JP2016056359A - Ethylene-based polymer composition and molded body containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene-based polymer composition excellent in moldability, durability and impact strength, hardly generating convexoconcave derived from high molecular weight gel and capable of manufacturing a molded body excellent in appearance and the molded body containing the same.SOLUTION: There is provided an ethylene-based polymer composition or the like containing an ethylene-based polymer (C) satisfying following properties (I) to (IV), a specific ethylene polymer (D) with specific amount respectively. Property (I): it is manufactured by multistage polymerization of specific component (A) and component (B). Property (II): density is 0.900 to 0.968 g/cm. Property (III): HLMFR (C) is 0.14 to 70 g/10 min. Property (IV): HLMFR(B)/HLMFR(A) is 1.5 to 200.SELECTED DRAWING: None

Description

  The present invention relates to an ethylene polymer composition and a molded body comprising the same, and more specifically, it is excellent in moldability, durability and impact strength, and is not easily formed with unevenness due to high molecular weight gel, and has excellent appearance. The present invention relates to an ethylene polymer composition capable of producing an article and a molded body comprising the same.

  Polyethylene resin is excellent in molding processability and various physical properties, and is highly economical and adaptable to environmental problems. Therefore, it is used as a material in a very wide technical field and is used for a wide range of applications. And in order to make the resin suitable for various usage requirements, the molecular weight distribution and composition of the polymer are controlled by combining two or more kinds of resin components, and various physical properties, moldability, molded product of the resin or molded product are controlled. Various techniques for improving the appearance and the like have been proposed.

  As a method of combining two or more kinds of resin components, there are a method of polymerizing each component and then blending by melt kneading or dry blending, a method of continuously performing multistage polymerization, a method of combining these, and the like. Proposed. And the method using the modifier for resin which modifies the physical property, the external appearance, etc. of the material to be reformed by blending with the material to be reformed has been proposed. At that time, if the mixing of each component and the modifying material is not good, the appearance of the molded product may be deteriorated and the physical properties such as mechanical strength may be deteriorated. It is preferable to mix.

  As an example of a resin modifier to be blended with a material to be reformed, as described in JP-A-2003-165873, a so-called Philips catalyst in which chromium trioxide is supported on an inorganic oxide, or a chromium compound is used. Polyethylene polymerized using a non-fired chromium-based catalyst supported on an inorganic oxide is used. Polyethylene polymerized by these methods has long-chain branching, and thus has a high elongation viscosity, a uniform thickness distribution of the molded product, and less uneven thickness. Even when molding large products Draw-down is unlikely to occur, and it is used in many products such as hollow, extruded, film, and sheet because of easy moldability.

Other examples of the resin modifier blended with the material to be modified include an ethylene / α-olefin copolymer having a relatively small molecular weight distribution using a catalyst having a single-site catalyst supported on a carrier. As described in JP-A-2005-239749, the polymer has excellent mechanical strength due to a narrow composition distribution, and can significantly improve the mechanical strength of the material to be reformed.
However, as described in JP-A-2005-239749, since the ethylene / α-olefin copolymer has a narrow molecular weight distribution, it is polymerized to a high molecular weight and added to the material to be reformed. When melt-kneaded, the ethylene / α-olefin copolymer is not sufficiently dispersed, resulting in a high molecular weight gel in the final blend material, which often impairs the appearance of the product. Such high molecular weight gels have a high viscosity and can be dispersed if the viscosity after blending with the material to be modified is sufficiently high, but this involves the weight fraction of the high molecular weight component. It needs to be quite expensive. For this reason, restrictions are imposed on the blend design, and the extrusion characteristics after blending are restricted, so that the production efficiency of the molded product is deteriorated.

As an example of blending a multi-stage polymer product and a single-stage polymer product, 85 to 99% by weight of the component (A) having a bimodal molecular weight distribution is provided for the purpose of providing a polyethylene composition having improved physical properties. And the polyethylene composition containing the component (B) which has a unimodal molecular weight distribution is known (refer patent document 1). In this patent document, the component (B) is a linear ethylene copolymer having a molecular weight of 150,000 to 600,000, a molecular weight distribution of 3.5 to 9.5, and a melt flow index MFR ₂₁ of 0.5. Between 10 and 10 with a controlled density in the range of 910-960 kg / m ³ , and said component B is made separately from component A using a Ziegler-Natta catalyst or a metallocene catalyst Wherein the amount of component (B) calculated from the end product is between 1 and 15% by weight, while component (A) creates a low molecular weight fraction in the first polymerization step. Is disclosed.
However, the thing of the patent document 1 has a high possibility that the component which contacts the component (B) which is a high molecular weight component at the time of melt-kneading will become a low molecular weight fraction, and the viscosity difference resulting from the molecular weight difference becomes large. Therefore, the high molecular weight component of the multi-stage polymer product and the high molecular weight component of the added single-stage polymer product may not be sufficiently dispersed. Therefore, a high molecular weight gel is generated, and a high appearance of the product is required. In use, there was a possibility of poor appearance.

As an example of blending a multi-stage polymer product and two types of single-stage polymer products, it comprises a polyethylene resin composition having a good appearance, excellent fluidity during molding, and excellent wear resistance, and the resin composition With the object of providing a molded article, (i) ultrahigh molecular weight polyethylene resin composition (A) 10 having a density of 930 to 980 kg / m ³ and an intrinsic viscosity [η] of 3 to 30 dl / g. 75% by mass and (ii) 5 to 80% by mass of a polyethylene component (b-1) having an MFR2 of 0.1 g / 10 min or more and less than 1 g / 10 min when measured at a load of 2.16 kg and 190 ° C. A polyethylene resin composition (B) comprising 5 to 80% by mass of a polyethylene component (b-2) having a MFR2 of 1 g / 10 min or more and 30 g / 10 min or less when measured at a load of 2.16 kg and 190 ° C. Polyethylene resin composition (C) is known comprising (see Patent Document 2). In this patent document, the ultrahigh molecular weight polyethylene resin composition (A) is composed of 10 to 75% by mass of a polyethylene component (a-1) composed of ultrahigh molecular weight polyethylene having an intrinsic viscosity [η] of 10 to 40 dl / g, It is disclosed that it comprises 25 to 90% by mass of a polyethylene component (a-2) composed of a low molecular weight or high molecular weight polyethylene having a viscosity [η] of 0.1 to 1 dl / g.

As described below, the dispersibility of the high molecular weight component is influenced by the viscosity difference between the components adjacent to the high molecular weight component during mixing, and the dispersibility of the high molecular weight component is considered to improve as the viscosity difference decreases.
Generally, 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, and when the viscosity ratio becomes too large, It is known that uneven distribution causes gelation and poor appearance due to poor dispersion.

For example, for Newtonian fluids, more detailed studies have been conducted, and when mixing liquids with different viscosity ratios, the conditions for the dispersion of high-viscosity liquids (number of capillaries) are the same depending on the kneading mode. It is reported that it can be arranged by ratio (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 simply applied, but it is considered that the above knowledge can be referred to.
The thing of the patent document 2 is not considered about the point of the viscosity difference of the component adjacent to the polyethylene component (a-1) which consists of ultra high molecular weight polyethylene at the time of blending a multistage polymerization product and a single stage polymerization product. There is no description. Therefore, in Patent Document 2, a method based on the gloss of an injection-molded product is demonstrated as an appearance evaluation, but when a more severe appearance evaluation is performed, a high molecular weight gel is generated and dispersibility is poor. There is a possibility that.

  Moreover, as an example of blending a polymerized product by a Ziegler-Natta catalyst or a metallocene catalyst with another polymerized product, for example, polyethylene resin compositions as described below are known (see Patent Documents 3 to 5).

Patent Document 3 discloses that a high molecular weight ethylene copolymer having a weight average molecular weight value of 300000 or more and a polydispersity Mw / Mn value of 1 to 12 is 40 to 80% by mass, and 20 to 60% by mass. A low molecular weight ethylene homopolymer or ethylene copolymer having a weight average molecular weight value of 8000 to 80000 and a polydispersity Mw / Mn value of 2.5 to 12 at a temperature of 190 ° C., The melt flow rate MFR value measured under a load of 21.6 kg is 6 to 14 g / 10 min, the density value is 0.94 to 0.97 g / cm ³ , and environmental stress crack resistance A bimodal polyethylene blend with an ESCR value greater than 150 h, wherein the blend blend quality of the polyethylene blend measured according to ISO 13949 is less than 3. A bimodal polyethylene blend is disclosed, characterized by:

In Patent Document 4, the melt flow rate is 0.01 to 10 g / 10 min, the density is 880 to 925 Kg / m ³ , and ethylene and an α-olefin having 4 to 12 carbon atoms are copolymerized using a metallocene catalyst. 5 to 95 parts by weight of the copolymer obtained, a melt flow rate of 1 to 100 g / 10 min, a density of 926 to 960 Kg / m ³ , and ethylene with a metallocene catalyst or a Ziegler-Natta catalyst 50 to 95 parts by weight of a component having a density of 890 to 940 Kg / m ³ , comprising 5 to 95 parts by weight of an ethylene / α-olefin copolymer obtained by copolymerizing an α-olefin having 4 to 12 carbon atoms; melt flow rate is 0.01 to 20 g / 10 min, an ethylene polymer or an ethylene · alpha-olefin copolymer having a density of 940~970Kg / ^{m 3} A resin composition comprising 5 to 50 parts by weight of a component which is a density polyethylene is disclosed, and the resin composition has transparency, rigidity, balance of tear strength in the machine direction (MD) and transverse direction (TD), and impact resistance. It is also disclosed that it is suitable for a stretched film having excellent properties, heat sealing properties, shrink pack properties and the like.

