass, the following polyethylene component (B) is 10% by mass to 80% by mass, and the following polyethylene component (C) is 10% by mass. It is contained in an amount of 80% by mass or more and satisfies the following characteristics (1) to (5).
Polyethylene component (A); Characteristic (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 characteristic (a2): density is Polyethylene which is 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 min or more and less than 400 g / 10 min, characteristic (b2): density is 0.940 g / cm ³ or more and 0.970 g / cm ³ or less Characteristic (b3): Temperature of 170 ° C., Elongation viscosity η (t) (unit: Pa · second) measured at an elongation strain rate of 0.1 (unit: 1 / second) and elongation time t (unit: second) Polyethylene in which an inflection point of elongational viscosity due to strain hardening is observed in a log-log plot.
Polyethylene component (C); property (c1): melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 10 g / 10 min or more and 200 g / 10 min or less, and property (c2): density is 0.1. 960 g / cm ³ or more 0.980 g / cm ³ or less polyethylene is.
Characteristic (1): MFR is 0.1 g / 10 min or more and 1 g / 10 min or less.
Characteristic (2): HLMFR is 10 g / 10 min or more and 50 g / 10 min or less.
Characteristic (3): Melt flow rate ratio (HLMFR / MFR) which is a ratio of HLMFR to MFR is 40 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 · second) and elongation time t (unit: second) measured at a temperature of 170 ° C. and an elongation strain rate of 0.1 (unit: 1 / second) In the logarithmic plot, an inflection point of elongational viscosity due to strain hardening is observed.

In the polyethylene resin composition of the present invention, the polyethylene component (A) preferably satisfies the following property (a3).
Characteristic (a3): Dynamic melt viscosity η _{H · 0.01} (unit: Pa · second) measured when the frequency ω is 0.01 rad / sec at a temperature of 190 ° C. exceeds 100,000, 1,000,000 Less than.

In the polyethylene resin composition of the present invention, the polyethylene component (A) preferably satisfies the following property (a4).
Characteristic (a4): Melt flow rate ratio (HLMFR / MFR) which is a ratio of HLMFR to MFR is 10 or more and 35 or less.

In the polyethylene resin composition of the present invention, the polyethylene component (C) preferably satisfies the following properties (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 min or more and 2,000 g / 10 min or less.
Characteristic (c4): Melt flow rate ratio (MLMFR / MFR) which is a ratio of MLMFR to MFR is 3 or more and 15 or less.

The polyethylene resin composition of the present invention preferably further satisfies the following property (6).
Characteristic (6): The melt tension (MT) measured at 190 ° C. is 60 mN or more.

  The molded body of the present invention is produced using the polyethylene resin composition.

  The container of the present invention is produced using the polyethylene resin composition.

According to the present invention, it has excellent hollow moldability, environmental stress crack resistance, and impact resistance, can be molded with a thinner and lighter weight, has high melt tension, excellent drawdown resistance, and good pinch-off characteristics. In addition, it is possible to provide a polyethylene resin composition that is capable of hollow molding with a complicated shape and that has a high compatibility of the resin components and is excellent in the appearance of the molded body.
Moreover, according to this invention, there exists an effect that it can provide the molded object and container which are excellent in environmental stress crack resistance and impact resistance, are excellent in surface properties, and are excellent in an external appearance.

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

In the polyethylene resin composition of the present invention, the following polyethylene component (A) is 10% by mass to 40% by mass, the following polyethylene component (B) is 10% by mass to 80% by mass, and the following polyethylene component (C) is 10% by mass. It is contained in an amount of 80% by mass or more and satisfies the following characteristics (1) to (5).
Polyethylene component (A); Characteristic (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 characteristic (a2): density is Polyethylene which is 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 min or more and less than 400 g / 10 min, characteristic (b2): density is 0.940 g / cm ³ or more and 0.970 g / cm ³ or less Characteristic (b3): Temperature of 170 ° C., Elongation viscosity η (t) (unit: Pa · second) measured at an elongation strain rate of 0.1 (unit: 1 / second) and elongation time t (unit: second) Polyethylene in which an inflection point of elongational viscosity due to strain hardening is observed in a log-log plot.
Polyethylene component (C); property (c1): melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 10 g / 10 min or more and 200 g / 10 min or less, and property (c2): density is 0.1. 960 g / cm ³ or more 0.980 g / cm ³ or less polyethylene is.
Characteristic (1): MFR is 0.1 g / 10 min or more and 1 g / 10 min or less.
Characteristic (2): HLMFR is 10 g / 10 min or more and 50 g / 10 min or less.
Characteristic (3): Melt flow rate ratio (HLMFR / MFR) which is a ratio of HLMFR to MFR is 40 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 · second) and elongation time t (unit: second) measured at a temperature of 170 ° C. and an elongation strain rate of 0.1 (unit: 1 / second) In the logarithmic plot, an inflection point of elongational viscosity due to strain hardening is observed.
Hereinafter, the present invention will be described in detail for each item.

1. Polyethylene component (A)
Characteristics (a1)
The polyethylene component (A) used in the present invention is selected from those having an HLMFR of 0.2 g / 10 min or more and less than 5 g / 10 min from the viewpoint of the effects of the present invention. The HLMFR of the polyethylene component (A) is preferably in the range of 0.3 g / 10 min or more and 1.0 g / 10 min or less, more preferably 0.4 g / 10 min or more and 0.7 g / 10 min or less. If this HLMFR is less than 0.2 g / 10 min, in the final resin composition, the HLMFR may not be within the specified range, and the fluidity may be reduced or the compatibility may be reduced. There is a risk of damaging the appearance. On the other hand, if the HLMFR is 5 g / 10 min or more, the final resin composition cannot achieve 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, a polyethylene component having a density of 0.915 g / cm ³ or more and 0.945 g / cm ³ or less is selected from the point of achieving the effects 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, the rigidity is insufficient, and the crystallization rate decreases, with the result that the molding cycle may decrease. . On the other hand, when the density exceeds 0.945 g / cm ³ , the environmental stress crack resistance may be lowered in the final resin composition.
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 polymerization of the polyethylene component (A).

Characteristic (a3)
The polyethylene component (A) used in the present invention preferably satisfies the following property (a3).
Property (a3): Dynamic melt viscosity η _{H · 0.01} (unit: Pa · second) 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 .
The polyethylene component (A) used in the present invention has a dynamic melt viscosity η _{H · 0.01} (unit: Pa · second) having a frequency ω of 0.01 rad / second in the characteristic (a3) of 1,000,000. Less than 000 is preferable, but less than 800,000 is more preferable, and less than 600,000 is even more preferable. On the other hand, the lower limit is not particularly limited, but preferably exceeds 100,000, more preferably 200,000 or more, for the reason that an appropriate molecular weight is required in order to maintain high environmental stress crack resistance in the final resin composition. Preferably, 300,000 or more is even more preferable. When the dynamic melt viscosity is less than 1,000,000, the viscosity of the polyethylene component (A) is kept 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 kept small, and a composition having excellent compatibility can be obtained. Therefore, it is easy to improve the appearance of the molded product, and it is easy to suppress deterioration in physical properties such as impact resistance.
The dynamic melt viscosity is obtained by blending 2000 ppm of an antioxidant (IRGANOX B225 manufactured by BASF Japan) into a sample and melt-kneading it into a 1.0 mm thick sheet by hot pressing, and using a rheometer (Ares manufactured by Rheometrics). Using a parallel plate, the sample is brought into close contact with the plate and melted, and then the stress is relaxed at a temperature of 210 to 220 ° C., and the temperature is lowered to 190 ° C. while adjusting the plate interval so that there is no gap between the plates. In this case, the measurement is performed in the range of the plate interval of about 1.0 mm and the strain of 0.2 to 1%, and the frequency ω can be measured at 0.01 rad / sec.
The dynamic melt viscosity of the polyethylene component (A) can generally be controlled by the molecular weight, molecular weight distribution, long chain branching structure, and the like. Therefore, in order to obtain a polyethylene component (A) having a dynamic melt viscosity in a specific range, a polyethylene having a specific molecular weight and molecular weight distribution and having an appropriate long chain branched structure can be obtained. It can obtain suitably by superposing | polymerizing using.

Characteristic (a4)
The polyethylene component (A) used in the present invention preferably satisfies the following property (a4).
Characteristic (a4): Melt flow rate ratio (HLMFR / MFR) which is a ratio of HLMFR to MFR is 10 or more and 35 or less.
According to characteristic (a4), HLMFR / MFR is preferably 30 or less, more preferably 25 or less, on the other hand, preferably 15 or more, more preferably 20 or more.
HLMFR / MFR has a strong correlation with the molecular weight distribution. When HLMFR / MFR takes a large value, the molecular weight distribution becomes wide, and when HLMFR / MFR takes a small value, the molecular weight distribution becomes narrow. When HLMFR / MFR exceeds 35, it is suggested that the influence by the long-chain branched structure appears strongly. When 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 body are easily smoothed, the appearance is excellent, and the 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 for the reason that impact resistance and environmental stress crack resistance (ESCR) are required.
MFR can be measured according to JIS K6922-2: 1997.
Moreover, the control method of HLMFR / MFR can be performed mainly according to the control method of molecular weight distribution.

Characteristics (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 the inflection point of the 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 both logarithmic plots of the viscosity η (t) (unit: Pa · second) and the extension time t (unit: second), it becomes easy to observe the inflection point of the extension viscosity due to strain hardening. By observing the inflection point, the polyethylene resin composition has an effect that the crystallization rate can be extremely effectively increased and the molding cycle is 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 branch structure, a component having a long relaxation time due to entanglement of long-chain branches increases. As a result, even in the same molecular weight and molecular weight distribution, the viscosity in the low shear rate region increases, so η ₀ (zero shear viscosity) shows a large value, MFR decreases, and HLMFR / MFR increases. . That is, taking a large value of HLMFR / MFR is regarded as one of the indicators suggesting an increase in the entanglement of long chain branching. Therefore, the inflection point of elongation viscosity is observed in the polyethylene resin composition, and the HLMFR / MFR in the polyethylene component (A) is 10 or more and 35 or less, the specific long chain in which the polyethylene component (A) is controlled. It suggests having 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 the strain hardening degree.
Regarding the method for measuring the strain hardening degree, as long as the uniaxial extensional viscosity can be measured, the same value can be obtained in principle by any method. For example, the measurement method and the measuring instrument are disclosed in publicly known document: Polymer 42 (2001) 8663. Details are described.
In the measurement of polyethylene according to the present invention, preferable measurement methods and measuring instruments include the following.

Measuring method:
・ Device: Ares manufactured by Rheometrics
-Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
・ Measurement temperature: 170 ℃
-Strain rate: 0.1 / second-Preparation of test piece: Press-molded to produce a sheet of 18 mm x 10 mm and a thickness of 0.7 mm.

Calculation method:
The elongational viscosity at 170 ° C. and a strain rate of 0.1 / second is plotted as a log-log graph of time t (second) on the horizontal axis and elongation viscosity η (t) (Pa · second) on the vertical axis. On the log-log graph, the maximum elongation viscosity until strain becomes 4.0 after strain hardening is η _Max (t1) (t1 is the time when the maximum elongation viscosity is shown), and the extension viscosity before strain hardening. when the approximate line and η _linear (t), defines the value calculated as _{η Max (t1) / η linear} (t1) strain hardening degree and (.lambda.max). The presence / absence of strain hardening is determined by whether or not there is an inflection point at which the extensional viscosity changes from an upward convex curve to a downward convex curve over time.
1 and 2 are typical plots of elongational viscosity. FIG. 1 shows a case where an inflection point of elongational viscosity is observed, and η _Max (t1) and η _Linear (t1) are shown in the figure. FIG. 2 shows a case where an inflection point of elongational viscosity is not observed.

  In order for the polyethylene component (A) to have a long-chain branched structure, it is preferable to perform polymerization by applying an appropriate polymerization catalyst, and it is preferable to select from polymerization catalysts as described later.

Characteristic (a6)
The polyethylene component (A) used in the present invention preferably satisfies the following property (a6).
Characteristic (a6): When the dynamic melt viscosity η ^* (Pa · sec) measured at a temperature of 190 ° C. in the frequency range of 100 rad / sec to 0.01 rad / sec 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 representing the relaxation time, and n is a parameter representing the shear rate dependence of the melt viscosity in the high shear rate region.)
The polyethylene component (A) used in the present invention preferably has a zero shear viscosity η ₀ (unit: Pa · second) of 1,000,000 or less in the characteristic (a6), but less than 800,000. 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 in order to maintain high environmental stress cracking resistance in the final resin composition. More preferably, it is 200,000 or more, More preferably, it is 400,000 or more. When the zero shear viscosity is 1,000,000 or less, the viscosity of the polyethylene component (A) is kept low, and the viscosity ratio between the low molecular weight component polyethylene component (C) and the high molecular weight component polyethylene component (A). Is preferable from the viewpoint that the composition can be kept small and a composition having excellent compatibility can be obtained. Therefore, it is easy to improve the appearance of the molded product, and it is easy to suppress deterioration in 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 is herein referred to as ANTEC '94 (The Society of Plastics Engineers, 1994) along with the relaxation time τ ₀ (sec). ), Page 1814 (written by S. Lai et al.), A value obtained by approximating the dynamic melt viscosity η ^* (unit: Pa · second) with the cross viscosity formula (the following relational expression (2)). Here, the dynamic melt viscosity η ^* is in the range of a plate interval of 1.0 mm using a parallel plate at 190 ° C., a strain of 0.2 to 1%, and a frequency ω of 100 to 0.01 (unit: rad / sec). The value obtained when measured with a rheometer (Ales manufactured by Rheometrics), and the approximation of the result to the following relational expression (2) uses a computer program marketed by the regression method 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 the melt viscosity in the high shear rate region, and τ ₀ is a parameter representing the relaxation time.