Patent Document 5 discloses a specific (I) copolymer of ethylene and α-olefin produced from a metallocene catalyst in an amount of 60 to 90% by weight, and a specific (II) ethylene polymer or ethylene and α-olefin. A polyethylene-based resin comprising 10 to 40% by weight of a copolymer and having a melt flow rate ratio of (II) to (I) of less than 0.8 at a melt flow rate at 190 ° C. and a load of 2.16 kg A composition is disclosed, and it is disclosed that the resin composition is suitable for a sealant film having good hot tack property, heat seal strength, etc., little fish eye, and excellent low odor.
However, these patent documents are insufficiently disclosed to suppress the generation of high molecular weight gel and to obtain a molded product having an even better appearance, and further improvements are desired.

  Under such circumstances, by highly dispersing the high molecular weight component, the generation of high molecular weight gel is suppressed, the moldability, durability and impact strength are excellent, and the unevenness derived from the high molecular weight gel is hardly generated, and the appearance is improved. Although research and development of an ethylene polymer composition capable of producing an excellent molded article and a molded article comprising the same are desired, it is still not sufficient.

Japanese National Patent Publication No. 10-51069 JP 2006-036988 A Special Table 2002-528586 JP 2005-096993 A JP 2007-137920 A

  The object of the present invention is to produce a molded article that is excellent in formability, durability, and impact strength, and that is free from unevenness due to a high molecular weight gel and that has an excellent appearance, in view of the above-mentioned problems of the prior art. Another object of the present invention is to provide an ethylene polymer composition that can be manufactured and a molded article comprising the same.

As a result of intensive studies to solve the above problems, the present inventors have obtained a multi-stage polymerization of a specific component (A) and component (B), resulting in density, high-load melt flow rate (according to JIS K7210). , Measured at a temperature of 190 ° C. and a load of 21.60 kg, hereinafter also referred to as “HLMFR”), the ratio of the HLMFR of the component (A) and the component (B) and the component (A) and the component (B). A specific amount of an ethylene polymer (C) having a specific content ratio by weight and an ethylene polymer (D) produced by a chromium catalyst and having a specific density and high load melt flow rate. An ethylene polymer in which the ethylene polymer composition contains an ethylene polymer (C) containing a high molecular weight component having a relatively narrow molecular weight distribution and the ethylene polymer (D) are excellent in compatibility. Composition It is an ethylene that can disperse a high molecular weight component and have excellent moldability, durability, and impact strength, and can produce a molded product that is less likely to have irregularities derived from a high molecular weight gel and has an excellent appearance. It discovered that it was a type | system | group polymer composition and a molded object consisting thereof, and came to complete this invention.
In addition, the inventors of the present invention have a molded article using the ethylene polymer composition that is excellent in moldability, durability, and impact strength, and that the unevenness derived from the high molecular weight gel hardly occurs and the appearance is excellent. The present inventors have found that it is a molded product and have completed the present invention.

That is, according to the first invention of the present invention, the ethylene polymer (C) satisfying the following characteristics (I) to (IV): 10 to 90% by weight, and the following characteristics (i) to (iii): The ethylene polymer composition characterized by containing 10 to 90% by weight of an ethylene polymer (D) satisfying the above.
Characteristic (I): formed by multistage polymerization of the following component (A) and component (B).
Component (A): Ethylene-based weight having a density (A) of 0.900 to 0.950 g / cm ³ and a high load melt flow rate (HLMFR (A)) of 0.1 to 10 g / 10 min Coalescence.
Component (B): Ethylene-based weight having a density (B) of 0.900 to 0.970 g / cm ³ and a high load melt flow rate (HLMFR (B)) of 0.5 to 100 g / 10 min Coalescence.
Characteristic (II): Density (C) is 0.900 to 0.968 g / cm ³ .
Characteristic (III): High load melt flow rate (HLMFR (C)) is 0.14 to 70 g / 10 min.
Characteristic (IV): The ratio of HLMFR (B) to HLMFR (A) (HLMFR (B) / HLMFR (A)) is 1.5 to 200.
Characteristic (i): produced with a chromium catalyst.
Characteristic (ii): The density (D) is 0.920 to 0.965 g / cm ³ .
Characteristic (iii): High load melt flow rate (HLMFR (D)) is 1 to 100 g / 10 min.

  In addition, according to the second invention of the present invention, there is provided an ethylene polymer composition obtained by multi-stage polymerization of the component (A) and the component (B) in this order in the first invention.

According to the third invention of the present invention, there is provided an ethylene polymer composition in which the component (A) and the component (B) in the first or second invention satisfy the following property (V). The
Characteristic (V): Component (A) content weight ratio (X (A)) to component (B) content weight ratio (X (B)) on the basis of the sum of component (A) and component (B) The ratio (X (A) / X (B)) is 0.11-4.

According to the fourth aspect of the present invention, in any one of the first to third aspects, the density (W) is 0.910 to 0.965 g / cm ³ and the melt flow rate (MFR (W ), Measured according to JIS K7210 at a temperature of 190 ° C. and a load of 2.16 kg) is 0.02 to 1 g / 10 min.

  According to the fifth invention of the present invention, in any one of the first to fourth inventions, HLMFR which is a ratio of the melt flow rate (MFR (W)) and the high load melt flow rate (HLMFR (W)). (W) / MFR (W) is 50-150, The ethylene polymer composition characterized by the above-mentioned is provided.

  According to the sixth invention of the present invention, in any one of the first to fifth inventions, the weight average molecular weight Mw and the number average molecular weight measured by gel permeation chromatography (GPC) of the component (A). The ratio of Mn (Mw / Mn (A)) is 2 or more and less than 5, and an ethylene polymer composition is provided.

  According to the seventh invention of the present invention, in any one of the first to sixth inventions, the component (A) and the component (B) are ethylene polymers polymerized by a metallocene catalyst. An ethylene-based polymer composition is provided.

  According to an eighth aspect of the present invention, in any one of the first to sixth aspects, the component (A) and the component (B) are ethylene polymers polymerized by a Ziegler catalyst. An ethylene-based polymer composition is provided.

  According to the ninth aspect of the present invention, in any one of the first to eighth aspects, the component (A) and the component (B) are polymerized by a gas phase polymerization method or a slurry polymerization method. An ethylene polymer composition is provided.

  According to the tenth aspect of the present invention, in any one of the first to ninth aspects, the component (A) and / or the component (B) is obtained by multistage polymerization of two or more stages. An ethylene polymer composition is provided.

  According to an eleventh aspect of the present invention, there is provided a molded body obtained by molding any one of the first to tenth ethylene polymer compositions.

According to a twelfth aspect of the present invention, there is provided a molded body characterized in that in the eleventh aspect, the sheet is molded.
According to the thirteenth aspect of the present invention, the ethylene polymer (C) satisfying the following characteristics (I) to (IV): 10 to 90% by weight, and the following characteristics (i) to (iii): An ethylene polymer composition (D) 10 to 90% by weight satisfying the above conditions is melt-mixed to provide a method for producing an ethylene polymer composition.
Characteristic (I): formed by multistage polymerization of the following component (A) and component (B).
Component (A): Density (A) is 0.900 to 0.950 g / cm ³ , high load melt flow rate (in accordance with HLMFR (A), JIS K7210, temperature 190 ° C., load 21.60 kg) Is an ethylene polymer having a molecular weight of 0.1 to 10 g / 10 min.
Component (B): Ethylene-based weight having a density (B) of 0.900 to 0.970 g / cm ³ and a high load melt flow rate (HLMFR (B)) of 0.5 to 100 g / 10 min Coalescence.
Characteristic (II): Density (C) is 0.900 to 0.968 g / cm ³ .
Characteristic (III): High load melt flow rate (HLMFR (C)) is 0.14 to 70 g / 10 min.
Characteristic (IV): The ratio of HLMFR (B) to HLMFR (A) (HLMFR (B) / HLMFR (A)) is 1.5 to 200.
Characteristic (i): produced with a chromium catalyst.
Characteristic (ii): The density (D) is 0.920 to 0.965 g / cm ³ .
Characteristic (iii): High load melt flow rate (HLMFR (D)) is 1 to 100 g / 10 min.

The ethylene polymer composition of the present invention and a molded product comprising the same are an ethylene polymer (C) having a structure obtained by multi-stage polymerization of the high molecular weight component (A) and the component (B), and an ethylene heavy polymer. Since it is an ethylene polymer composition containing a specific amount of the polymer (D), the component (C) can be used even when the high molecular weight component (A) has a high viscosity and a relatively narrow molecular weight distribution. The component (B) present in the center part of the particles is an ethylene polymer composition that is excellent in compatibility with each other because it promotes dispersion of the component (A) when melt-kneaded with the material to be modified. effective. In addition, it contains relatively low molecular weight components with a relatively narrow molecular weight distribution, and can be highly dispersed without significantly increasing the viscosity after blending with the material to be modified, with formability, durability and impact strength. In addition, it is difficult to produce irregularities derived from high molecular weight gels, and it is possible to produce a molded product with excellent appearance and extrusion characteristics, so that it is particularly an ethylene polymer composition suitable for sheet molded products. effective.
In particular, these effects are even more remarkable when the ethylene polymer (C) has a structure obtained by multistage polymerization of the component (A) and the component (B) in this order.
Therefore, the ethylene polymer composition of the present invention and a molded article comprising the same can be used for applications in fields where high physical properties and appearance are required because a molded article having excellent physical properties and appearance can be obtained. There is an effect that it can be used.

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.

The present invention relates to 10 to 90% by weight of an ethylene polymer (C) satisfying characteristics (I) to (IV), and 10 to 90 ethylene polymer (D) satisfying characteristics (i) to (iii). The present invention relates to an ethylene-based polymer composition characterized by containing wt%, and a molded body comprising the same.
Hereinafter, the ethylene polymer (C) of the present invention, in particular, the characteristics (I) to (IV) characterizing it, the process for producing the ethylene polymer (C), the resin modifier, and the ethylene polymer (D), in particular, characteristics (i) to (iii) that characterize it, and a method for producing the ethylene polymer (D), and further, an ethylene polymer composition, a molded product, etc. explain.

1. Ethylene polymer (C)
The ethylene polymer (C) used in the ethylene polymer composition of the present invention preferably satisfies the following characteristics (I) to (V).
Characteristic (I): formed by multistage polymerization of the following component (A) and component (B). That is, the ethylene polymer (C) is a multistage polymer of the component (A) and the component (B). In addition, in the multistage polymerization, the order of polymerization of the component (A) and the component (B) is not particularly limited, but from the viewpoint of the characteristics of the obtained resin composition and the work surface, the component (A) and the component ( It is desirable to polymerize B) in this order.
Component (A): Ethylene-based weight having a density (A) of 0.900 to 0.950 g / cm ³ and a high load melt flow rate (HLMFR (A)) of 0.1 to 10 g / 10 min Coalescence.
Component (B): Ethylene-based weight having a density (B) of 0.900 to 0.970 g / cm ³ and a high load melt flow rate (HLMFR (B)) of 0.5 to 100 g / 10 min Coalescence.
Characteristic (II): Density (C) is 0.900 to 0.968 g / cm ³ .
Characteristic (III): High load melt flow rate (HLMFR (C)) is 0.14 to 70 g / 10 min.
Characteristic (IV): The ratio of HLMFR (B) to HLMFR (A) (HLMFR (B) / HLMFR (A)) is 1.5 to 200.
Characteristic (V): Component (A) content weight ratio (X (A)) to component (B) content weight ratio (X (B)) on the basis of the sum of component (A) and component (B) The ratio (X (A) / X (B)) is 0.11-4.

(1) Characteristics (I)
(1-1) Component (A)
The component (A) is an ethylene polymer, the density (A) is 0.900 to 0.950 g / cm ³ , and the HLMFR (A) is 0.1 to 10 g / 10 minutes. is necessary.

The density of the component (A) (A) in the present invention is required to be 0.900~0.950g / cm ^3, preferably 0.910 to 0.935 g / cm ^3, more preferably 0. 915 to 0.935 g / cm ³ . If the density (A) is less than 0.900 g / cm ³ , the rigidity becomes insufficient, such being undesirable. On the other hand, if the density (A) is larger than 0.950 g / cm ³ , the mechanical strength becomes insufficient, which is not preferable.
In addition, in this specification, the density of an ethylene-type polymer and an ethylene-type polymer composition means the value when measured by JISK7112 (1999 edition): A method (underwater substitution method).
A density (A) can be adjusted with the quantity of the alpha olefin at the time of manufacture of a component (A) mainly.

The high load melt flow rate (HLMFR (A)) of the component (A) in the present invention needs to be 0.1 to 10 g / 10 min. Preferably it is 0.1-5 g / 10min, More preferably, it is 0.1-3 g / 10min, It is 0.1 or more and less than 1 g / 10min suitably. When HLMFR (A) is less than 0.1 g / 10 min, the mixing property becomes insufficient, which is not preferable. On the other hand, if HLMFR (A) is greater than 10 g / 10 minutes, the mechanical strength becomes insufficient, such being undesirable.
In the present specification, the HLMFR of the ethylene-based polymer and the ethylene-based polymer composition is JIS K7210 “Testing method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastic”. The value when measured according to the above.
HLMFR (A) can be adjusted mainly by the amount of hydrogen during production of component (A).

The ratio (Mw / Mn (A)) between the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) of the component (A) is preferably 2 or more and less than 5. An Mw / Mn (A) of less than 2 is not preferable because the mixing property becomes insufficient. On the other hand, if Mw / Mn (A) is greater than 5, the mechanical strength becomes insufficient, such being undesirable.
In the present specification, Mw / Mn of the ethylene polymer and the ethylene polymer composition is calculated from the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC). Value.
Mw / Mn (A) can be adjusted mainly by the catalyst species of component (A).

(1-2) Component (B)
The component (B) is an ethylene polymer, the density (B) is 0.900 to 0.970 g / cm ³ , and the HLMFR (B) is 0.5 to 100 g / 10 minutes. is necessary.

The density of the component (B) (B) in the present invention is required to be 0.900~0.970g / cm ^3, preferably 0.910~0.965g / cm ^3, more preferably 0. 915 to 0.965 g / cm ³ . If the density (B) is less than 0.900 g / cm ³ , the rigidity becomes insufficient, such being undesirable. On the other hand, if the density (B) is greater than 0.970 g / cm ³ , the mechanical strength becomes insufficient, such being undesirable.
A density (B) can be adjusted with the quantity of the alpha olefin at the time of manufacture of a component (B) mainly.

The high load melt flow rate (HLMFR (B)) of the component (B) in the present invention needs to be 0.5 to 100 g / 10 min. Preferably it is 0.5-80 g / 10min, More preferably, it is 0.5-50 g / 10min. When the HLMFR (B) is in this range, the high molecular weight component (A) is more highly dispersed when the ethylene polymers (C) and (D) are melt-kneaded. When the HLMFR (B) is less than 0.5 g / 10 minutes, a high molecular weight gel of the component (B) is generated, and the mixing property becomes insufficient. On the other hand, if HLMFR (B) is greater than 100 g / 10 min, the dispersion of component (A) becomes insufficient, such being undesirable.
HLMFR (B) can be adjusted mainly by the amount of hydrogen during production of component (B).

(2) Characteristics (II) to (V)
The ethylene polymer (C) of the present invention preferably satisfies the following characteristics (II) to (V) in addition to the characteristic (I).
Characteristic (II): Density (C) is 0.900 to 0.968 g / cm ³ .
Characteristic (III): HLMFR (C) is 0.14 to 70 g / 10 min.
Characteristic (IV): The ratio of HLMFR (B) to HLMFR (A) (HLMFR (B) / HLMFR (A)) is 1.5 to 200.
Characteristic (V): Component (A) content weight ratio (X (A)) to component (B) content weight ratio (X (B)) on the basis of the sum of component (A) and component (B) The ratio (X (A) / X (B)) is 0.11-4.

(2-1) Characteristics (II)
The density of the ethylene polymer of the present invention (C) (C) is required to be 0.900~0.968g / cm ^3, preferably 0.910~0.959g / cm ^3, more preferably Is 0.915 to 0.956 g / cm ³ . If the density (C) is less than 0.900 g / cm ³ , the rigidity becomes insufficient, which is not preferable. On the other hand, if the density (C) is greater than 0.968 g / cm ³ , the mechanical strength becomes insufficient, such being undesirable.
The density (C) can be adjusted mainly by the amount of α-olefin at the time of production of each of the components (A) and (B) and the polymerization ratio of the components (A) and (B).

(2-2) Characteristic (III)
The high load melt flow rate (HLMFR (C)) of the ethylene-based polymer (C) in the present invention needs to be 0.14 to 70 g / 10 minutes. Preferably it is 0.15-40g / 10min, More preferably, it is 0.16-20g / 10min. When HLMFR (C) is less than 0.14 g / 10 minutes, the mixing property becomes insufficient, which is not preferable. On the other hand, if HLMFR (C) is greater than 70 g / 10 min, the mechanical strength becomes insufficient, such being undesirable.
HLMFR (C) can be adjusted mainly by the amount of hydrogen during production of each of components (A) and (B) and the polymerization ratio of components (A) and (B).