In general, when polyethylenes having different molecular weights, in other words, polyethylenes having different viscosities are melt-mixed, the smaller the viscosity ratio of the two, the easier it is to mix. It is known that the component is unevenly distributed due to poor dispersion and becomes a gel, which causes poor appearance. For example, more detailed research has been conducted on Newtonian fluids. When liquids with different viscosity ratios are mixed together, the conditions for dispersing high-viscosity liquids: the number of capillaries depends on the kneading mode and the viscosity ratio between the two. It has been reported that it can be arranged (HP Grace: Chem. Eng. Commun., 14, 225 (1982)). It is also reported that when the same strain is applied to a system in which liquids with different viscosity ratios are mixed, the higher the viscosity ratio, the lower the strain rate of the high-viscosity liquid and the cause of poor dispersion. (A. Biswas et al .: SPE-ANTEC, 336 (1994)).
On the other hand, since polyethylene resins and the like are non-Newtonian fluids, the viscosity depends on the shear rate, so the above knowledge cannot be applied simply, but it is considered that the above knowledge can be referred to. Therefore, in the dispersion of polyethylene having a large viscosity ratio, it is considered that the viscosity in the region where the strain rate of the high viscosity component is small is an important factor, and the viscosity in the region where the strain rate of the resin is small is within the scope of the present invention. It is assumed that the polyethylene component (A) is 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 molecular weight, molecular weight distribution, long chain branching, and the like. Therefore, in order to obtain the zero shear viscosity η ₀ in a specific range, a long chain branched structure having a specific molecular weight and molecular weight distribution and appropriately controlled may be used. By using the catalyst, it can be suitably produced.

  From the above, it is considered that the resin composition containing a component having a long-chain branched structure may have poor compatibility. However, even if it has a long-chain branch structure, the length and / or number of long-chain branches can be obtained by using a component having a specific melt flow rate ratio (HLMFR / MFR) and a specific viscosity characteristic. In the resin composition, while the compatibility is improved, the effect of having a long-chain branched structure is also exhibited, and the effect of the present invention as described above is exhibited. It 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. Preferably, the polymerization catalyst is a specific metallocene catalyst, that is, a catalyst having a specific structure metallocene complex. Can be produced by polymerization.
In addition, the polyethylene component (A) having a long-chain branched structure can be obtained by forming polyethylene (macromonomer) having a terminal vinyl group by chain transfer to ethylene and copolymerizing the macromonomer and ethylene.
Among the metallocene catalysts, catalysts having a metallocene complex having a specific structure are preferred, particularly metallocene complexes having a cyclopentadienyl ring and a heterocyclic aromatic group, or metallocene complexes having a cyclopentadienyl ring and a fluorenyl ring. 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 co-catalyst and a complex called a metallocene complex in which a ligand having a cyclopentadiene skeleton is coordinated to 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 Group 3 elements 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 includes the following catalyst component (i) and catalyst component (ii), and is a catalyst combined with the catalyst component (iii) as necessary.
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 Group 4 transition metal of the periodic table is used. Specifically, compounds represented by the following general formulas (I) to (VII) are used.

^{_{(C 5 H 5-a R}} 1 a) (C 5 H 5-b R 2 b) MXY 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 binding groups that bridge two conjugated five-membered ring ligands, Q ² is a binding group that bridges conjugated five-membered ring ligands and Z groups, Q ³ is a bonding group that bridges R ⁴ and R ⁵ , M is a transition metal of Group 3-12 of the periodic table, X, Y, and W are each independently hydrogen, halogen, C 1-20 Hydrocarbon group, oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or silicon-containing hydrocarbon having 1 to 20 carbon atoms Z represents oxygen, a ligand containing sulfur, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms. 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, silicon A hydrocarbon-containing group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group; Among these, it is preferable that at least one of R ^{1 to} R ⁵ is a heterocyclic aromatic group. Among the heterocyclic aromatic groups, a furyl group, a benzofuryl group, a thienyl group, and a benzothienyl group are preferable, and a furyl group and a benzofuryl group are more preferable. These heterocyclic aromatic groups include hydrocarbon groups having 1 to 20 carbon atoms, halogen groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups, silicon-containing hydrocarbon groups, and phosphorus-containing carbon groups. Although it may have a hydrogen group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, in that case, a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing hydrocarbon group are preferable. Also, two adjacent R ¹ , 2 R ² , 2 R ³ , 2 R ⁴ , 2 R ⁵ , 2 R ⁶ , or 2 R ⁷ are bonded to each other. Thus, a ring having 4 to 10 carbon atoms may be formed. a, b, c, d, e, f, g, h, i, and j are 0 ≦ a ≦ 5, 0 ≦ b ≦ 5, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, and 0 ≦ e ≦, respectively. 4, 0 ≦ f ≦ 5, 0 ≦ g ≦ 5, 0 ≦ h ≦ 5, 0 ≦ i ≦ 3, 0 ≦ j ≦ 3.

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

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

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

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

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

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

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

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

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

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

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

Among these, a compound of a combination of secondary carbon and primary carbon is preferable, and rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (CHMe ₂ )-is more preferable. _{5-Me} 2 ZrCl 2,} rac- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2, meso- (Me 2 Si) 2 {η 5 _{-C 5 H-3- (CHMe 2} ) -5-Me} 2 ZrCl 2, meso- (Me 2 Si) 2 {η 5 -C 5 H-3- (CHMe 2) -5-Me} 2 ZrMe 2 Rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (dimethylsilyl) -5-Me} ₂ ZrCl ₂ , rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- _{(dimethylsilyl) -5-Me} 2 ZrMe 2} , meso- ^{_{Me 2 Si) 2 {η 5}} -C 5 H-3- ( _{butyldimethylsilyl) -5-Me} 2 ZrCl 2} , meso- (Me 2 Si) 2 {η 5 -C 5 H-3- ( dimethylsilyl) −5-Me} ₂ ZrMe ₂ .
In addition, the compound which replaced the silylene group of the compound of these specific examples with the germylene group is illustrated as a suitable compound.
As specific examples of the metallocene complex, JP-A-7-188335, Journal of American Chemical Society, 1996, Vol. A transition metal compound having a ligand containing one or more elements other than carbon in a 5-membered ring or a 6-membered ring disclosed in 118, 2291 can also be used.
An example of a metallocene complex having a heterocyclic hydrocarbon group as a substituent is disclosed in Japanese Patent No. 3675509.

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

As an example of a preferable 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 a furyl group, a benzofuryl group, a thienyl group, and a benzothienyl group. These substituents may further have a substituent such as a silicon-containing group. Of the substituents selected from the group consisting of furyl, benzofuryl, thienyl and benzothienyl, furyl and benzofuryl are more preferred. Further, these substituents are preferably 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 is added. It is particularly preferred that the compound has.

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

  These metallocene complexes are preferably used as supported catalysts as described later. In the first group of compounds, the interaction between the so-called hetero atom contained in the furyl group and thienyl group and the solid acid on the carrier causes non-uniformity in the active site structure, and long chain branching is likely to occur. I think. Also in the second compound group, it is thought that the use of a supported catalyst changed the space around the active site, so that long chain branching was easily generated.

(2) Catalyst component (ii)
The method for producing a polyethylene component (A) according to the present invention forms a cationic metallocene compound by reacting with the metallocene compound of the catalyst component (i) in addition to the catalyst component (i) as an essential component of the olefin polymerization catalyst. And a fine particle carrier (catalyst component (iii)) as necessary.

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

As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any 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 formula (VIII)
(In the general formula (VIII), R ^a represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, aralkyl group or the like having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, 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 the 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. It is particularly preferred that
Two or more of the above organoaluminum compounds can be mixed and used.

The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably 0.25 / 1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1/1, and the reaction temperature is Usually, it is -70-100 degreeC, Preferably it exists in the range of -20-20 degreeC. 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 crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like and components capable of generating water in the reaction system can be used.
Of the organoaluminum oxy compounds described above, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, particularly methylaluminoxane (including those substantially consisting of methylaluminoxane (MAO)). Is suitable as an organoaluminum oxy compound.
Of course, as the organoaluminum oxy compound, two or more of the above organoaluminum oxy compounds may be used in combination, and a solution obtained by dispersing or dispersing the organoaluminum oxy compound in the above-described inert hydrocarbon solvent. You may use.

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 ( Perfluoroanthryl) borane, tris (perfluorobi) Fuchiru) such as borane and the like.

  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, and tris (perfluorobinaphthyl) borane are more preferred, and tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris ( Perfluoronaphthyl) borane and tris (perfluorobiphenyl) borane are exemplified as preferred compounds.

When the borate compound is specifically represented, 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 a Bronsted acid such as ammonium, anilinium, or phosphonium.
Examples of ammonium include trialkylammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.

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

In 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, As the substituent of the substituted aromatic hydrocarbon group, an alkyl group typified 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. .
Furthermore, ^Xb and ^Xc are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted carbon atom 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-difluorophene) L) borate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium 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-ditrifluoromethylphenyl) borate, triethyl Ammonium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, di (1 -Propyl) ammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate and the like.

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

Moreover, the 2nd example of a 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 a carbocation, a methyl cation, an ethyl cation, a propyl cation, an isopropyl cation, a butyl cation, an isobutyl cation, a tert-butyl cation, a pentyl cation, a tropinium cation, a benzyl cation, a trityl cation, A sodium cation, a proton, etc. are mentioned. 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, Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoro) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) Rate, 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, tropicity tetra (perfluoro-naphthyl) _{borate, NaBPh 4, NaB (o-} CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 - Ph) ₄ , Na _{B (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 _{^{ethers, 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, can be exemplified _{H + B (C 10 H 7} ) 4 · 2 diethyl ether it can.

Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, Tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) 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, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (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.

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

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

Further, as the metal oxide, either alone oxide or composite oxide of the Periodic Table 1-14 Group elements include, 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 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 represents not the molecular formula but only the composition, and the structure and the catalyst component ratio of the composite oxide used in the present invention are not particularly limited.
In addition, the metal oxide used in the present invention may absorb a small amount of moisture or may contain a small amount of impurities.

As the metal chloride, for example, an alkali metal or alkaline earth metal chloride is preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable.
As the metal carbonate, carbonates of alkali metals and alkaline earth metals are preferable, and specific examples 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 suitably used in the present invention, but the use of metal oxides, silica, alumina and the like is particularly preferable.

These inorganic carriers are usually baked in air or an inert gas such as nitrogen or argon at 200 to 800 ° C., preferably 400 to 600 ° C., and the amount of surface hydroxyl group is 0.8 to 1.5 mmol / g. It is preferable to adjust to use.
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 mm, preferably 50 to 500 mm, and the specific surface area is 150 to 1000 m. ² / g, preferably 200-700 m ² / g, pore volume 0.3-2.5 cm ³ / g, preferably 0.5-2.0 cm ³ / g, apparent specific gravity 0.10-0. It is preferable to use an inorganic carrier having 50 g / cm ³ .

  Of course, the above-mentioned inorganic carriers can be used as they are, but as a pretreatment, these carriers are trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, It can be used after contacting 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 employing specific polymerization conditions, the polyethylene component (A) preferred in the present invention can be easily produced.

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

Contact method (1): After contacting the catalyst component (i) and the catalyst component (ii), the catalyst component (iii) is contacted.
Contact method (2): After contacting the catalyst component (i) and the catalyst component (iii), the catalyst component (ii) is contacted.
Contact method (3): The catalyst component (ii) and the catalyst component (iii) are contacted, and then the catalyst component (i) is contacted.

Of these contact methods, contact methods (1) and (3) are preferred, and contact method (1) is most preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually 6 to 12 carbon atoms), heptane, hexane, decane and dodecane. 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, a method of bringing each component into contact with stirring or non-stirring is employed.
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, more preferably. It is desirable to carry out in 30 minutes to 12 hours.

  In addition, when contacting the catalyst component (i), the catalyst component (ii) and the catalyst component (iii), as described above, an aromatic hydrocarbon solvent in which a certain component is soluble or hardly soluble, and a certain component Any insoluble or hardly soluble aliphatic or alicyclic hydrocarbon solvent can be used.

  In the case where the contact reaction between the components is performed stepwise, this may be used as it is as the solvent for the subsequent contact reaction without removing the solvent used in the previous step. In addition, after the previous catalytic reaction using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.) Hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons) and the desired product is recovered as a solid or once or part of the soluble solvent is removed by means such as drying. 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 this invention, it does not prevent performing contact reaction of each component in multiple times.