(2-3) Characteristic (IV)
In the ethylene-based polymer (C) of the present invention, the ratio of HLMFR (B) to HLMFR (A) (HLMFR (B) / HLMFR (A)) needs to be 1.5 to 200. Preferably it is 1.5-100, More preferably, it is 1.5-70.
The value of HLMFR (B) / HLMFR (A) is considered to represent the difference in viscosity between component (A) and component (B). Accordingly, when HLMFR (B) / HLMMFR (A) is within this range, the difference in viscosity between component (A) and component (B) becomes small, and the ethylene polymer (C) and the ethylene polymer (D) are reduced. This is preferable because the high molecular weight component (A) is more highly dispersed during melt kneading. When HLMFR (B) / HLMFR (A) is less than 1.5, there is almost no difference in viscosity between component (A) and component (B), so the molecular weight of component (B) approaches component (A) and component (A) A) The same high viscosity is exhibited, and when the component (B) itself melts and kneads the ethylene polymer (C) and the ethylene polymer (D) together with the component (A), it becomes a high molecular weight gel. Therefore, it is not preferable. On the other hand, if HLMFR (B) / HLMMFR (A) is greater than 200, the difference in viscosity between component (A) and component (B) is too large, and the dispersion of component (A) becomes insufficient.
HLMFR (B) / HLMFR (A) can be adjusted mainly by the amount of hydrogen during production of each of components (A) and (B).

(2-4) Characteristics (V)
In the ethylene-based polymer (C) of the present invention, the content of the component (A) relative to the content weight ratio (X (B)) of the component (B) on the basis of the sum of the component (A) and the component (B) The ratio (X (A) / X (B)) of the ratio (X (A)) is preferably 0.11 to 4. Preferably it is 0.3-3, More preferably, it is 0.4-2.5.
When component (A) and component (B) are subjected to multi-stage polymerization in this order, the value of X (A) / X (B) is the high molecular weight produced earlier, present on the outer surface of the particles of component (C). It is considered that the component (A) represents how much the component (B) produced after being present in the center is spread and diffused in the state of the particles of the component (C) before melt kneading. . Therefore, it is preferable that X (A) / X (B) is within this range, because the diffusion of the high molecular weight component (A) existing on the outer surface of the component (C) particles before melt-kneading is sufficient. When X (A) / X (B) is less than 0.11, in the case of actual multistage polymerization, it is necessary to lower the catalytic activity for adjusting the ratio in the production of component (A), and the productivity of component (C) It is not preferable because it drops. On the other hand, when X (A) / X (B) is larger than 4, it is not preferable because the diffusion of the high molecular weight component (A) present on the outer surface of the component (C) particles before melt kneading is insufficient.
X (A) / X (B) can be adjusted mainly by the respective polymerization amounts of component (A) and component (B).

(3) Manufacturing method of ethylene polymer (C) The ethylene polymer (C) of the present invention must be obtained by multistage polymerization of the component (A) and the component (B).
In the multistage polymerization of the present invention, the order of polymerization of the component (A) and the component (B) is not particularly limited, but from the viewpoint of the characteristics of the resin composition obtained and the work surface, the component (A) and the component (B) is preferably subjected to multistage polymerization in this order. The multistage polymerization is preferably continuous multistage polymerization.
In general, the dispersibility of a high molecular weight component is influenced by the viscosity difference between components adjacent to the high molecular weight component at the time of mixing. The smaller the viscosity difference, the better the dispersibility of the high molecular weight component.
The ethylene-based polymer (C) of the present invention satisfies the above-mentioned specific physical properties, and preferably, the component (A) is polymerized first, and then the specific component (B) is produced by multistage polymerization. After the high-molecular-weight component (A) previously produced, which exists at a high probability on the outer surface of the ethylene polymer (C) particles, is present at a high probability at the center. It is presumed that the produced component (B) spreads and diffuses in the state of particles of the ethylene polymer (C) before melt kneading.
The ethylene polymer (C) has a high probability that the component (A) is present on the outer surface of the particles of the ethylene polymer (C), and the component (B) is a particle of the ethylene polymer (C). A structure having a high probability in the center is preferable. The weight ratio of the component (A) to the component (B) in the ethylene polymer (C) is as described above.
As the component adjacent to the high molecular weight component (A) at the time of melt kneading with the material to be reformed, the material to be reformed can be considered in addition to the component (B). ) And the viscosity difference between the materials to be modified are considered to be small compared to the effect of the viscosity difference between the component (A) and the component (B). This is because the component (A) has a high affinity with the component (B) produced by continuous polymerization, so that the viscosity ratio with the component (B) is higher than the viscosity ratio with the material to be reformed added later. This is thought to be strongly influenced.
Thus, in the molded article of the composition using the ethylene polymer (C) of the present invention, the component (A) which is a high molecular weight component is highly dispersed, the generation of high molecular weight gel is also suppressed, and the appearance It is considered that the mechanical strength of the molded product can be improved to a high degree without impairing the strength.
Here, “highly dispersed” specifically means that when the fish eye is measured by the measurement method described below (<Mixability evaluation method>), the evaluation is 4 or less. Say.
Therefore, in the molded product of the composition in which the ethylene polymer (C) of the present invention is mixed, the generation of high molecular weight gel is suppressed, and a high molecular weight component having a relatively narrow molecular weight distribution is used to improve physical properties and the like. When it is made into a molded product even though it contains a relatively small amount and the viscosity after blending with the material to be modified is not so high, irregularities due to high molecular weight gel resulting from poor dispersibility do not occur, and the appearance is excellent Presumed to be.

<Mixability evaluation method>
The fish eye of the composition of the present invention can be measured by the following 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 is cut into test pieces of 50 × 50 × 0.4 mm.
Next, the test piece is stretched with a biaxial stretching apparatus. As the biaxial stretching apparatus, for example, a biaxial stretching apparatus SS-60 manufactured by Shibayama Scientific Instruments Co., Ltd. is used, and the test piece is stretched twice at a temperature of 150 ° C. and a stretching speed of 60 mm / min. The stretching procedure is such that a 1 cm portion of the end of the test piece is chucked by the four chuck portions of the biaxial stretching apparatus, and the unchucked central portion of the press sheet is 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. create.
The surface of a square area of 30 × 30 mm located almost at the center of the biaxially stretched sheet is 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 is 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 is binarized into a fish eye part and a non-fish eye part (a uniform matrix part). The condition of the binarization process can be appropriately searched and set by the measurer.
The binarized image is 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. For example, a scanner GT-F670 (manufactured by EPSON, resolution: 4800 dpi) can be used as the scanner.
The analysis of the image data is realized by, for example, a personal computer and a software program executed on the personal computer. By processing the image data with a personal computer, it is possible to calculate characteristic parameters such as the area of each particle, the perimeter, the major / minor diameter ratio, the particle diameter, and the circularity. In this case, the feature parameters can be calculated using commercially available image processing software. As commercially available image analysis software, for example, WinROOF manufactured by Mitani Corporation can be 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 can be appropriately searched and set by the measurer.
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. Can be calculated. The calculated parameters are the equivalent circle diameter of the particle (diameter of the circle with the area equal to the area of the image of the particle), circularity (ratio of the circumference of the circle with the area equal to the area of the image of the particle and the circumference of the image) ), Aspect ratio (ratio of maximum length of image of particle and maximum length of vertical length).
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 particle image) / (maximum vertical length of particle image).
In the present invention, as the measurement of fish eye, the area ratio of fish eye in the image is obtained. For the area ratio of one sample of fish eye, the average value of the measured values obtained for each of four fields of view taken on one test piece is calculated.
For example, 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”, and more than 0.5 to 3.0% The case is “3”, the case of over 3.0 to 5.0% is “4”, the case of over 5.0 to 10.0% is “5”, and the case of over 10.0% is “6” Can be evaluated.

  According to the above measurement method, for example, a finer fish eye can be measured than when evaluated by the gloss of an injection-molded product, and therefore, it can be used as an advanced evaluation of dispersibility.

The type of the ethylene polymer of component (A) and component (B) is preferably an ethylene homopolymer and / or a copolymer of ethylene and α-olefin, that is, an ethylene polymer. Although it is preferable, in order to further improve the mechanical strength, it is more preferable that the component (A) and the component (B) are ethylene / α-olefin copolymers.
Component (A) and component (B) are homopolymerization 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- It can be obtained by copolymerization with pentene, 1-octene or the like. Also, copolymerization with a diene for the purpose of modification is possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, and the like.
In addition, although the comonomer content rate in the case of superposition | polymerization of a component (A) and a component (B) can be selected arbitrarily, for example, in the case of copolymerization with ethylene and a C3-C12 alpha olefin. The α-olefin content in the ethylene-based polymer is 0 to 40 mol%, preferably 0 to 30 mol%.

The polymerization catalyst of the ethylene polymer of component (A) and component (B) is not particularly limited, but a metallocene catalyst or Ziegler catalyst is preferably used from the balance of HLMFR and density in the scope of the present invention, and more preferably A metallocene catalyst is used.
The Ziegler catalyst includes a Ziegler-Natta catalyst as an olefin coordination polymerization catalyst comprising a combination of a transition metal compound and a typical metal alkyl compound, in particular, a solid catalyst component in which a titanium compound is supported on a magnesium compound and an organoaluminum compound. See the so-called combined Mg-Ti Ziegler catalysts (for example, “Catalyst Application Dictionary; Issued by the 2004 Industrial Research Committee”, “Application System Diagram—Transition of Olefin Polymerization Catalysts; Published by the Invention Association of 1995”). ) Is suitable because it is inexpensive, highly active and excellent in polymerization process suitability.
Among them, an inert carrier material-supported Mg / Ti catalyst as described in JP 54-142192 A and JP 54-148093 A, for example, anhydrous MgCl ₂ in tetrahydrofuran and TiCl ₃ or A catalyst obtained by impregnating porous silica previously treated with triethylaluminum with a uniform mixed solution of TiCl ₄ and drying and drying, or an organic aluminum as described in JP-A-63-117019. A catalyst obtained by subjecting a Mg / Ti catalyst to olefin prepolymerization in the presence of, for example, a solid component obtained by the reaction of MgCl ₂ , Ti (OnBu) ₄ and methylhydropolysiloxane is mixed with TiCl ₄ and methyl hydrodiene. The catalyst obtained by introducing the mixed solution of empolysiloxane is treated with triethylaluminum. Ethylene prepolymerized prepolymerized catalyst thus obtained, and the like. Further, a catalyst component containing a low-valence titanium atom obtained by reacting a magnesium-aluminum complex and a tetravalent titanium compound as described in JP-A-60-195108 and organoaluminum A catalyst for olefin polymerization in combination with a compound, ethylaluminum sesquichloride, etc. to a homogeneous mixture of magnesium ethoxide, tri-n-butoxymonochlorotitanium, n-butanol as described in JP-A-56-61406, etc. Examples thereof include a solid catalyst obtained by dropping, a solid catalyst for olefin polymerization containing magnesium, halogen, titanium and an electron donor as described in JP-A No. 2001-139635.
In the present invention, preferably, for the reason that an ethylene polymer having a narrow molecular weight distribution or copolymer composition distribution can be produced with high activity, the magnesium compound group represented by the following general formula (a) is preferably used. An Mg—Ti Ziegler catalyst characterized in that it contains at least a compound selected from the group and a compound selected from the titanium compound group represented by the following general formula (b) is used.
General formula (a): Mg, MgO, or MgX ¹ _m R ¹ _n (OR ² ) _2-mn

Here, X ¹ is a halogen atom, preferably a chlorine atom, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably methyl, ethyl, propyl, butyl, R ² is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably methyl, ethyl, propyl, butyl. m and n are numbers satisfying 0 ≦ m ≦ 2, 0 ≦ n ≦ 2, and 0 ≦ m + n ≦ 2, respectively.

An example of a preferable embodiment of the general formula (a) is Mg, MgO, MgClR ¹ _n (OR ² ) _1-n , MgCl ₂ , MgX ¹ _m R ¹ _1-m (OR ² ), Mg (OR ² ) ₂ However, 0 ≦ m ≦ 1, 0 ≦ n ≦ 1, and an example of a more preferable embodiment is Mg, MgO, MgClR ¹ , MgCl ₂ , MgX ¹ (OR ² ), Mg (OR ² ) ₂ , An example of a particularly preferred embodiment is MgCl ₂ or Mg (OR ² ) ₂ . However, the definitions of R ¹ , R ² and X ¹ are as described above.

Specifically, the magnesium compound contained in the said general formula (a) can be enumerated below.
_{(1) Mg, MgO, MgF} 2, MgCl 2, MgBr 2, MgI 2, MgClF, MgBrCl, MgClI like,
(2) Mg (CH ₃ ) ₂ , Mg (C ₂ H ₅ ) ₂ , Mg (C ₃ H ₇ ) ₂ , Mg (C ₄ H ₉ ) ₂ , Mg (C ₆ H ₁₃ ) ₂ , Mg (C _{8 H 17) 2, Mg (C} 10 H 21) 2, Mg (C 3 H 5) 2, Mg (C 6 H 11) 2, Mg (C 6 H 5) 2, Mg (C 6 H 4 -CH 3 ) ₂ , Mg (C ₆ H ₄ -C ₂ H ₅ ) ₂ , Mg (C ₆ H ₄ -C ₄ H ₉ ) ₂ , Mg (C ₆ H ₃ (CH ₃ ) ₂ ) ₂ , Mg (CH ₂ — _{C 6 H 5) 2, Mg} (C 2 H 4 -C 6 H 5) 2, Mg (CH 3) (C 2 H 5), Mg (C 2 H 5) (C 4 H 9), Mg (CH _{3) (C 4 H 9)} , Mg (C 4 H 9) (C 6 H 5) or the like,
_{(3) Mg (OH) 2} , Mg (OCH 3) 2, Mg (OC 2 H 5) 2, Mg (OC 3 H 7) 2, Mg (OC 4 H 9) 2, Mg (OC 6 H 13) ₂ , Mg (OC ₆ H ₁₁ ) ₂ , Mg (OC ₆ H ₅ ) ₂ , Mg (OCH ₂ C ₆ H ₅ ) ₂ , Mg (OH) (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ( _{OC 4 H 9), Mg (} OC 6 H 4 CH 3) 2 , etc. _{Mg (C 2 H 5) Cl} , Mg (C 2 H 5) Br, Mg (C 2 H 5) I, Mg (C 4 H 9 ) Cl, (4) Mg (C ₄ H ₉ ) Br, Mg (C ₄ H ₉ ) I, etc.
(5) Mg (OH) Cl , Mg (OH) Br, Mg (OH) I, Mg (OC 2 H 5) Cl, Mg (OC 2 H 5) Br, Mg (OC 2 H5) I, Mg (OC ₄ H ₉ ) Cl, Mg (OC ₄ H ₉ ) Br, Mg (OC ₄ H ₉ ) I, etc.
_{(6) Mg (C 2 H} 5) (OC 2 H 5), Mg (C 2 H 5) (OC 3 H 7), Mg (C 2 H 5) (OC 4 H 9), Mg (C 2 H ₅ ) (OC ₆ H ₁₃ ) etc.

Among them, Mg, MgO, MgCl ₂ , MgBr ₂ , MgI ₂ , Mg (CH ₃ ) ₂ , Mg (C ₂ H ₅ ) ₂ , Mg (C ₃ H ₇ ) ₂ , Mg (C ₄ H ₉ are preferable. ) ₂ , Mg (C ₂ H ₅ ) (C ₄ H ₉ ), Mg (OCH ₃ ) ₂ , Mg (OC ₂ H ₅ ) ₂ , Mg (OC ₃ H ₇ ) ₂ , Mg (OC ₄ H ₉ ) ₂ Mg (OC ₆ H ₁₃ ) ₂ , Mg (C ₂ H ₅ ) Cl, Mg (C ₂ H ₅ ) Br, Mg (C ₂ H ₅ ) I, Mg (C ₄ H ₉ ) Cl, Mg (C ₄ H ₉ ) Br, Mg (C ₄ H ₉ ) I, Mg (OC ₂ H ₅ ) Cl, Mg (OC ₂ H ₅ ) Br, Mg (OC ₂ H ₅ ) I, more preferably MgO, MgCl ₂ , Mg (C ₂ H ₅ ) ₂ , Mg (C ₄ H ₉ ) ₂ , Mg (C ₂ H ₅ ) (C ₄ H ₉ ), Mg (OCH ₃ ) ₂ , Mg (OC ₂ H ₅ ) ₂ , Mg (OC ₃ H ₇ ) ₂ , Mg (OC ₄ H ₉ ) ₂ , particularly preferably MgCl ₂ , Mg (C ₂ H ₅ ) ₂ , Mg (C ₄ H ₉ ) ₂ , Mg (C ₂ H ₅ ) (C ₄ H ₉ ), Mg (OC ₂ H ₅ ) ₂ .
Formula ^{_{(b): TiX 2 p (}} OR 3) 4-p

Here, X ² is a halogen atom, preferably a chlorine atom, R ³ is a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably methyl, ethyl, propyl, Butyl. p is a number satisfying 0 ≦ p ≦ 4.
An example of a preferable aspect of the general formula (b) is TiCl (OR ³ ) ₃ , TiCl ₂ (OR ³ ) ₂ , TiCl ₃ (OR ³ ), TiCl ₄ , and an example of a more preferable aspect is TiCl (OR ³⁾ _3, is TiCl _4.
However, the definition of R ³ is as described above. When p = 0, that is, when Ti (OR ³ ) ₄ is used, a halogenating agent is used in combination.
Here, the halogenating agent is not particularly limited as long as it is a compound having an action of substituting one or more hydrocarbon oxy groups (OR ³ ) of Ti (OR ³ ) ₄ with halogen. Among the magnesium compounds, aluminum compounds, and silicon compounds described in the above, compounds containing halogen atoms, or halogens in elemental state, hydrogen halides such as hydrogen chloride, haloalkanes such as chloroform, thionyl chloride, phosphorus oxychloride, Oxyhalides such as acyl chloride, non-metallic halides such as phosphorus trichloride, phosphorus pentachloride, ammonium chloride, boron chloride, sodium chloride, calcium chloride, zirconium chloride, vanadium chloride, chromium chloride, manganese chloride, iron chloride, chloride Metal halides such as nickel, tin chloride, and zinc chloride are used.