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

When an organoaluminum oxy compound is used as the catalyst component (ii), the atomic ratio (Al / M) of the aluminum of the organoaluminum 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 / M) is usually selected in the range of 0.01 to 100, preferably 0.1 to 50, more preferably 0.2 to 10.
Further, when a mixture of an organoaluminum oxy compound, a borane compound, and a borate compound is used as the catalyst component (ii), the same use as described above for the transition metal (M) for each compound in the mixture It is desirable to select by percentage.

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

  The catalyst component (i), the catalyst component (ii), and the catalyst component (iii) are brought into contact with each other by any one of the contact methods (1) to (3), and then the solvent is removed. The catalyst for olefin polymerization can be obtained as a solid catalyst. The removal of the solvent is desirably carried out 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 contacted to remove the solvent, and this is used as a solid catalyst component, and an organoaluminum oxy compound, borane compound, borate compound or these under polymerization conditions In contact with the mixture.
Contact method (5): The organoaluminum oxy compound, borane compound, borate compound or mixture thereof and catalyst component (iii) are contacted to remove the solvent, which is used as a solid catalyst component, and the catalyst component ( Contact with i).
In the case of the contact methods (4) and (5), the same conditions as described above can be used for the component ratio, contact conditions, and solvent removal conditions.

Moreover, a layered silicate can also be used as a component which 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 or the like are stacked in parallel with each other with a weak binding force.
Most layered silicates are naturally produced mainly as the main component of clay minerals, but these layered silicates are not limited to natural ones and may be artificially synthesized.

  Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite and the like, smectite group, vermiculite group and mica group are preferable.

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

  The layered silicate can control the particle properties by pulverization, granulation, sizing, fractionation, etc. at any time before, during, or after all the steps. The method can be any purposeful. In particular, for granulation methods, for example, spray granulation method, rolling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation Method, emulsion granulation method and submerged granulation method. Particularly preferable granulation methods are the spray granulation method, the rolling granulation method and the compression granulation method.

  Of course, 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 organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

In the metallocene 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), the organoaluminum compound The layered silicates may be brought into contact with each other.
The contact method of each component is not specifically limited, For example, the following methods are arbitrarily employable.
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) and the layered silicate support are contacted, and then contacted with the organoaluminum compound.
Contact method (8): The organoaluminum compound and the layered silicate support are contacted, and then contacted with the catalyst component (i).

  Of these contact methods, contact methods (6) and (8) are preferred. In any contact method, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually 6 to 12 carbon atoms), heptane, hexane, decane and dodecane. 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, a method of bringing each component into contact with stirring or non-stirring is employed.

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

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

  As an example of producing a metallocene catalyst, for example, it can be produced by referring to “catalyst” and “mixing 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, and can be controlled by, for example, the methods described in JP-A-2-269705 and JP-A-3-21607.

The polyethylene component (A) is a homopolymer of ethylene or ethylene and an α-olefin having 3 to 12 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 -Obtained by copolymerization with octene or the like. Also, copolymerization with a diene for the purpose of modification is possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, and the like. The comonomer content during the polymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, an ethylene / α-olefin copolymer is used. The α-olefin content is 0 to 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 ordinary fossil raw materials, or may be ethylene derived from plants. . Examples of the plant-derived ethylene and polyethylene include ethylene and polymers thereof described in JP-T 2010-511634. Plant-derived ethylene and its polymers have the property of carbon neutral (does not use fossil raw materials and does not lead to an increase in carbon dioxide in the atmosphere), and can provide environmentally friendly products.

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 the molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system. Can do.
Moreover, even if a component for the purpose of removing moisture, a so-called scavenger, is added to the polymerization system, the polymerization can be carried out without any trouble.
Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, the organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethyl zinc and dibutyl zinc, diethyl Organic magnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and grinier compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Of these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable.
The present invention can also be applied to a multistage polymerization system having two or more stages having different polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature without any trouble.

  The polyethylene component (A) can be produced by a production process such as a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method, preferably a slurry polymerization method. Among the polymerization conditions of the polyethylene component (A), the polymerization temperature can be selected from the range of 0 to 200 ° C. In slurry polymerization, polymerization is performed at a temperature lower than the melting point of the produced polymer. The polymerization pressure can be selected from the range of atmospheric pressure to about 10 MPa. From an aliphatic hydrocarbon such as hexane, heptane and isobutane, an aromatic hydrocarbon such as benzene, toluene and xylene, an alicyclic hydrocarbon such as cyclohexane and methylcyclohexane, etc., in a state where oxygen, water, etc. are substantially cut off. It can be produced by carrying out slurry polymerization of ethylene and α-olefin in the presence of a selected inert hydrocarbon solvent.

  As long as the polyethylene component (A) satisfies the specified range in the present invention, polymerization is successively performed in a single polymerizer, a plurality of reactors connected in series or in parallel, and a plurality of ethylene polymers are polymerized separately. It is also possible to mix them.

2. Polyethylene component (B)
Characteristic (b1)
The polyethylene component (B) used in the present invention is selected from those having an HLMFR of 2 g / 10 min or more and less than 400 g / 10 min from the viewpoint of the effects of the present invention. The HLMFR of the polyethylene component (B) is preferably in the range of 10 g / 10 min to 370 g / 10 min.
If this HLMFR is less than 2 g / 10 minutes, the molecular weight increases, and there is a possibility that fluidity and moldability cannot be ensured. Further, in the final resin composition, HLMFR cannot be achieved within the specified range, and the fluidity may be lowered, and the compatibility may be lowered, so that the appearance of the molded product may be impaired.
On the other hand, if the HLMFR is 400 g / 10 min or more, impact resistance may not be ensured due to an increase in the amount of low molecular weight components.
HLMFR can be measured in the same manner 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)
As the polyethylene component (B) used in the present invention, a polyethylene component having a density of 0.940 g / cm ³ or more and 0.970 g / cm ³ or less is selected from the point of achieving the effects of the present invention.
When the density of the polyethylene component (B) is less than 0.940 g / cm ³ , the density range in the final resin composition cannot be achieved, the rigidity is insufficient, and the crystallization speed is reduced, resulting in a molding cycle. May decrease. In addition, the rigidity of the container is inferior and the container tends to be deformed at a high temperature, and the container may be deformed and cause leakage due to the influence of the container internal pressure or the like.
On the other hand, when the density exceeds 0.970 g / cm ³ , the impact performance of the final resin composition may be lowered, and the impact resistance of the container may be deteriorated.
The density can be measured in the same manner as described above.
The density can be adjusted mainly by the amount of α-olefin during polymerization of the polyethylene component (B).

Characteristic (b3)
The polyethylene component (B) used in the present invention has an elongation viscosity η (t) (unit) measured at a temperature of 170 ° C. and an elongation strain rate of 0.1 (unit: 1 / second) in order to achieve the effects of the present invention. : Pa · second) and a logarithmic plot of elongation time t (unit: seconds), polyethylene is selected from which an inflection point of elongational viscosity due to strain hardening is observed.
The presence or absence of an inflection point of elongational viscosity resulting from 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 degree of strain hardening 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 perform polymerization by applying an appropriate polymerization catalyst, and it is preferable to use a metallocene catalyst as described later.

Characteristic (b4)
The polyethylene component (B) used in the present invention preferably satisfies the following property (b4).
Characteristic (b4): Strain hardening degree [λmax (2.0)] measured at a temperature of 170 ° C. and an elongation strain rate of 2 (unit: 1 / second) is 1.2 to 10.0.
The polyethylene component (B) used in the present invention has an elongation viscosity η (t) (unit: Pa · second) and an elongation time t (unit: unit) measured at a temperature of 170 ° C. and an elongation strain rate of 2 (unit: 1 / second). In the logarithmic plot (second), an inflection point of the extension viscosity due to strain hardening is observed, the maximum extension viscosity after strain hardening is η _Max (t1), and the approximate straight line of extension viscosity before hardening is η _Linear (t ), The strain hardening degree [λmax (2.0)] defined by η _Max (t1) / η _Linear (t1) is 1.2 to 10.0, preferably 1.7 to 8.0, More preferably, it is 2.4-6.0, More preferably, it is 3.0-5.0.
When [λmax (2.0)] is less than 1.2, the fluidity and melt tension of the polyethylene resin composition and the molded article become insufficient, and the molding process characteristics deteriorate. When [λmax (2.0)] is greater than 10.0, the fluidity and melt tension are excellent, but the impact strength of the polyethylene resin composition and the molded article may be lowered, which is not preferable.
In this way, to devise the long-chain branching structure, which is the main dominating factor of the elongational viscosity characteristics, to improve the molding process surface and to overcome the disadvantages of the mechanical properties of the molded body due to the elongational flow characteristics of polyethylene. As a result of diligent investigation on the polyethylene resin composition to solve the above problem, the polyethylene component (A) having a small long-chain branched structure was used as the high MFR main component, that is, the low molecular weight side main component of the resin composition, and the above characteristics A polyethylene component (B) having a long chain branching structure represented by the elongation strain hardening degree [λmax (2.0)] defined in (b4) is used as a low MFR main component, that is, a high molecular weight main component of the resin composition. As a result, it can be seen that not only the molding process characteristics are improved but also the mechanical characteristics, in particular, the rigidity and impact strength are excellent. Furthermore, the long chain of the polyethylene component (B) When the branch structure has a characteristic represented by the following characteristic (b5), which is different from the conventionally used strain rate dependency of the elongation strain hardening degree, the molding process characteristic and mechanical characteristic of the polyethylene resin composition In any case, it was found that the improvement effect was extremely excellent.

Characteristic (b5)
The polyethylene component (B) used in the present invention preferably satisfies the following property (b5).
Characteristic (b5): strain hardening degree [λmax (2.0)] measured at a temperature of 170 ° C. and an elongation strain rate of 2 (unit: 1 / second), and an elongation strain rate of 0.1 (unit: 1 / second) The ratio [λmax (2.0)] / [λmax (0.1)] to the degree of strain hardening [λmax (0.1)] measured in (1) is 1.2 to 10.0.
The polyethylene component (B) used in the present invention was measured in the same manner with [λmax (2.0)] defined in (b4) above and an elongation strain rate of 0.1 (unit: 1 / second) [ The ratio [λmax (2.0) / λmax (0.1)] to λmax (0.1)] is 1.2 to 10.0, preferably 1.3 to 5.0, more preferably 1.4. It is -4.0, More preferably, it is 1.5-3.0.
If [λmax (2.0) / λmax (0.1)] is less than 1.2, the polyethylene resin composition or the molded body may not be uniformly melted or may have a thermally unstable structure. And there is a possibility that the impact strength may be reduced due to the strength anisotropy of the molded product due to the presence of a very long long-chain branched structure. When [λmax (2.0) / λmax (0.1)] is greater than 10.0, the melt strength and fluidity during molding are excellent, but the impact strength of the polyethylene resin composition and the molded product is lowered. This is not preferable because of fear.

In the polyethylene component (B) used in the present invention, the molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 4 or more and 10 or less.
The molecular weight distribution (Mw / Mn) measured by GPC is related to improvements in various physical properties and moldability of the polymer, and is also related to improvements in 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 hollow molding processability can be exhibited. Further, when the molecular weight distribution (Mw / Mn) is 4 or more, the compatibility with the polyethylene component (A) and the polyethylene component (C) is improved, and the product appearance is excellent, and the resin pressure during extrusion molding Is suitable, and is less likely to cause flow instability such as shark skin and melt fracture, and is preferable from the viewpoint of easily suppressing poor appearance. On the other hand, when the molecular weight distribution (Mw / Mn) is 10 or less, deterioration of the pinch-off shape of the molded product is easily suppressed, and the impact strength as a hollow molded product is easily improved.
The molecular weight distribution within a predetermined range can be achieved by employing a catalyst capable of controlling the molecular weight distribution and appropriate 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 Japan Waters Co., Ltd. Measurement temperature: 145 ° C
Solvent: orthodichlorobenzene (ODCB)
Column: Showex Denko Shodex HT-806M x 2 + HT-G
Flow rate: 1.0 mL / min Injection rate: 0.3 mL

[Sample preparation]
A 3 mL sample and 3 mL of orthodichlorobenzene (containing 0.1 mg / mL 1,2,4-trimethylphenol) were weighed into a 4 mL vial, and capped with a resin screw cap and a Teflon (registered trademark) septum. Then, it melt | dissolves for 2 hours using the SSC-9300 type | mold high temperature shaker by Senshu Scientific which set the temperature to 150 degreeC. After completion of dissolution, it is visually confirmed that there are no insoluble components.
[Create calibration curve]
Four 4 mL glass bottles are prepared, and 0.2 mg each of monodisperse polystyrene standard samples or n-alkanes of the combinations (1) to (4) below are weighed, followed by orthodichlorobenzene (0.1 mg / mL). SSC-9300 type manufactured by Senshu Kagaku Co., Ltd., which was set at a temperature of 150 ° C. after weighing 3 mL of (including 1,2,4-trimethylphenol) and capping with a resin screw cap and a Teflon (registered trademark) septum. Dissolve for 2 hours using a high temperature shaker.
(1) Shodex S-1460, S-66.0, n-eicosane (2) Shodex S-1950, S-152, n-tetracontane (3) Shodex S-3900, S-565, S -5.05
(4) Shodex S-7500, S-1010, S-28.5
The vial containing the sample solution is set in the apparatus, the measurement is performed under the above-mentioned conditions, and the chromatogram (the retention time and the differential refractometer detector response data set) is recorded at a sampling interval of 1 second. From the obtained chromatogram, the retention time (peak apex) of each polystyrene standard sample is read 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. A nonlinear least square method is applied to this plot, and the obtained quartic curve is used as a calibration curve.