Specific examples of the titanium compound included in the general formula (b) can be listed below.
(1) TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , TiFCl ₃ , TiBrCl ₃ , TiBr ₂ Cl ₂ , TiBr ₃ Cl, TiBrCl ₂ I, etc.
(2) Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₆ H ₁₃ ) ₄ , Ti (OC ₆₎ H ₁₁ ) ₄ , Ti (OC ₆ H ₅ ) ₄ , Ti (OC ₈ H ₁₇ ) ₄ , Ti (OC ₁₀ H ₂₁ ) ₄ , Ti (OCH ₂ C ₆ H ₅ ) ₄ , Ti (OCH ₂ C ₃ H ₅ ) ₄ , Ti (OCH ₂ C ₆ H ₁₁ ) ₄ , Ti (OC ₃ H ₅ ) ₄ , Ti (OC ₂ H ₅ ) (OC ₄ H ₉ ) ₃ , Ti (OC ₂ H ₅ ) ₂ (OC _{4 H 9) 2, Ti (OC} 2 H 5) 3 (OC 4 H 9), Ti (OC 6 H 4 CH 3) 4, Ti (OC 2 H 5) (OC 4 H 9) (OC 6 H 13) ₂ etc. (3) Ti (OCH ₃ ) Cl ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₂ H ₅ ) (OC ₄ H _{9 ) Cl 2, Ti (OC 2} H 5) Br 3, Ti (OC 2 H 5) I 3, Ti (OC 2 H 5) Cl 2 Br, Ti (OC 2 H 5) Cl 2 I, Ti (OC 2 H ₅ ) ClBrI, Ti (OC ₃ H ₇ ) Cl ₃ , Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (OC ₃ H ₇ ) ₃ Cl, Ti (OC ₄ H ₉ ) Cl ₃ , Ti (OC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₄ H ₉ ) ₃ Cl, Ti (OC ₄ H ₉ ) Br ₃ , Ti (OC ₄ H ₉ ) I ₃ , Ti (OC ₅ H ₁₁ ) ₃ Cl, Ti (OC _{6 H 13) 3 Cl, Ti} (OC 6 H 5) 3 Cl, Ti (O _{6 H 5) 2 Cl 2,} Ti (OC 6 H 5) Cl 3 , etc.,

Among them, TiCl ₄ , Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₆ H ₁₃ ) are preferable. ₄ , Ti (OC ₆ H ₁₁ ) ₄ , Ti (OC ₆ H ₅ ) ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₃ H ₇ ) Cl ₃ , Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (OC _{3 H 7) 3 Cl, Ti} (OC 4 H 9) Cl 3, Ti (OC 4 H 9) 2 Cl 2, Ti (OC 4 H 9) 3 Cl, Ti (OC 5 H 11) 3 Cl, Ti ( _{OC 6 H 13) 3 Cl,} Ti (OC 6 H _{) 3 Cl, Ti (OC 6} H 5) 2 Cl 2, Ti (OC 6 H 5) is Cl _3, more _{preferably, TiCl 4, Ti (OC 2} H 5) 4, Ti (OC 3 H 7) ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₃ H ₇ ) Cl ₃ , Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (OC ₃ H ₇ ) ₃ Cl, Ti (OC ₄ H ₉ ) Cl ₃ , Ti (OC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₄ H ₉ ) ₃ are Cl, particularly _{preferably, TiCl 4, Ti (OC 2} H 5) 4, Ti (OC 3 H 7) 4, Ti (OC 4 H 9) 4, Ti (OC 2 H 5) 3 Cl, _{Ti (OC 3 H 7) 3} Cl, Ti (OC 4 H 9) 3 A l.

As the metallocene catalyst, as an example of a polymerization catalyst suitable for multistage polymerization of the component (A) and the component (B), a metallocene catalyst (for example, “metallocene catalyst” which is an olefin polymerization catalyst comprising a metallocene transition metal compound and a promoter component. Next-generation polymer industrialization technology (up / down volume; published by InterResearch, Inc., 1994)) is relatively inexpensive, highly active, excellent in polymerization process, and has a narrow molecular weight distribution and copolymer composition distribution. It is used because an ethylene polymer is obtained.
Among them, a catalyst system for olefin polymerization comprising a so-called metallocene complex and an alumoxane as described in JP-A-60-35007, JP-A-8-34809, JP-A-8-127613, etc. A catalyst system using a promoter component other than alumoxane as described in JP-A-11-193306, JP-A-2002-515522, and the like is preferably used. As the metallocene complex, Ti, Zr, and Hf whose central metal is Group 4 of the periodic table are preferably used because they exhibit high activity for ethylene polymerization. Various structures of these ligands of the central metal are currently known, and the polymerization performance such as the molecular weight of the produced polyethylene and the α-olefin copolymerizability is investigated. As described above, the ethylene polymer (A) of the present invention preferably has no long-chain branched structure or contains only a small amount, but for producing an ethylene polymer having such characteristics, a conjugated five member The ring structure ligand is preferably a so-called non-crosslinked complex that is not crosslinked with another ligand by a crosslinking group. For example, the following general formula [1] as disclosed in JP-A-11-310612 , [2], [3] or [4], the compound [1] and the compound [3] are preferable, and the compound [1] is more preferable. However, it is said that the higher the concentration of ethylene or α-olefin in the polymerization field and the shorter the polymerization reaction time, the more disadvantageous for the generation of the long chain branched structure. Needless to say, these are limited to relative ones assuming that they are implemented under the same conditions. Further, metallocene complexes described in JP-A-5-132518, JP-A-2000-154196, JP-A-2004-161760 and the like are also preferably used, and for example, described in JP-T-2002-535339. A metallocene complex having a monocyclic or polycyclic heteroaromatic group containing a heteroatom as a substituent on a conjugated five-membered ring structure ligand is also preferably used.

Wherein A ^{1 to} A ⁴ are ligands having a conjugated five-membered ring structure (A ^{1 to} A ⁴ may be the same or different in the same compound), and Q 1 is two conjugated five-membered rings A bonding group that bridges the ligand at an arbitrary position, Z ¹ and Z ² are a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom bonded to M, a hydrogen atom, A halogen atom or a hydrocarbon group, Q ² is a bonding group that bridges Z2 with an arbitrary position of the conjugated five-membered ring ligand, M is a metal atom selected from Group 4 of the periodic table, and X and Y Represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group bonded to M, respectively. The above detailed definition shall be in accordance with the publication. ]

  In the present invention, as an example of a suitable metallocene complex, an ethylene polymer having a high molecular weight and a narrow molecular weight distribution or copolymer composition distribution can be produced with high polymerization activity. At least one of the five H atoms on the ligand having a conjugated five-membered ring structure represented by the formula: cyclopentadienyl ring ligand is halogen, hydrocarbon group having 1 to 20 carbon atoms, silicon number C1-C18 silicon-containing hydrocarbon group containing 1-6, C1-C20 halogenated hydrocarbon group or C1-C20 hydrocarbon group-substituted silyl group, C1-C20 containing oxygen Hydrocarbon groups (including alkoxy groups directly bonded to the ring by oxygen atoms, etc., the same applies to sulfur, nitrogen and phosphorus), sulfur-containing hydrocarbon groups having 1 to 20 carbon atoms, and nitrogen-containing carbon atoms 1 ~ 2 It may be mentioned hydrocarbon groups, metallocene complex, characterized in that it is substituted by a substituent selected from a hydrocarbon group having 1 to 20 carbon atoms containing phosphorus. These substituents on the cyclopentadienyl ring may form a ring together with the carbon atoms of the cyclopentadienyl ring to which they are bonded, in which case A1 to A4 are indenyl ring, azulenyl ring, benzoindene. It is possible to be a ligand having a secondary ring typified by a nyl ring, a fluorenyl ring and the like, and is more preferable in that a higher molecular weight ethylene polymer can be obtained.

  As the production process, the component (A) and the component (B) can be produced by a production process such as a gas phase polymerization method, a solution polymerization method, a slurry polymerization method, and the like. As described above, a gas phase polymerization method or a slurry polymerization method is desirable in that the viscosity of the reaction system does not increase even when polyethylene having a relatively low HLMFR, that is, a high molecular weight is produced, so that productivity is excellent. Among the polymerization conditions for the ethylene polymer, the polymerization temperature can be selected from the range of 0 to 300 ° C. In the case of gas phase polymerization, the polymerization is performed at a temperature lower than the melting point of the produced polymer. The polymerization pressure can be selected from the range of atmospheric pressure to about 4 MPa. It can be produced by conducting vapor phase polymerization of ethylene and α-olefin in the absence of a solvent in a state where oxygen, water and the like are substantially cut off. An inert hydrocarbon having a relatively low boiling point such as propane, butane, pentane, and hexane may coexist as long as the flow of the polymer powder in the reactor is not hindered.