[Calculation of molecular weight]
Measure under the above conditions and record the chromatogram at a sampling interval of 1 second.
From this chromatogram, Sadao Mori “Size Exclusion Chromatography” (Kyoritsu Shuppan), Chapter 4, p. The differential molecular weight distribution curve and average molecular weight values (Mn, Mw, and Mz) are calculated by the method described in 51-60. However, in order to correct the molecular weight dependency of dn / dc, the height H from the baseline in the chromatogram is corrected by the following equation. Chromatogram recording (data acquisition) and average molecular weight calculation are performed using an in-house program (created with Microsoft Visual Basic 6.0 from Microsoft) on a PC on which Microsoft Windows (registered trademark) XP is installed.
H ′ = H / [1.032 + 189.2 / M (PE)]
In addition, the following formula is used for molecular weight conversion from polystyrene to polyethylene.
M (PE) = 0.468 × M (PS)

The ethylene polymer of the polyethylene component (B) of the present invention can be produced by a method of polymerizing ethylene or the like using a catalyst for olefin polymerization, preferably a specific metallocene catalyst.
Various types of catalysts for olefin polymerization are known today, and ethylene-based polymers that satisfy the above conditions can be prepared within the scope of the composition of the catalyst components and polymerization conditions and post-treatment conditions. As long as it is not limited at all, an example of a suitable production method for simultaneously realizing the specific long chain branched structure, composition distribution structure, MFR, and density of the ethylene polymer of the present invention will be described below. The method using the catalyst for olefin polymerization containing the specific catalyst component (A), (B) and (C) to perform can be mentioned.
Catalyst component (A): Bridged cyclopentadienylindenyl compound containing a transition metal element Catalyst component (B): Compound that reacts with the compound of catalyst component (A) to form a cationic metallocene compound Catalyst component (C): Inorganic compound carrier

[Catalyst component (A)]
Preferred catalyst component (A) for producing the ethylene / α-olefin copolymer of the present invention is a bridged cyclopentadienyl indenyl compound containing a transition metal element having a five-membered ring structure substituent on the indenyl ring. More preferably, it is a metallocene compound represented by the following general formula [1], and more preferably the following general formula [2]
It is a metallocene compound represented by these.
In the present invention, the specific ethylene polymer of the present invention is produced exclusively and efficiently by using the ligand represented by the formula [2] and (1-c) as a polymerization catalyst component. Can be manufactured well. One feature of the ethylene polymer of the present invention is that it is produced by a polymerization method using such a specific polymerization catalyst.

[1]

[However, in the formula [1], M represents a transition metal of Ti, Zr or Hf. A ¹ represents a ligand having a cyclopentadienyl ring (conjugated five-membered ring) structure, A ² represents a ligand having an indenyl ring structure with a five-membered ring structure substituent, and Q ¹ represents A ¹ A binding group that crosslinks A ² at an arbitrary position is shown. X and Y are σ-bonding groups, and each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, A hydrocarbon group-substituted amino group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms is shown. ]

[2]

[In the formula [2], M represents a transition metal of Ti, Zr or Hf. Q ¹ represents a binding group that bridges the cyclopentadienyl ring and the indenyl ring. X and Y are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, or a carbon atom having 1 to 20 carbon atoms. A hydrogen-substituted amino group or an alkoxy group having 1 to 20 carbon atoms is shown. 10 Rs are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, 20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing an oxygen atom or a C1-C20 hydrocarbon group-substituted silyl group, wherein at least one R attached to the indenyl ring side is Has a five-membered ring structure. ]

  A particularly preferable catalyst component (A) for producing the ethylene / α-olefin copolymer of the present invention is a metallocene represented by the general formula (1c) described in paragraph 0007 and below of JP2013-227271A. A compound.

[However, in the formula (1c), all of the abbreviations are described in JP 2013-227271 A. That is, M ^1c represents a transition metal of Ti, Zr, or Hf. X ^1c and X ^2c each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom or a nitrogen atom, or 1 to 20 carbon atoms. A hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q ^1c and Q ^2c each independently represent a carbon atom, a silicon atom, or a germanium atom. R ^1c independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least two of the four R ^1cs are bonded to form a ring together with Q ^1c and Q ^2c. Also good. ^mc is 0 or 1, and when ^mc is 0, Q ^1c is directly bonded to a conjugated 5-membered ring containing R ^2c . R ^2c and R ^4c are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, or 1 carbon atom. -20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing an oxygen atom, or a C1-C20 hydrocarbon group-substituted silyl group. R ^3c represents a substituted aryl group represented by the following general formula (1-ac). ]

[However, in the formula (1-ac), Y ^1c represents an atom of Group 14, 15 or 16 of the periodic table. R ^5c , R ^6c , R ^7c , R ^8c and R ^9c are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, a carbon number containing oxygen or nitrogen 1-20 hydrocarbon group, C1-C20 hydrocarbon group-substituted amino group, C1-C20 alkoxy group, C1-C18 silicon-containing hydrocarbon group containing 1-6 silicon atoms, carbon A halogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, wherein R ^5c , R ^6c , R ^7c , R ^8c and R ^9c are bonded to each other with adjacent groups; And may form a ring together with atoms bonded to them. n ^c is 0 or 1, if ^{n c} is ^0, there is no substituent ^{R 5c} to ^{Y 1c. pc} is 0 or 1, and when ^pc is 0, the carbon atom to which R ^7c is bonded and the carbon atom to which R ^9c are bonded are directly bonded. When Y ^1c is a carbon atom, at least one of R ^5c , R ^6c , R ^7c , R ^8c , and R ^9c is not a hydrogen atom. ^Pc is 0 when R ^2c is not a five-membered ring structure substituent. ]

  All further specific examples of the abbreviations in the general formula (1c) are as described in JP-A-2013-227271 unless otherwise specified.

  The most preferred catalyst component (A) for producing the ethylene / α-olefin copolymer of the present invention is a metallocene compound represented by the general formula (3c) described in paragraph 0013 of JP2013-227271A It is.

(3c)

In the metallocene compound represented by the above general formula (3c), M ^1c , X ^1c , X ^2c , Q ^1c , R ^1c , R ^2c and R ^4c are the descriptions of the metallocene compound represented by the above general formula (1c). The structure similar to the atom and group shown in the above can be selected including preferred embodiments, but R ^2c is most preferably a hydrogen atom or a methyl group, and among the four R ^4c , a carbon atom having a bridging group Q ^1c attached. The two R ^4c 's attached to both adjacent carbon atoms are most preferably a hydrogen atom, and the remaining R ^4c is most preferably a hydrogen atom or a methyl group. R ^12c , R ^13c, and R ^14c are the same as the atoms and groups of R ^5c , R ^6c , R ^7c , R ^8c , and R ^9c shown in the description of the metallocene compound represented by the general formula (1c). A structure can be selected. Z ^1c represents an oxygen atom or a sulfur atom.

  As specific examples of the metallocene compound, 55c to 94c and 224c to 303c are preferable among the compounds described in Table 1c of JP2013-227271A, but are not limited thereto.

Among the specific compounds exemplified above, more preferable ones are shown below.
Listed in Table 1c are 55c to 72c, 81c to 86c, 224c to 231c, and the like.
Moreover, the compound which replaced the zirconium of said compound with titanium or hafnium, etc. are mentioned as a preferable thing.

Further, among the specific compounds exemplified above, further preferred ones are shown below. In Table 1c, 55c to 66c, 81c, 82c, 224c to 227c and the like can be mentioned.
Moreover, the compound which replaced the zirconium of said compound with titanium or hafnium is mentioned as a preferable thing.
The compound of the above specific example is preferably a zirconium compound or a hafnium compound, and more preferably a zirconium compound.

  As a preferred catalyst component (A) for producing the ethylene polymer of the present invention, two or more of the above-mentioned crosslinked cyclopentadienylindenyl compounds can be used. In that case, molecular weight distribution and copolymer composition distribution are used. It goes without saying that care must be taken not to spread too much.

[Catalyst component (B)]
A preferred catalyst component (B) for producing the ethylene-based polymer of the present invention is a compound that reacts with the compound of component (A) to form a cationic metallocene compound. A borane compound and a borate compound are mentioned.
More preferred are the components (B) described in JP 2013-227271 A [0064] to [0083], and still more preferred are organoaluminum oxy compounds described in the above [0065] to [0069].

[Catalyst component (C)]
Examples of the catalyst component (C) include widely used inorganic carriers, particulate polymer carriers, or mixtures 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.
A preferable catalyst component (C) for producing the ethylene polymer of the present invention is an inorganic compound carrier, and more preferably an inorganic compound described in JP2013-227271A [0084] to [0088]. is there. At this time, the metal oxide described in the publication [0085] is preferable as the inorganic compound.

[Production of olefin polymerization catalyst]
The ethylene-based polymer of the present invention is suitably produced by a method of polymerizing ethylene using an olefin polymerization catalyst containing the catalyst components (A) to (C). The contact method of each component when obtaining the catalyst for olefin polymerization from the catalyst components (A) to (C) of the present invention is not particularly limited. For example, the following methods (I) to (III) are optional. Can be adopted.

(I) A catalyst that is a compound that forms a cationic metallocene compound by reacting with the catalyst component (A) that is a bridged cyclopentadienylindenyl compound containing the transition metal element and the compound of the catalyst component (A). After contacting the component (B), the catalyst component (C), which is an inorganic compound carrier, is contacted.
(II) After contacting the catalyst component (A) and the catalyst component (C), the catalyst component (B) is contacted.
(III) After contacting the catalyst component (B) and the catalyst component (C), the catalyst component (A) is contacted.

Of these contact methods, (I) and (III) are preferred, and (I) is most preferred.
In any contact method, usually in an inert atmosphere such as nitrogen or argon, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually having 6 to 12 carbon atoms), pentane, heptane, hexane and decane. In the presence of liquid inert hydrocarbons such as aliphatic or alicyclic hydrocarbons (usually having 5 to 12 carbon atoms) such as dodecane and cyclohexane, a method of bringing each component into contact with stirring or non-stirring is employed. . 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, more preferably. It is desirable to carry out in 30 minutes to 12 hours.

  In addition, when contacting the catalyst component (A), the catalyst component (B), and the catalyst component (C), as described above, an aromatic hydrocarbon solvent in which a certain component is soluble or hardly soluble, and a certain component Any insoluble or hardly soluble aliphatic or alicyclic hydrocarbon solvent can be used.

  In the case where the contact reaction between the components is performed stepwise, this may be used as it is as the solvent for the subsequent contact reaction without removing the solvent used in the previous step. In addition, after the previous catalytic reaction using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.) Hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons) and the desired product is recovered as a solid or once or part of the soluble solvent is removed by means such as drying. 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 this invention, it does not prevent performing contact reaction of each component in multiple times.

In the present invention, the use ratio of the catalyst component (A), the catalyst component (B) and the catalyst component (C) is not particularly limited, but the following ranges are preferable.
When an organoaluminum oxy compound is used as the catalyst component (B), the atomic ratio (Al / M) of the aluminum of the organoaluminum oxy compound to the transition metal (M) in the catalyst component (A) is usually 1 to 100, 000, preferably 5 to 1,000, more preferably 50 to 500, particularly preferably 100 to 400, and when a borane compound or a borate compound is used, the transition metal (M The atomic ratio (B / M) of boron to) is usually selected in the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10. Further, when a mixture of an organoaluminum oxy compound, a borane compound, and a borate compound is used as the catalyst component (B), the same use as described above with respect to the transition metal (M) for each compound in the mixture It is desirable to select by percentage.

The catalyst component (C) is used in an amount of 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, based on the transition metal in the catalyst component (A). Per gram.
In the present invention, the ratio of the number of moles of the metal of the catalyst component (B) to 1 g of the catalyst component (C) is preferably 0.001 to 0.020 (mol / g), more preferably 0.003. -0.012 (mol / g), More preferably, it is 0.004-0.010 (mol / g).

  The catalyst component (A), the catalyst component (B) and the catalyst component (C) are brought into contact with each other by appropriately selecting the contact methods (I) to (III) described above, and then the solvent is removed, An olefin polymerization catalyst can be obtained as a solid catalyst. The removal of the solvent is performed at normal pressure or reduced pressure at 0 to 200 ° C., preferably 20 to 150 ° C., more preferably 20 to 100 ° C. for 1 minute to 100 hours, preferably 10 minutes to 50 hours, more preferably 30 minutes. It is desirable to perform in ~ 20 hours.

The olefin polymerization catalyst can also be obtained by the following methods (IV) and (V).
(IV) The catalyst component (A) and the catalyst component (C) are contacted to remove the solvent, which is used as a solid catalyst component, and an organoaluminum oxy compound, borane compound, borate compound or a mixture thereof under polymerization conditions Make contact.
(V) The catalyst component (B), which is an organoaluminum oxy compound, borane compound, borate compound or a mixture thereof, is contacted with the catalyst component (C) to remove the solvent, and this is used as a solid catalyst component. In contact with the catalyst component (A).
In the case of the contact methods (IV) and (V), the same conditions as described above can be used for the component ratio, contact conditions, and solvent removal conditions.

  Further, as an olefin polymerization catalyst suitable for obtaining the ethylene / α-olefin copolymer of the present invention, a catalyst component (B) which reacts with the catalyst component (A) to produce a cationic metallocene compound and a catalyst component ( As a component also serving as C), a well-known layered silicate described in JP-A Nos. 05-301917 and 08-127613 can be used. The layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with a weak binding force. Most layered silicates are naturally produced mainly as the main component of clay minerals, but these layered silicates are not limited to natural ones and may be artificially synthesized. These layered silicates may be subjected to chemical treatment with acid or alkali.

  Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite, and other smectites, vermiculites, and mica are preferred.

  The use ratio of the catalyst component (A) and the layered silicate support is not particularly limited, but the following range is preferable. The supported amount of the catalyst component (A) is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, per 1 g of the layered silicate support.

  The olefin polymerization catalyst thus obtained may be used after prepolymerization of ethylene or / and an appropriate α-olefin monomer, if necessary.

Polymerization Method of Ethylene Polymer The ethylene polymer of the present invention is preferably produced by polymerizing ethylene or copolymerizing ethylene with an α-olefin using the olefin polymerization catalyst prepared by the above production method. The

  As the α-olefin, which is a comonomer, an α-olefin having 3 to 20 carbon atoms can be used, and two or more types of α-olefin can be copolymerized with ethylene. It is also possible to use a small amount.

  In the present invention, the above polymerization reaction can be preferably performed using a gas phase continuous polymerization apparatus or a slurry continuous polymerization apparatus. The continuous polymerization apparatus refers to a polymerization reaction apparatus having an apparatus capable of continuously supplying a raw material necessary for polymerization such as a catalyst and a monomer, and an apparatus capable of continuously discharging a produced polymer. In the case of gas phase continuous polymerization, ethylene or the like is polymerized in a reactor in which a gas flow of ethylene or comonomer is introduced, circulated or circulated with oxygen and water substantially cut off. In the case of slurry continuous polymerization, an inert hydrocarbon selected from aliphatic hydrocarbons such as isobutane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Ethylene or the like is continuously polymerized in the presence or absence of a hydrogen solvent. Needless to say, liquid monomers such as liquid ethylene and liquid propylene can also be used as the solvent. In the present invention, more preferred polymerization is gas phase continuous polymerization.

The polymerization temperature is usually from 0 to 250 ° C., preferably from 60 to 110 ° C., more preferably from 65 to 95 ° C. In the case of gas phase polymerization or slurry polymerization, the flow of the generated polymer particles is not hindered by softening or melting. In the range, an ethylene-based polymer having a smaller g _L value can be obtained by performing polymerization at a higher temperature.
The ethylene partial pressure is usually in the range of normal pressure to 10 MPa, preferably 0.2 to 1.9 MPa, more preferably 0.3 to 1.8 MPa, and particularly preferably 0.4 to 1.6 MPa. The average residence time is usually 5 minutes to 20 hours, preferably 1 to 15 hours, more preferably 3 to 12 hours.

  The molecular weight of the produced copolymer can be adjusted to some extent by changing the polymerization conditions such as the type of catalyst component (A) and catalyst component (B), the molar ratio of the catalyst, and the polymerization temperature. The molecular weight can be adjusted more effectively by adding.

Moreover, even if a component for the purpose of removing moisture, a so-called scavenger, is added to the polymerization system, the polymerization can be carried out without any trouble.
Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethylzinc and dibutylzinc, diethylmagnesium. Organic magnesium compounds such as dibutylmagnesium and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride are used.
Of these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable.

The long-chain branched structure (that is, g _L , g _m ) and comonomer copolymer composition distribution of the produced copolymer are the types of catalyst component (A) and catalyst component (B), molar ratio of catalyst, polymerization temperature, pressure, time It can be adjusted by changing the polymerization conditions and the polymerization process.
Even if a catalyst component type that easily forms a long-chain branched structure is selected, a polymer having a small long-chain branched structure can be produced, for example, by lowering the polymerization temperature or increasing the ethylene partial pressure. Even if a catalyst component species having a broad molecular weight distribution or copolymer composition distribution is selected, a copolymer having a narrow molecular weight distribution or copolymer composition distribution is produced by changing the catalyst component molar ratio, polymerization conditions, or polymerization process, for example. There are some cases that require attention.

  Even in a two-stage or more multi-stage polymerization system in which polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, polymerization temperature and the like are different from each other, if the polymerization conditions are set appropriately, the ethylene polymer of the present invention can be produced. However, when the ethylene-based polymer of the present invention is produced by a one-step polymerization reaction, it is preferable because it can be produced more economically without setting complicated polymerization operation conditions.

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 min or more and 200 g / 10 min or less at a temperature of 190 ° C. and a load of 2.16 Kg in order to achieve the effects of the present invention. Select. The MFR of the polyethylene component (C) is preferably in the range of 11 g / 10 min to 198 g / 10 min, more preferably 11 g / 10 min to 195 g / 10 min.
If the MFR is less than 10 g / 10 minutes, the molecular weight increases, and there is a possibility that fluidity and moldability cannot be ensured. In addition, in the final resin composition, HLMFR cannot be achieved within the specified range, and flowability is reduced, and flow instability such as shark skin and melt fracture is likely to occur. May be damaged.
On the other hand, if the MFR exceeds 200 g / 10 min, impact resistance may not be ensured due to the effect of increasing the amount of low molecular weight components. Moreover, in the final resin composition, impact resistance cannot be achieved, and the drop impact resistance of the molded product may be reduced.
MFR can be measured in the same manner as described above.
MFR can be adjusted mainly by the amount of hydrogen and the polymerization temperature during the polymerization of the polyethylene component (C).

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.
If 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, the rigidity of the container is inferior and easily deformed at high temperatures, The container may deform and cause leakage.
On the other hand, when the density exceeds 0.980 g / cm ³ , the impact resistance performance of the final resin composition may be lowered, and the drop impact resistance of the container may be inferior.
The density can be measured in the same manner as described above.
The density can be adjusted mainly by the amount of α-olefin during polymerization of the polyethylene component (C).

Characteristic (c3) and characteristic (c4)
The polyethylene component (C) preferably 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 min or more and 2,000 g / 10 min or less.
The MLMFR of the polyethylene component (C) is more preferably 70 g / 10 min or more and 1,700 g / 10 min or less.
If this MLMFR is less than 50 g / 10 min, the molecular weight increases, and there is a possibility that fluidity and moldability cannot be ensured. In addition, in the final resin composition, HLMFR cannot be within the specified range, and flowability is reduced, and fluid instability such as shark skin and melt fracture is likely to occur. There is a risk of damage.
On the other hand, if this MLMFR exceeds 2000 g / 10 min, impact resistance may not be ensured due to an increase in the amount of low molecular weight components. Moreover, in the final resin composition, impact resistance cannot be achieved, and the drop impact property of the molded product may be lowered.
Characteristic (c4): Melt flow rate ratio (MLMFR / MFR) which is a ratio of MLMFR to MFR is 3 or more and 15 or less.
When the MLMFR / MFR of the polyethylene component (C) is within this 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 specification can be satisfied. The polyethylene component (C) used in the present invention can be produced by polymerization using a Ziegler-Natta catalyst or a metallocene catalyst, preferably polyethylene derived from a Ziegler-Natta catalyst, and the polyethylene component (A) or polyethylene It can manufacture according to the polymerization method of a 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 comprises the polyethylene component (A) in an amount of 10% by mass to 40% by mass, the polyethylene component (B) in an amount of 10% by mass to 80% by mass, and the polyethylene component ( C) is a polyethylene resin composition containing 10% by mass or more and 80% by mass or less. Preferably, the composition contains 15% to 40% by weight of the polyethylene component (A), 10% to 45% by weight of the polyethylene component (B), and 30% to 70% by weight of the polyethylene component (C). It is a thing.
It is important that the polyethylene resin composition of the present invention satisfies the following characteristics (1) to (5).
Characteristic (1): MFR is 0.1 g / 10 min or more and 1 g / 10 min or less.
Characteristic (2): HLMFR is 10 g / 10 min or more and 50 g / 10 min or less.
Characteristic (3): Melt flow rate ratio (HLMFR / MFR) which is a ratio of HLMFR to MFR is 40 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 · second) and elongation time t (unit: second) measured at a temperature of 170 ° C. and an elongation strain rate of 0.1 (unit: 1 / second) In the logarithmic plot, an 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.

Characteristics (1)
The polyethylene resin composition of the present invention has an MFR of 0.1 g / 10 min or more and 1 g / 10 min or less. The MFR is preferably in the range of 0.15 g / 10 min to 0.8 g / 10 min, more preferably 0.25 g / 10 min to 0.7 g / 10 min.
If this MFR is less than 0.1 g / 10 min, the fluidity is lowered, which may cause an increase in the amount of heat generated by the extruder motor at the time of molding, the resin heat generation due to shearing, and the flow instability phenomenon such as shark skin. Since it becomes easy to generate | occur | produce, there exists a possibility of impairing the external appearance of a molded article.
On the other hand, if the MFR exceeds 1 g / 10 min, impact resistance and environmental stress crack resistance cannot be achieved, and the drop impact resistance and long-term durability of the molded product may be reduced.
The MFR of the polyethylene resin composition can be adjusted by the respective hydrogen amounts and temperatures during polymerization of the polyethylene component (A), the polyethylene component (B) and the polyethylene component (C), and the blending amount of each component.

Characteristics (2)
The polyethylene resin composition of the present invention has an HLMFR of 10 g / 10 min or more and 50 g / 10 min or less. The HLMFR is preferably in the range of 12 g / 10 min or more and 48 g / 10 min or less, more preferably 15 g / 10 min or more and 46 g / 10 min or less.
If this HLMFR is less than 10 g / 10 min, flowability may decrease, resulting in an increase in the amount of heat generated by the extruder motor during molding and resin heat generation due to shear, and flow instability phenomena such as sharkskin and melt fracture. May occur, the appearance of the molded product may be impaired.
On the other hand, if the HLMFR exceeds 50 g / 10 minutes, impact resistance and environmental stress crack resistance cannot be achieved, and the 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 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) that is a ratio of HLMFR to MFR of 40 or more and 140 or less. The melt flow rate ratio is preferably in the range of 50 to 139.
HLMFR / MFR has a strong correlation with the molecular weight distribution. When HLMFR / MFR takes a large value, the molecular weight distribution becomes wide. When HLMFR / MFR takes a small value, the molecular weight distribution becomes narrow. If HLMFR / MFR exceeds 140, compatibility of each component may deteriorate, impact resistance may decrease, and flow instability such as melt fracture may easily occur. If HLMFR / MFR is less than 40, melt tension decreases. And ESCR may be reduced.
The control method of HLMFR / MFR can be performed mainly according to the control method of 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 is insufficient and the crystallization rate is lowered, and as a result, the molding cycle may be lowered. On the other hand, when the density exceeds 0.965 g / cm ³ , the environmental stress crack resistance may be deteriorated.
The density can be adjusted mainly by the amount of α-olefin during 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 elongational viscosity η (t) (unit: Pa · second) measured at a temperature of 170 ° C. and an elongation strain rate of 0.1 (unit: 1 / second) and an elongation time t (unit: unit). Second) is a polyethylene resin composition in which an inflection point of elongational viscosity due to strain hardening is observed.
The presence or absence of an inflection point of elongational viscosity resulting from 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 degree of strain hardening of the polyethylene component (A) described above. it can.
In order for the polyethylene resin composition to have 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 further to a polyethylene component (A) having a long-chain branched structure. A predetermined amount of the polyethylene component (B) having a chain branching structure is preferably used in combination.

Characteristic (6)
The polyethylene resin composition of the present invention preferably further satisfies the following property (6) from the viewpoint of hollow moldability such as drawdown resistance.
Characteristic (6): The melt tension (MT) measured at 190 ° C. is 60 mN or more. The melt tension is more preferably 65 mN or more. Further, those satisfying the following relational expression (3) are preferred, and those satisfying the following relational expression (4) are preferred, since the melt tension corresponding to HLMFR is high.
MT> −22.45 × ln (HLMFR) +137.82 Relational expression (3)
MT> −22.45 × ln (HLMFR) +157.82 Relational expression (4)
Here, MT (mN) is the melt tension, and HLMFR (g / 10 min) is the melt flow rate at a temperature of 190 ° C. and a load of 21.6 Kg.
In the present invention, when the horizontal axis is HLMFR, the vertical axis is the melt tension, and the example data of the present invention is plotted, the relational expression (3) is an equation for distinguishing the preferred range of the present invention from the prior art. Yes, 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 molten ethylene polymer is stretched at a constant speed, and can be measured under the following conditions.
[Measurement condition]
Model used: Toyo Seiki Seisakusho, Capillograph 1B
Nozzle diameter: 2.095mm
Nozzle length: 8.0mm
Inflow angle: 180 ° (flat)
Extrusion speed: 15 mm / min Take-off speed: 6.5 m / min Measuring temperature: 190 ° C.
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 are mixed at a predetermined blending ratio. Is preferred.