The hydrogen supplied to the polymerization vessel in the slurry polymerization is consumed as a chain transfer agent, determines the average molecular weight of the produced ethylene-based polymer, and partly dissolves in a solvent and is discharged from the polymerization vessel. The solubility of hydrogen in the solvent is small, and the hydrogen concentration near the polymerization active point of the catalyst is low unless a large amount of gas phase is present in the polymerization vessel. Therefore, if the hydrogen supply amount is changed, the hydrogen concentration at the polymerization active point of the catalyst changes rapidly, and the molecular weight of the produced ethylene polymer changes following the hydrogen supply amount in a short time. Therefore, a more homogeneous product can be produced by changing the hydrogen supply rate in a short cycle. For these reasons, it is preferable to employ a slurry polymerization method as the polymerization method. In addition, the aspect of changing the hydrogen supply amount is preferably changed discontinuously rather than continuously because the effect of broadening the molecular weight distribution can be obtained.
In the component (A) and the component (B) of the present invention, as described above, it is important to change the hydrogen supply amount, but other polymerization conditions such as polymerization temperature, catalyst supply amount, olefin such as ethylene, etc. It is also important to appropriately change the supply amount, the supply amount of a comonomer such as 1-hexene, the supply amount of a solvent, etc. simultaneously with or separately from the change of hydrogen.

In a preferred method for producing the ethylene polymer (C) according to the present invention, the step of polymerizing the component (A) and the step of polymerizing the component (B) satisfy the following conditions (J) and (K). Is preferred.
Condition (J): In the step of polymerizing component (A), the molar ratio of hydrogen to ethylene in the gas phase part in the polymerization reactor (H ₂ / C _{2 [gas phase part A]} ) is 0.00-0. .40.
Condition (K): Average molar ratio of hydrogen and ethylene in the gas phase in the polymerization reactor in the step of polymerizing component (A) (H ₂ / C _{2 [gas phase A average]} ), and component (B) The ratio of the average molar ratio of hydrogen to ethylene (H ₂ / C _{2 [gas phase B average]} ) ([H ₂ / C _{2 [gas phase B average]} in the polymerization reactor in the step of polymerizing _] / [H ₂ / C _{2 [vapor phase part A average]} ]) is 1.05 to 10.0.

[H ₂ / C _{2 [vapor phase B average]} ] / [H ₂ / C _{2 [vapor phase A average]} ] is more preferably 1.1 to 7.0, and even more preferably 1.10 to 6. .0. At this time, H ₂ / C _{2 [gas phase average]} refers to an average value of measured values at the initial 10 minutes and at the end of each polymerization step. When [H ₂ / C _{2 [vapor phase part B average]} ] / [H ₂ / C _{2 [gas phase A average]} ] is less than 1.05, the difference in molecular weight between component (A) and component (B) is small. Therefore, the compatibility improving effect with the material to be modified is not exhibited, which is not preferable. When [H ₂ / C _{2 [gas phase B average]} ] / [H ₂ / C _{2 [gas phase A average]} ] is greater than 10.0, the molecular weight difference between component (A) and component (B). Is too large, and the dispersion of the component (A) becomes insufficient, so that the effect of improving the compatibility with the material to be modified is hardly exhibited, which is not preferable. In the case of slurry polymerization using a polymerization liquid-filled loop reactor, which will be described later, there may be a case where a gas phase portion does not exist in the polymerization reactor. Therefore, it goes without saying that the definition of H ₂ / C _{2 [gas phase part]} in the present invention can be applied as it is.

As a method for producing an ethylene polymer (C) according to the present invention, the case where the step of polymerizing component (A) and the step of polymerizing component (B) satisfy the following conditions (L) and (M) are preferable. Can also be mentioned as a simple method.
Condition (L): Ethylene homopolymerization or ethylene / α-olefin copolymerization is carried out using an olefin polymerization catalyst containing the following components (a), (b) and (c).
Component (a): 1 to 18 carbon atoms in which at least one of the 5 H atoms on the cyclopentadienyl ligand contains halogen, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 6 silicon atoms. A silicon-containing hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing oxygen (directly bonded with an oxygen atom) Including an alkoxy group bonded to a ring, etc. Hereinafter, sulfur, nitrogen and phosphorus are also included), a hydrocarbon group having 1 to 20 carbon atoms containing sulfur, a hydrocarbon group having 1 to 20 carbon atoms containing nitrogen and phosphorus. Ti, Zr or Hf metallocene compound having a structure substituted by a group selected from hydrocarbon groups having 1 to 20 carbon atoms Component (b): reacting with the metallocene compound of component (a) to form a cationic metallocene compound Compound to be generated Minute (c): Fine particle carrier Condition (M): Weight ratio of the produced ethylene polymer and the olefin polymerization catalyst described in the above condition (L) (weight of ethylene polymer (g) / olefin polymerization) The catalyst weight (g)) is 3000-50000.

  Here, the component (a) refers to the metallocene compound described above, and more preferably a ligand having a conjugated five-membered ring structure represented by the above-described A1 to A4, that is, 5 on the cyclopentadienyl ring ligand. Of the two H atoms, at least 2 or more, more preferably 3 or more, and particularly preferably 4 or more are halogen, a hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms including 1 to 6 silicon atoms. 18 silicon-containing hydrocarbon group, halogenated hydrocarbon group having 1 to 20 carbon atoms, or hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, hydrocarbon group having 1 to 20 carbon atoms including oxygen (directly with an oxygen atom) Including an alkoxy group bonded to the ring, etc. Hereinafter, sulfur, nitrogen and phosphorus are also the same), a hydrocarbon group having 1 to 20 carbon atoms containing sulfur, a hydrocarbon group having 1 to 20 carbon atoms containing nitrogen and phosphorus. Contains 1-20 hydrocarbons More preferably 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, and a halogenated hydrocarbon having 1 to 20 carbon atoms. Group or a C1-C20 hydrocarbon group-substituted silyl group, a C1-C20 hydrocarbon group containing oxygen, a C1-C20 hydrocarbon group containing sulfur, more preferably C1-C20 Hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including 1 to 6 silicon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen, particularly preferably a hydrocarbon group having 1 to 20 carbon atoms It is substituted by a C1-C18 silicon-containing hydrocarbon group containing 1 to 6 silicon atoms or a C1-C20 hydrocarbon group containing oxygen.

  These substituents on the cyclopentadienyl ring may form a ring together with the carbon atoms of the cyclopentadienyl ring to which they are bonded, in which case A1 to A4 are indenyl ring, azulenyl ring, benzoindene. It is possible to be a ligand having a secondary ring typified by a nyl ring, a fluorenyl ring and the like, and is more preferable in that a higher molecular weight ethylene polymer is obtained, and an indenyl ring is more preferable. When the ring is an indenyl ring, a compound represented by the above general formula [2], that is, a bridged bisindenyl complex structure is preferable, and the two indenyl rings are a known carbon bridge group or Si bridge group at the 1-position. A crosslinked structure is more preferable, and in addition, the above-described halogen at the 2-position, 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, C1-C20 halogenated hydrocarbon group or C1-C20 hydrocarbon group-substituted silyl group, C1-C20 hydrocarbon group containing oxygen (an alkoxy group bonded directly to the ring with an oxygen atom, etc.) Hereinafter, sulfur, nitrogen and phosphorus are also the same), a hydrocarbon group having 1 to 20 carbon atoms containing sulfur, a hydrocarbon group having 1 to 20 carbon atoms containing nitrogen, and a carbon group having 1 to 20 carbon atoms containing phosphorus. With substituents selected from hydrogen groups A compound is more preferable, and in addition, the above-described halogen at the 4-position, 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 halogenated hydrocarbon groups or hydrocarbon group-substituted silyl groups having 1 to 20 carbon atoms, hydrocarbon groups having 1 to 20 carbon atoms including oxygen (including alkoxy groups directly bonded to the ring by oxygen atoms, etc.) , Sulfur, nitrogen and phosphorus as well), a hydrocarbon group having 1 to 20 carbon atoms including sulfur, a hydrocarbon group having 1 to 20 carbon atoms including nitrogen, and a hydrocarbon group having 1 to 20 carbon atoms including phosphorus. Are particularly preferred, and the substituents at the 2-position and 4-position are hydrocarbon groups having 1 to 20 carbon atoms and silicon-containing hydrocarbon groups having 1 to 18 carbon atoms including 1 to 6 silicon atoms. , Selected from oxygen-containing hydrocarbon groups having 1 to 20 carbon atoms Compounds having a substituent that is most preferred.