Characteristic (7)
The polyethylene resin composition of the present invention preferably further satisfies the following property (7) from the viewpoint of improving impact resistance.
Characteristic (7): A 1.5 mm compression molded sheet was prepared according to JIS K6922-2, and a test piece punched with an S-type dumbbell was prepared according to ASTM D1822, at 23 ° C. and 50% RH. The tensile impact test value measured under the conditions is 70 KJ / m ² or more.
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 are mixed at a predetermined blending ratio. Is preferred.

Characteristic (8)
The polyethylene resin composition of the present invention further preferably satisfies the following property (8) from the viewpoint of good dispersion of the polyethylene component (A). If the polyethylene component (A) can be highly dispersed in the polyethylene component (B) and the polyethylene component (C), the surface property of the molded product becomes smooth and the appearance is particularly excellent.
Characteristic (8): Dynamic melt viscosity η _{W · 0.01} (unit: Pa · second) 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} is obtained by using a sample molded into a sheet having a thickness of 2.0 mm by hot pressing, using a rheometer (Ales manufactured 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, the strain 10%, and the frequency ω 0.01 rad / sec is expressed as the dynamic melt viscosity (η _{W · 0. 01} ).
[Measurement condition]
Apparatus: Ales manufactured by Rheometrics
Jig: 25mm diameter parallel plate, plate spacing approx. 1.7mm
Measurement temperature: 190 ° C
Frequency range: 0.01 to 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 are mixed at a predetermined blending ratio. Is preferred.

Characteristic (9)
The polyethylene resin composition of the present invention preferably satisfies the following property (9) from the viewpoint of good dispersion of the polyethylene component (A).
Characteristic (9): Dynamic melt viscosity η of the polyethylene component (A) with respect to the dynamic melt viscosity η _{W · 0.01} of the polyethylene resin composition measured when the frequency ω is 0.01 rad / sec at a temperature of 190 ° C. the ratio of _{H · 0.01 η H · 0.01 /} η W · 0.01 1 exceeded, less than 15, more preferably 1 excess, less than 14.6.
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 are mixed at a predetermined blending ratio. Is preferred.

Characteristic (10)
The polyethylene resin composition of the present invention preferably further satisfies the following relational expression (1) from the viewpoint of particularly excellent balance of rigidity (density) and long-term durability such as environmental stress crack resistance.
log (FNCT) ≧ −257.5 × (density) +247.9 Relational expression (1)
Here, FNCT (time) is the rupture time of the all notched creep test shown below, and D is the density (g / cm ³ ). The longer the notch creep test (FNCT) time, 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 (1) represents the preferred range of the present invention. It is a mathematical formula for distinguishing from technology.
The full notched creep test can be performed according to ISO DIS 16770. A sample is prepared by preparing a test piece having a cross section of 4 mm × 4 mm in which a 1 mm notch is made with a razor blade around a 6 mm × 6 mm × 11 mm square pillar, and pure water at 80 ° C. Among them, a tensile stress corresponding to 3.7 MPa is given to the specimen, and the time until the specimen breaks is measured to obtain the FNCT breaking time.
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 at a predetermined blending ratio. Is preferred.

Characteristic (11)
The polyethylene resin composition of the present invention preferably further satisfies the following property (11).
Characteristic (11): The proportion (Y) of the component eluted at 0 ° C. or less by temperature rising elution fractionation (TREF) is less than 0.8 wt%, preferably less than 0.7 wt%, more preferably 0.6 wt% Is less than. The temperature rising elution fractionation (TREF) is a conventional means for fractionating a polymer according to non-crystallinity and crystallinity.
When the low-temperature elution component amount Y value is 0.8% by weight or more, the low molecular weight component and low density component contained in the ethylene polymer increase, and the surface of the molded article such as a film becomes easy to stick or the product is a container. In the case of a bag or a bag, the components may be mixed into the inclusion to contaminate the inclusion, and mechanical strength such as impact strength may be deteriorated. In addition, Y value is 0 weight% or more.

[TREF measurement conditions]
A sample is dissolved in orthodichlorobenzene (containing 0.5 mg / mL BHT) at 140 ° C. to obtain a solution. After this is introduced into a 140 ° C. TREF column, it is cooled to 100 ° C. at a rate of temperature decrease of 8 ° C./min, subsequently cooled to 40 ° C. at a rate of temperature decrease of 4 ° C./min, and then the temperature is decreased to 1 ° C./min. Cool to -15 ° C at speed and hold for 20 minutes.
Thereafter, orthodichlorobenzene (containing 0.5 mg / mL BHT) as a solvent is passed through the column at a flow rate of 1 mL / min, and the components dissolved in orthodichlorobenzene at −15 ° C. are eluted in the TREF column for 10 minutes. Next, the column is linearly heated to 140 ° C. at a temperature increase rate of 100 ° C./hour to obtain an elution curve. At this time, the amount of the component eluted between 85 ° C. and 140 ° C. is X (unit: wt%).

The equipment used is as follows.
(TREF part)
TREF column: 4.3 mmφ × 150 mm stainless steel column Column packing: 100 μm surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Digital Program Controller KP1000
(Valve oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve, 4-way valve (sample injection part)
Injection method: Loop injection method Injection amount: Loop size 0.1ml
Inlet heating method: Aluminum heat block Measurement temperature: 140 ° C
(Detection unit)
Detector: Fixed wavelength type infrared detector FOXBORO, MIRAN, 1A
Detection wavelength: 3.42 μm
High-temperature flow cell: LC-IR micro flow cell, optical path length 1.5 mm, window shape 2φ × 4 mm oval, synthetic sapphire window Measurement temperature: 140 ° C
(Pump part)
Liquid feed pump: manufactured by Senshu Kagaku Co., Ltd., SSC-3461 pump (measurement conditions)
Solvent: Orthodichlorobenzene (with 0.5 mg / mL BHT)
Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min

Characteristic (12)
The polyethylene resin composition of the present invention preferably further satisfies the following property (12).
Characteristic (12): Minimum value (g _L ) of molecular weight between 100,000 and 1,000,000 in the branching index g ′ measured by a GPC measuring device combining a differential refractometer, a viscosity detector, and a light scattering detector Is 0.30 to 0.70, preferably 0.0.35 to 0.0.65, more preferably 0.40 to 0.60, still more preferably 0.45 to 0.55.
The branching index g ′ is a measure of the degree of long chain branching, and (g _L ) can be achieved by introducing a certain amount of long chain branching into the polyethylene resin composition. .
If the g _L value is greater than 0.70, the effect of improving the molding processability and fluidity may be reduced, such being undesirable. If the g _L value is less than 0.30, the molding processability and fluidity are improved, but the impact strength may be lowered or the transparency may be deteriorated, which is not preferable.
In the present invention, the g _L value of the polyethylene resin composition is a method for evaluating the amount of long chain branching using a molecular weight distribution curve or branching index (g ′) calculated from the following GPC-VIS measurement.

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

References:
1. Developments in polymer characterization, vol. 4). Essex: Applied Science; 1984. Chapter 1.
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4). Macromolecules, 33, 6945-6925 (2000).

[Calculation of branching index (g ′)]
The branching index (g ′) is calculated as a ratio (ηbranch / ηlin) between the intrinsic viscosity (ηbranch) obtained by measuring the sample with the above Viscometer and the intrinsic viscosity (ηlin) obtained separately by measuring a linear polymer. To do.
When long chain branching is introduced into a polymer molecule, the radius of inertia is reduced compared to a linear polymer molecule of the same molecular weight. Since the intrinsic viscosity decreases as the inertia radius decreases, the ratio (ηbranch / ηlin) of the intrinsic viscosity (ηbranch) of the branched polymer to the intrinsic viscosity (ηlin) of the linear polymer having the same molecular weight decreases as long chain branching is introduced. It will become.
Therefore, when the branching index (g ′ = ηbranch / ηlin) is smaller than 1, it means that a branch is introduced, and the introduced long chain branching increases as the value decreases. Means that. In particular, in the present invention, as the absolute molecular weight obtained from the MALLS, the minimum value of the g 'in the molecular weight 100,000 from 1,000,000, calculated as _{g L.}
Here, linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology) was used as the linear polymer.

Characteristic (13)
The polyethylene resin composition of the present invention preferably further satisfies the following property (13).
Characteristic (13): The value (g _m ) at a molecular weight of 100,000 of the branching index g ′ measured in the same manner as g _L described above is 0.50 to 0.90, preferably 0.55 to 0.85. More preferably, it is 0.60-0.80, More preferably, it is 0.65-0.79.
Within this range, melt processability and fluidity are further improved, and the molding process can be performed at a temperature lower than that of the prior art, so that the effect of reducing the amount of electric power is increased. If the g _m value is larger than 0.75, the effect of improving the molding processability and fluidity becomes small, which may not be preferable.
If the g _m value is less than 0.50, the moldability and fluidity are improved, but the impact strength may be lowered, which may not be preferable.
The long-chain branched structure (ie, g _L , g _m ) and comonomer copolymer composition distribution of the resulting copolymer change the polymerization conditions such as catalyst type, catalyst molar ratio, polymerization temperature, pressure, and time, and the polymerization process. Is adjustable by.

According to the polyethylene resin composition of the present invention, since it is a polyethylene material having the above characteristics (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 form a molded body that has excellent pinch-off characteristics and high compatibility of the resin components and excellent appearance of the molded body.
Furthermore, preferably, in addition to the above characteristics (1) to (5), a polyethylene resin composition having one or more of the above characteristics (6) to (13) exhibits the above effects even better.

The above effect will be further described below.
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 or a Ziegler system The melt tension is higher than that of an ethylene polymer composition using a catalyst or an ethylene polymer composition in which they are mixed, and the drawdown resistance during molding can be improved.

In general, polyethylene is processed into an industrial product by a molding method that passes through a molten state such as film molding, blow molding, foam molding, etc., but at this time, elongation flow characteristics represented by the above-mentioned elongation viscosity and strain hardening degree are used. It is well known that has a great influence on the ease of molding.
That is, polyethylene having a narrow molecular weight distribution and no long chain branching has poor moldability due to low melt strength, whereas polyethylene having an ultrahigh molecular weight component or long chain branching component is strain-hardened (strain Hardening), that is, polyethylene having a characteristic that the extensional viscosity rapidly increases on the high strain side, and it is said that polyethylene exhibiting this characteristic is excellent in moldability. Polyethylene resin having such elongation flow characteristics can prevent, for example, uneven thickness and blow-through of products in film molding and hollow molding, enables high-speed molding, and can increase the closed cell ratio during foam molding. There are benefits, such as improved strength of the molded product, improved design, lighter weight, improved molding cycle, improved heat insulation, etc. The strength anisotropy presumed to be caused by orientation causes inconveniences such as a reduction in impact strength of the molded product.
On the other hand, the long chain branching structure, which is the main governing factor of the elongational viscosity property, is devised to improve the molding process surface and to overcome the disadvantages of the mechanical property surface of the molded product due to the elongational flow property of polyethylene In order to solve this problem, the polyethylene resin composition was intensively studied. According to the present invention, as described above, the polyethylene component (B) that satisfies the specific physical property balance and is an intermediate molecular weight component and in which an inflection point of elongational viscosity resulting from strain hardening is observed is a high molecular weight component. And a low molecular weight component as a compatibilizing agent, a polyethylene component (A) having specific physical properties, a low melt flow component of the composition, that is, a high molecular weight component, and a polyethylene component (C) having specific physical properties. By using a combination of high melt flow components, that is, low molecular weight components and high density components, it contributes to the improvement of rigidity, environmental stress crack resistance and impact resistance, as well as molding processing characteristics, especially drawdown resistance. It has excellent hollow moldability such as moldability and pinch-off moldability, can be molded thinner and lighter, has high melt tension and excellent draw-down resistance, and has a complicated shape. It can be considered to be. In particular, the polyethylene component of the inflection point of elongational viscosity of a medium molecular weight component due to the strain hardening is observed (B), HLMFR, and select the ones gm, and the g _L satisfies the specific value By containing appropriately, there is a feature that it is excellent in the melt tension of elongation viscosity characteristics and fluidity, and there is an advantage that, for example, it has excellent drawdown resistance and can easily make the thickness balance of the molded product uniform.

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. A polyethylene resin composition having excellent appearance is obtained. Further, since the polyethylene component (B) satisfying the specific physical property balance has a high elongation viscosity, it is presumed that the appearance of the molded product is particularly excellent because it is easy to suppress appearance defects such as shark skin.
Among them, when the polyethylene component (A) has an appropriate long-chain branched structure, the melt flow rate ratio is specific, and thereby, the polyethylene component (A) is converted into the polyethylene component (B) and the polyethylene component (C). Since the high degree of dispersion is possible, the compatibility is good. Therefore, in the molded product, the surface properties become smooth and the appearance is particularly excellent.
Since the polyethylene resin composition of the present invention is a polyethylene resin composition having the above physical properties, it is excellent in moldability, high fluidity, odor, food safety, rigidity, heat resistance and the like.

5). Manufacturing method of polyethylene resin composition The polyethylene resin composition of the present invention is also necessary by melt-mixing the polyethylene component (A) with the polyethylene component (B) and the polyethylene component (C) at a predetermined blending ratio. Depending on the case, it can be produced by adding and mixing other components.
In the polyethylene resin composition in the present invention, the polyethylene component (A), which is an essential component of the polyethylene resin composition, contains the following substances as long as the object of the present invention is not impaired, in addition to the polyethylene component (B) and the polyethylene component (C). It can be blended as an optional component.
For example, various ethylene polymers such as high-density polyethylene, low-density polyethylene, high-pressure polyethylene, polar monomer graft-modified polyethylene, ethylene wax, ultrahigh molecular weight polyethylene, and 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 preferable for improving flexibility, easy adhesion, transparency, low-temperature strength, moldability, and the like. Addition of polar monomer graft-modified polyethylene such as maleic acid-modified polyethylene, ethylene / acrylic acid derivative copolymer, ethylene / vinyl acetate copolymer, flexibility, easy adhesion, colorability, compatibility with various materials, gas barrier properties, etc. It is preferable to improve. Addition of an ethylene-based wax is preferable for improving colorability, compatibility with various materials, moldability, and the like. Addition of ultrahigh 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, Natural rubbers, polyurethanes, polyvinyl chloride, fluorine resins such as Teflon (registered trademark), inorganic polymers such as silicon resins, and the like.

The polyethylene resin composition of the present invention can be pelletized by mechanical melt mixing with a pelletizer, homogenizer, or the like according to a conventional method, and then molded by various molding machines to obtain a desired molded product.
In addition to the other olefin polymers and rubbers, the polyethylene resin composition obtained by the above-mentioned method is not limited to 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 blended.
As additives, for example, one or more antioxidants (phenolic, phosphorus, sulfur), lubricants, antistatic agents, light stabilizers, ultraviolet absorbers, and the like can be used in combination as appropriate. As filler, calcium carbonate, talc, metal powder (aluminum, copper, iron, lead, etc.), silica, diatomaceous earth, alumina, gypsum, mica, clay, asbestos, graphite, carbon black, titanium oxide, etc. can be used. Of these, calcium carbonate, talc and mica are preferably used. In any case, the polyethylene resin composition can be blended with various additives as necessary and kneaded with a kneading extruder, a Banbury mixer, or the like to obtain a molding material.

In the present invention, it is also an effective technique to use a nucleating agent in order to further accelerate the crystallization rate of the polyethylene resin composition.
As the nucleating agent, generally known nucleating agents can be used, and general organic or inorganic nucleating agents 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 rosin acid partial metal salt, an inorganic fine particle such as talc, an imide Amides, quinacridone quinones, or mixtures thereof.
Among them, a dibenzylidene sorbitol derivative, an organic phosphate 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 Sorbitol is mentioned, and specific examples of the metal salt of benzoic acid include hydroxy-di (t-butylbenzoic acid) aluminum.

  When mix | blending a nucleating agent with the polyethylene resin composition of this invention, the compounding quantity of a nucleating agent has preferable 0.01-5 mass parts with respect to 100 mass parts of this composition, More preferably, 0.01-3. Part by mass, more preferably 0.01 to 1 part by mass, particularly preferably 0.01 to 0.5 part by mass. If the nucleating agent is less than 0.01 parts by mass, the effect of improving the high-speed moldability is not sufficient. On the other hand, if it exceeds 5 parts by mass, there is a problem that the nucleating agent is likely to aggregate and become loose.

6). A molded object and a container The molded object of this invention is a molded object created using the polyethylene resin composition which concerns on the said this invention.
Moreover, the container of this invention is a container created using the polyethylene resin composition which concerns on the said this invention.
Using the polyethylene resin composition of the present invention as a raw material, a molded product can be produced by various molding methods. Preferably, it is mainly molded by a hollow molding method or the like, and various molded products such as a hollow container are preferably obtained.

Since the polyethylene resin composition of the present invention satisfies the above characteristics, the molded product of the present invention using the polyethylene resin composition is excellent in environmental stress crack resistance, impact resistance, odor, food safety, rigidity, In addition to excellent heat resistance, the compatibility of the resin components is high, the surface properties of the molded article are excellent, and the appearance is good. Further, it can be formed thinner and lighter and has good pinch-off characteristics.
Therefore, it is suitable for applications such as containers that require such characteristics, and in particular, containers for cosmetics, detergents, shampoos and rinses, or food containers such as edible oils that are required to have a good appearance. It can use suitably for a use.
Since the polyethylene resin composition of the present invention satisfies the above characteristics, it can be suitably used for the various small containers.

  In particular, a container which is a molded body using the polyethylene resin composition of the present invention is suitable as a container for detergents, shampoos, rinses and the like, which are excellent in product characteristics and economically advantageous.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.

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

(5) Melt tension:
The melt tension (MT) was determined by measuring the stress when the molten ethylene polymer was stretched at a constant speed, and was measured under the following conditions.
[Measurement condition]
Model used: Toyo Seiki Seisakusho, Capillograph 1B
Nozzle diameter: 2.095mm
Nozzle length: 8.0mm
Inflow angle: 180 ° (flat)
Extrusion speed: 15 mm / min Take-off 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. A sample is prepared by preparing a test piece having a cross section of 4 mm × 4 mm in which a 1 mm notch is made with a razor blade around a 6 mm × 6 mm × 11 mm square pillar, and pure water at 80 ° C. Among them, a tensile stress corresponding to 3.7 MPa was applied to the specimen, and the time until the specimen broke was measured to obtain the FNCT breaking time.

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

(8) Melting point and crystallization time (crystallization rate):
Melting | fusing point and crystallization temperature were measured with the differential scanning calorimeter (DSC-7 by Perkin-Elmer Co.). That is, about 5 mg of a sample obtained by cutting a 0.2 mm thick press sheet into a circle is packed in an aluminum pan, heated to 200 ° C. in a nitrogen atmosphere, held at the same temperature for 5 minutes, and 30 at 10 ° C./min. After cooling to 0 ° C. and holding at that temperature for 5 minutes, the temperature was raised to 200 ° C. at 10 ° C./min, and the temperature at which the change in the amount of heat with melting was maximized was taken as the melting point (Tm).
In addition, the sample was allowed to stand at 190 ° C. for 5 minutes using a differential scanning calorimeter (Perkin Elmer DSC-7), and then cooled to 121.5 ° C. at a rate of 120 ° C./min. The peak top was detected and measured at the time when crystallization was completed at an isothermal temperature of 121.5 ° C., and this was taken as the crystallization time.

(9) Presence or absence of long-chain branched structure:
Using a test piece prepared by press forming a sheet of 18 mm × 10 mm and thickness 0.7 mm, using a rheometer (Ales manufactured by Rheometrics), measurement of elongational viscosity at 170 ° C. and strain rate of 0.1 / second is performed. The presence or absence of a long chain branched structure was confirmed by the presence or absence of strain hardening (presence or absence of rising of elongational viscosity).
[Measurement condition]
Apparatus: Ales manufactured by Rheometrics
Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
Measurement temperature: 170 ° C
Strain rate: 0.1 / second Preparation of test piece: A sheet of 18 mm × 10 mm and a thickness of 0.7 mm was formed by press molding.
[Calculation method]
The elongational viscosity at 170 ° C. and strain rate of 0.1 / second was plotted on 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 log-log graph, the maximum elongation viscosity until strain becomes 4.0 after strain hardening is η _Max (t1) (t1 is the time when the maximum elongation viscosity is shown), and the extension viscosity before strain hardening. when the approximate line was η _linear (t), defines the value calculated as _{η Max (t1) / η linear} (t1) strain hardening degree and (.lambda.max). The presence or absence of strain hardening was determined by whether or not there was an inflection point at which the extensional viscosity changed from an upward convex curve to a downward convex curve over time.
1 and 2 are typical plots of elongational viscosity. FIG. 1 shows a case where an inflection point of elongational viscosity is observed, and η _Max (t1) and η _Linear (t1) are shown in the figure. FIG. 2 shows a case where an inflection point of elongational viscosity is not observed.

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

[Sample preparation]
A 3 mL sample and 3 mL of orthodichlorobenzene (containing 0.1 mg / mL 1,2,4-trimethylphenol) were weighed into a 4 mL vial, and capped with a resin screw cap and a Teflon (registered trademark) septum. Then, it melt | dissolved for 2 hours using the SSC-9300 type | mold high temperature shaker by Senshu Scientific set to the temperature of 150 degreeC. After dissolution, it was visually confirmed that there were no insoluble components.
[Create calibration curve]
Four 4 mL glass bottles are prepared, and 0.2 mg each of monodisperse polystyrene standard samples or n-alkanes of the combinations (1) to (4) below are weighed, followed by orthodichlorobenzene (0.1 mg / mL). Of SSC-9300 model manufactured by Senshu Kagaku, which was set at a temperature of 150 ° C. after weighing 3 mL (including 1,2,4-trimethylphenol) and capping with a resin screw cap and a Teflon (registered trademark) septum. Dissolution was carried out for 2 hours using a shaker.
(1) Shodex S-1460, S-66.0, n-eicosane (2) Shodex S-1950, S-152, n-tetracontane (3) Shodex S-3900, S-565, S -5.05
(4) Shodex S-7500, S-1010, S-28.5
The vial containing the sample solution was set in the apparatus, and measurement was performed under the above-described conditions. A chromatogram (retention time and differential refractometer detector response data set) 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 molecular weight. Here, the molecular weights of n-eicosane and n-tetracontane were 600 and 1200, respectively. A nonlinear least square method was applied to this plot, and the obtained quartic curve was used as a calibration curve.

[Calculation of molecular weight]
Measurement was performed under the above-mentioned conditions, and a chromatogram was recorded at a sampling interval of 1 s. This chromatogram by Sadao Mori “Size Exclusion Chromatography” (Kyoritsu Shuppan) Chapter 4 p. The differential molecular weight distribution curve and average molecular weight values (Mn, Mw and Mz) were calculated by the method described in 51-60. However, in order to correct the molecular weight dependency of dn / dc, the height H from the baseline in the chromatogram was corrected by the following equation. Chromatogram recording (data acquisition) and average molecular weight calculation were performed on a PC on which Microsoft Windows OS (registered trademark) XP was installed by using a program (manufactured by Microsoft Visual Basic 6.0 manufactured by Microsoft).
H ′ = H / [1.032 + 189.2 / M (PE)]
In addition, the following formula was used for the molecular weight conversion from polystyrene to polyethylene.
M (PE) = 0.468 × M (PS)

(11) Dynamic melt viscosity (η _{H · 0.01} ):
A sample prepared by blending 2000 ppm of antioxidant (IRGANOX B225 manufactured by BASF Japan), melt kneaded into a 1.0 mm thick sheet by hot pressing, and using a rheometer (Ares manufactured by Rheometrics), using a parallel plate 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) when the frequency ω was measured at 0.01 rad / sec was defined as the dynamic melt viscosity (η _{H · 0.01} ) at a low strain rate.
[Measurement condition]
Apparatus: Ales manufactured by Rheometrics
Jig: 25mm diameter parallel plate, plate spacing about 1.0mm
Measurement temperature: 190 ° C
Frequency range: 0.01 to 100 (unit: rad / sec)
Strain range: 0.2 to 1%

(12) Dynamic melt viscosity (ηW _{· 0.01} ) of polyethylene resin composition:
Using a sample molded into a sheet having a thickness of 2.0 mm by hot pressing, using a rheometer (Ales manufactured by Rheometrics), using a parallel plate at a temperature of 190 ° C., a plate interval of 1.7 mm, a strain of 10%, and a frequency ω The dynamic melt viscosity (unit: Pa · sec) measured at 0.01 rad / sec was defined as the dynamic melt viscosity (η _{W · 0.01} ) at a low strain rate.
[Measurement condition]
Apparatus: Ales manufactured by Rheometrics
Jig: 25mm diameter parallel plate, plate spacing approx. 1.7mm
Measurement temperature: 190 ° C
Frequency range: 0.01 to 100 (unit: rad / sec)
Distortion: 10%

(13) Surface properties:
The area ratio of fish eyes was measured by the following mixing property evaluation method, and this was used as the evaluation of surface properties.
[Mixability evaluation method]
The sample to be measured is compressed 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 and cooling. In the second step, a press sheet having a thickness of 0.4 mm is formed by cooling at a temperature of 30 ° C. and a pressure of 50 kgf / cm ² . This press sheet was cut into a 50 × 50 × 0.4 mm test piece.
Next, the test piece was stretched with a biaxial stretching apparatus. As the biaxial stretching apparatus, a biaxial stretching apparatus SS-60 manufactured by Shibayama Scientific Instruments Co., Ltd. was used, 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 the 1 cm portion of the end of the test piece was chucked by four chuck portions of the biaxial stretching device, and the unchucked central portion of the press sheet was set to a 30 × 30 mm square. Thereafter, the test piece is heated to a temperature of 130 to 170 ° C., biaxially stretched until the distance between diagonal chucks becomes 60 mm, and a sheet in which the center portion not chucked is stretched about twice is obtained. Created.
The surface of a 30 × 30 mm square region located approximately at 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 (one field of view) of the photographed sheet is 10 × 10 mm. In order to increase the reliability of the measurement, the measurement was performed four times with respect to one sample in a 30 × 30 mm square range located in the center of the sheet so that the respective fields of view do not overlap. The photographed image was binarized into a fish eye part and a non-fish eye part (uniform matrix part). The condition of the binarization process was set by a 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 the 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 diameter, the circularity The characteristic parameters such as were calculated. In this case, the feature parameters can be calculated using commercially available image processing software or the like, and as a commercially available image analysis software, WinROOF manufactured by Mitani Corporation is used.
The image data defines a threshold value for the color arrangement of the black and white portions of the image, and is binarized and processed at an appropriate level. The condition of the binarization process was set by a measurer, and the condition was used for all measurements.
Image analysis calculates the area, perimeter, maximum length, maximum length vertical length (length in the direction perpendicular to the maximum length), etc. of each particle using known means, and the various parameters of the particles are calculated for each particle. The parameters that can be calculated are the equivalent circle diameter of the particle (diameter of the circle with the area equal to the area of the particle image), the circularity (peripheral length of the circle with the area equal to the area of the particle image) And the ratio of the perimeter of the image) and the aspect ratio (ratio of the maximum length of the particle image to the maximum vertical length of the particle).
The equivalent circle diameter is equivalent circle diameter = (area value of particle image / π) ^1/2 × 2, and the circularity is circularity = (peripheral length of circle having area value of particle image) / ( The peripheral length of the particle image) and the aspect ratio are calculated by (maximum length of the particle image) / (maximum vertical length of the particle image).
In the present invention, as the measurement of fish eyes, the area ratio of fish eyes in the image was determined. For the area ratio of one sample of fish eye, the average value of the measured values obtained for each of the four visual fields photographed on one test piece was calculated.
And, when the area ratio of the fish eye in the image is 0.2% or less, “1”, when it is more than 0.2 to 0.5%, “2”, more than 0.5 to 3.0% The case was evaluated as “3”, the case of over 3.0 to 5.0% as “4”, and the case of over 5% as “5”. The evaluation results are shown in Table 1.

(14) Overall evaluation:
The suitability of the hollow moldability as a polyethylene resin composition was evaluated, and all the following items were evaluated as “◯” and the other items as “×”.
That is, the following pinch-off characteristics, drawdown resistance and elongational viscosity were measured.
1) Pinch-off characteristics: The tan δ measurement at 150 ° C. and 100 rad / sec measured by a rheometer is performed using a sample adjusted by a hot press, using a rheometer (Ales manufactured by Rheometrics) 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 measurement conditions are described below. A pin having a tan δ of 0.50 to 0.80 was considered to have good pinch-off characteristics.
[Measurement condition]
Apparatus: Ales manufactured by Rheometrics
Jig: 25mm diameter parallel plate, plate spacing approx. 1.7mm
Measurement temperature: 150 ° C
Distortion: 10%
2) Draw-down resistance: Good with a melt tension (MT) of 60 mN or more.
3) Those in which the rising of the extensional viscosity was confirmed were considered good.

2. Examples and Comparative Examples <Synthesis of Metallocene Catalyst>
³ g of silica (average particle size 11 μm, surface area 313 m ² / g, pore volume 1.6 cm ³ / g) was charged into a cylindrical flask equipped with an induction stirrer that was sufficiently purged with nitrogen, and 75 ml of toluene was added. And heated to 75 ° C. with an oil bath. In a separate flask, 8.0 ml of a toluene solution of methylaluminoxane (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, heated to 75 ° C., and stirred for 1 hour. Subsequently, this toluene solution was added to a toluene slurry of silica heated to 75 ° C. while stirring and held for 1 hour. Thereafter, 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 the catalyst was sufficiently settled, the supernatant was removed and 200 ml of n-hexane was added. After stirring once, it was allowed to stand again to remove the supernatant. This operation was repeated 3 times to remove components liberated in n-hexane. Furthermore, the solvent was distilled off under reduced pressure while being heated at 40 ° C. After the degree of vacuum became 0.8 mmHg or less, vacuum drying was further continued for 15 minutes to obtain a metallocene catalyst (i).
<Manufacture of anti-fouling ingredients>
100 g of xylene, 3 g of n-octylated polyethyleneimine derived from polyethyleneimine (molecular weight 10,000) (in which 0.5 n-octyl groups are introduced per monomer unit of polyethyleneimine) and phosphate ester 1 g of phytic acid as a compound was mixed and stirred at room temperature to form a salt. Thereafter, 6 g of dioctylsulfosuccinate magnesium salt was mixed to obtain a fouling prevention component.

<Production of polyethylene component (A1)>
A polyethylene component (A1) was produced by carrying out ethylene / 1-hexene copolymerization using the metallocene catalyst. That is, dehydrated and purified isobutane 115 L / h, triisobutylaluminum 0.13 mol / h, and fouling prevention component B 6 ml / h were supplied to a loop type slurry reactor having an internal volume of 290 L, and the temperature in the reactor was 70 ° C. As the pressure is maintained at 4.2 MPaG, ethylene, 1-hexene and hydrogen are supplied while being intermittently discharged from the reactor so that the molar ratio of 1-hexene and ethylene in the liquid during polymerization is 0. 007, the molar ratio of hydrogen to ethylene was adjusted to 3.2 × 10 −4. Next, the catalyst A hexane slurry diluted to 0.3 g / L with hexane is supplied to the reactor at 3 L / h to start polymerization, and ethylene is supplied so that the ethylene concentration in the reactor becomes 10 vol%. did. The produced polyethylene was intermittently discharged together with isobutane, flushed, and 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) exhibited a relatively large HLMFR / MFR in proportion to the molecular weight distribution, and thus had a long chain branched structure.

<Polyethylene component (B1)>
An ethylene polymer polymerized with a metallocene catalyst produced according to the examples of JP-A-2015-63515 was used. The polymer had an HLMFR of 360 g / 10 min, a density of 0.9605 g / cm ³ , Mw of 61,000, and Mw / Mn of 7.2.
<Polyethylene component (B2)>
An ethylene polymer polymerized with a metallocene catalyst was used. The polymer had an HLMFR of 16.9 g / 10 min, a density of 0.9495 g / cm ³ , Mw of 108,000, and Mw / Mn of 4.7.
<Polyethylene component (B3)>
An ethylene polymer polymerized with a metallocene catalyst was used. The polymer had an MFR of 240 g / 10 min, a density of 0.9699 g / cm ³ , Mw of 29,000, and Mw / Mn of 5.7.

<Polyethylene component (C1)>
An ethylene polymer polymerized with a Ziegler catalyst was used. The polymer had an MFR of 192 g / 10 min, a density of 0.9694 g / cm ³ , an Mw of 37,000, and an Mw / Mn of 7.7.
<Polyethylene component (C2)>
An ethylene polymer polymerized with a Ziegler catalyst was used. The polymer had an MFR of 50 g / 10 min, a density of 0.9660 g / cm ³ , Mw of 49,000, and Mw / Mn of 6.8.
<Polyethylene component (C3)>
An ethylene polymer polymerized with a Ziegler catalyst was used. The polymer had an MFR of 11 g / 10 min, a density of 0.9632 g / cm ³ , an Mw of 73,000, and an Mw / Mn of 6.5.
<Polyethylene component (C4)>
An ethylene polymer polymerized with a Ziegler catalyst was used. The polymer had an MFR of 33 g / 10 min, a 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 catalyst was used. The polymer had an MFR of 17 g / 10 min, a density of 0.9640 g / cm ³ , Mw of 63,000, and Mw / Mn of 6.5.

[Example 1]
<Manufacture of polyethylene resin composition>
The polyethylene component (A) (A1), the polyethylene component (B), the polyethylene component (B1), and the polyethylene component (C), the polyethylene component (C3), were melted at the ratio shown in Table 1 under the following kneading conditions. By mixing, a polyethylene resin composition was produced.
[Kneading conditions]
Equipment used: Laboplast mill roller mixer manufactured by Toyo Seiki Seisakusho (mixer model: R100 / blade shape: roller type R100B)
Additive formulation: 2,000 ppm of IRGANOX B225 manufactured by BASF Japan and 1,000 ppm of calcium stearate manufactured by Tannan Chemical Industry Co., Ltd. Filling amount: 70 g / batch
Kneading temperature: 190 ° C
Blade rotation speed: 40rpm
Preheating time: 5 minutes Kneading time: 2 minutes

  The physical properties and evaluation results of the polyethylene resin composition are shown in Table 1. The resulting composition has extremely good compatibility of each component, a short crystallization time, excellent molding high cycleability, excellent fluidity and high melt tension, excellent hollow moldability, and high density. Excellent mechanical properties such as environmental stress crack resistance balance and impact resistance.

[Examples 2 to 8]
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 had good compatibility of each component, high melt tension, excellent molding high cycle property, and excellent mechanical properties such as environmental stress crack resistance and impact resistance.

[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 was a two-component composition, had low melt tension, no rise in elongational viscosity, and poor mixing.

[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 was a two-component composition, had low melt tension, no rise in elongational viscosity, and poor mixing.

[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 obtained polyethylene resin composition had a large HLMFR, the melt tension of the composition was low, and the mixing was not good.

[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 obtained polyethylene resin composition had a low melt tension of the composition.

[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 obtained polyethylene resin composition had a low melt tension of the composition.

According to the present invention, it is excellent in hollow moldability, environmental stress crack resistance, impact resistance, thinner and lighter, excellent in high-speed moldability, good pinch-off characteristics, and resin. It is possible to provide a polyethylene resin composition having high component compatibility and 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 excellent in odor, food safety, rigidity, heat resistance and the like.
Therefore, the polyethylene resin composition of the present invention and the molded product thereof are suitable for uses such as containers that require such characteristics, and in particular, cosmetic containers, detergents, shampoos and rinse containers with excellent appearance, edible oils, etc. It can use suitably for uses, such as a food container.
Furthermore, the container using the polyethylene resin composition of the present invention can be molded at high speed, has excellent product characteristics, and is suitable as an economically advantageous container for cosmetic containers, detergents, shampoos, rinses and the like. is there.
Further, since the polyethylene resin composition of the present invention is excellent in 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 containers. This is very useful in industry.

Claims (7)

10 mass% or more and 40 mass% or less of the following polyethylene component (A), 10 mass% or more and 80 mass% or less of the following polyethylene component (B), and 10 mass% or more and 80 mass% or less of the following polyethylene component (C). A polyethylene resin composition satisfying the following characteristics (1) to (5).
Polyethylene component (A); Characteristic (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 characteristic (a2): density is Polyethylene which is 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 min or more and less than 400 g / 10 min, characteristic (b2): density is 0.940 g / cm ³ or more and 0.970 g / cm ³ or less Characteristic (b3): Temperature of 170 ° C., Elongation viscosity η (t) (unit: Pa · second) measured at an elongation strain rate of 0.1 (unit: 1 / second) and elongation time t (unit: second) Polyethylene in which an inflection point of elongational viscosity due to strain hardening is observed in a log-log plot.
Polyethylene component (C); property (c1): melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg is 10 g / 10 min or more and 200 g / 10 min or less, and property (c2): density is 0.1. 960 g / cm ³ or more 0.980 g / cm ³ or less polyethylene is.
Characteristic (1): MFR is 0.1 g / 10 min or more and 1 g / 10 min or less.
Characteristic (2): HLMFR is 10 g / 10 min or more and 50 g / 10 min or less.
Characteristic (3): Melt flow rate ratio (HLMFR / MFR) which is a ratio of HLMFR to MFR is 40 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 · second) and elongation time t (unit: second) measured at a temperature of 170 ° C. and an elongation strain rate of 0.1 (unit: 1 / second) In the logarithmic plot, an inflection point of elongational viscosity due to strain hardening is observed. The polyethylene resin composition according to claim 1, wherein the polyethylene component (A) satisfies the following property (a3).
Characteristic (a3): Dynamic melt viscosity η _{H · 0.01} (unit: Pa · second) measured when the frequency ω is 0.01 rad / sec at a temperature of 190 ° C. exceeds 100,000, 1,000,000 Less than. The polyethylene resin composition according to claim 1 or 2, wherein the polyethylene component (A) satisfies the following property (a4).
Characteristic (a4): Melt flow rate ratio (HLMFR / MFR) which is a ratio of HLMFR to MFR is 10 or more and 35 or less. The polyethylene resin composition according to any one of claims 1 to 3, wherein the polyethylene component (C) satisfies the following properties (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 min or more and 2,000 g / 10 min or less.
Characteristic (c4): Melt flow rate ratio (MLMFR / MFR) which is a ratio of MLMFR to MFR is 3 or more and 15 or less. Furthermore, the polyethylene resin composition as described in any one of Claims 1-4 which satisfies the following characteristic (6).
Characteristic (6): The melt tension (MT) measured at 190 ° C. is 60 mN or more.   The molded object created using the polyethylene resin composition as described in any one of Claims 1-5.   The container created using the polyethylene resin composition as described in any one of Claims 1-5.