  Regarding the component (b) and the component (c), together with the method for producing an olefin polymerization catalyst, a method described in JP 2011-137146 A (paragraphs [0068] to [0069]) and other known techniques are used. Is applicable.

  As a suitable production method for the ethylene polymer (C) of the present invention to exhibit its reforming performance, it is desired that the amount of the ethylene polymer produced per olefin polymerization catalyst is sufficiently high. A more preferable range of the weight ratio (ethylene polymer weight (g) / olefin catalyst weight (g)) is 5000 to 30000, and a more preferable range is 7000 to 25000. When the weight ratio is lower than 3000, the catalyst itself may cause a poor appearance or prevent mixing of the component (A), which is not preferable. On the other hand, if the weight ratio is higher than 50000, it is difficult to control the production ratio of the component (A) and the component (B), or the mixing of the component (A) and the component (B) is unfavorably caused. .

  The component (A) and the component (B) can be composed of a plurality of components. Component (A) and component (B) may be a polymer continuously polymerized in a multistage polymerization reactor using one type of catalyst, and are produced in a multistage polymerization reactor using a plurality of types of catalysts. It may be a polymer.

The component (A) and the component (B) preferably use a so-called multistage polymerization method in which polymerization is continuously performed in a plurality of reactors connected in series. However, continuous multi-stage polymerization is preferred for reasons of stability of the catalyst used and sustained activity.
In the multistage polymerization, the order of the component (A) and the component (B) is not particularly limited, but the order is the order of the component (A) and the component (B), that is, after the step of polymerizing the component (A), When the reaction system containing (A) is transferred to the reaction conditions of component (B) as it is and the step of polymerizing component (B) is carried out, it is more effective in preventing poisoning of the catalyst and preventing diffusion of the solvent / raw material. preferable.
In addition, the component (A) and / or the component (B) is a component having a higher molecular weight than the component (A) so that the ethylene polymer (C) of the present invention exhibits more excellent resin modification performance. For the purpose of designing as an ethylene-based polymer, or in order to increase the melt fluidity while the ethylene-based polymer (C) of the present invention maintains better resin modification performance, the component (B) is added. For the purpose of designing as an ethylene polymer containing a component having a lower molecular weight, it can be obtained by multistage polymerization of two or more stages.
A specific preferable polymerization method is the following method. That is, a metallocene catalyst and two reactors are used, ethylene and α-olefin are introduced into the first-stage reactor, and a low-density polymer having a high molecular weight component is produced. In this method, the polymer extracted from the vessel is transferred to the second-stage reactor, and ethylene and hydrogen are introduced into the second-stage reactor to produce a high-density, low-molecular-weight polymer. .
In the case of multistage polymerization, the amount of ethylene-based polymer produced in the second and subsequent polymerization zones and its properties are determined by determining the amount of polymer produced in each stage (which can be determined by analysis of unreacted gas, etc.) The physical properties of the polymer extracted after each stage can be measured, and the physical properties of the polymer produced at each stage can be determined based on the additivity.

(4) Modifier for resin The ethylene polymer (C) used in the present invention is an ethylene polymer excellent in compatibility with the material to be modified, and highly disperses the high molecular weight component, and has an appearance. The physical properties of the molded product can be highly modified without impairing the properties, and can be suitably used as a resin modifier. Ethylene polymer (C) is a resin modifier, such as flow characteristics, extrudability, thickness uniformity during blow molding, drawdown properties, etc., moldability, impact strength, rigidity, etc. It can be used for the purpose of expression of mechanical strength and smoothness of appearance.
When it is used as a resin modifier, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, an antistatic agent, an antifogging agent, an antiblocking agent, a processing aid, a coloring content, a crosslinking agent, a foaming agent, Components such as ordinary additives such as inorganic or organic fillers and flame retardants can be added.
The resin modifier of the present invention can be applied to various resins such as other olefin polymers and rubbers. Among them, the resin modifier is preferably applied to ethylene-based polymers. In the present invention, the following explanation will be given. It is necessary to apply to the specific ethylene polymer (D) to form the ethylene polymer composition of the present invention.

2. Ethylene polymer (D)
The ethylene polymer (D) of the present invention is required to satisfy the above-mentioned characteristics (i) to (iii). The characteristics (i) to (iii) and the manufacturing method thereof will be described below.

(1) Characteristics (i)
The ethylene polymer (D) of the present invention is produced with a chromium catalyst. As the chromium catalyst, a catalyst in which a chromium compound is supported on an inorganic oxide support and at least a part of chromium element is hexavalent is used. The detailed description of the chromium catalyst is as described in publicly known documents including, for example, Japanese Patent Application Laid-Open No. 2011-190437.
The ethylene polymer (D) is a polyethylene having a so-called long chain branching, and the molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) is usually more than 7 and 50 or less, and the temperature In both logarithmic plots of elongational viscosity η (t) (unit: Pa · second) and elongation time t (unit: second) measured at 170 ° C. and elongational strain rate of 0.1 (unit: 1 / second) An inflection point of the extension viscosity is observed, and polyethylene having a strain hardening degree (λmax) of usually 1.05 to 5.00 is preferable.
The inflection point of elongation viscosity and strain hardening degree (λmax) resulting from strain hardening can be obtained as follows. That is, the elongational viscosity at 170 ° C. and a strain rate of 0.1 / second is plotted on a logarithmic graph with time t (second) on the horizontal axis and elongation viscosity η (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.
The method for producing the ethylene polymer (D) will be described in detail below.

(2) Characteristics (ii)
The density of the ethylene polymer of the present invention (D) (D) is required to be 0.920~0.965g / cm ^3, preferably 0.920~0.964g / cm ^3, more preferably Is 0.920 to 0.963 g / cm ³ . If the density (D) is less than 0.920 g / cm ³ , the rigidity becomes insufficient, which is not preferable. On the other hand, if the density (D) is larger than 0.965 g / cm ³ , the durability becomes insufficient, which is not preferable.
The density (D) can be controlled mainly by changing the α-olefin content of the component (D), and the α-olefin content can be controlled in the polymerization reactor during the production of the component (D). It can be controlled by changing the ratio of the amount of α-olefin and the amount of ethylene.

(3) Characteristics (iii)
The high load melt flow rate (HLMFR (D)) of the ethylene-based polymer (D) of the present invention is 1 to 100 g / 10 minutes. Preferably it is 1-75 g / 10min, More preferably, it is 1-50 g / 10min. When HLMFR (D) is less than 1 g / 10 minutes, the fluidity is lowered and the extrusion characteristics become insufficient, which is not preferable. On the other hand, if HLMFR (D) is greater than 100 g / 10 min, the durability becomes insufficient, such being undesirable.
HLMFR (D) can be adjusted mainly by the amount of hydrogen during production of component (D).

(4) Manufacturing method of ethylene polymer (D) The ethylene polymer (D) is an ethylene homopolymer or ethylene and an α-olefin having 3 to 12 carbon atoms, such as propylene, 1-butene, 1-pentene. , 1-hexene, 4-methyl-1-pentene, 1-octene and the like. Also, copolymerization with a diene for the purpose of modification is possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, and the like.
The comonomer content in the polymerization of the ethylene polymer (D) can be arbitrarily selected. For example, the α-olefin content in the ethylene polymer is preferably 0 to 20 mol%. Is 0 to 10 mol%.

  As described above, a chromium catalyst is used as the polymerization catalyst for the ethylene-based polymer (D).

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

The hydrogen supplied to the polymerization vessel in the slurry polymerization is consumed as a chain transfer agent, determines the average molecular weight of the produced ethylene-based polymer, and partly dissolves in a solvent and is discharged from the polymerization vessel. The solubility of hydrogen in the solvent is small, and the hydrogen concentration near the polymerization active point of the catalyst is low unless a large amount of gas phase is present in the polymerization vessel. Therefore, if the hydrogen supply amount is changed, the hydrogen concentration at the polymerization active point of the catalyst changes rapidly, and the molecular weight of the produced ethylene polymer changes following the hydrogen supply amount in a short time. Therefore, a more homogeneous product can be produced by changing the hydrogen supply rate in a short cycle. For these reasons, it is preferable to employ a slurry polymerization method as the polymerization method. In addition, the aspect of changing the hydrogen supply amount is preferably changed discontinuously rather than continuously because the effect of broadening the molecular weight distribution can be obtained.
In the ethylene polymer (D) of the present invention, as described above, it is important to change the hydrogen supply amount, but other polymerization conditions, for example, the polymerization temperature, the catalyst supply amount, and the supply amount of olefins such as ethylene. It is also important to change the supply amount of a comonomer such as 1-hexene, the supply amount of a solvent, and the like as appropriate simultaneously or separately with the change of hydrogen.

  The ethylene polymer (D) can be composed of a plurality of components. The ethylene-based polymer (D) may be a polymer successively polymerized in a multistage polymerization reactor using one type of catalyst, or produced in a multistage polymerization reactor using a plurality of types of catalysts. It may be a polymer.

A specific preferable polymerization method of the ethylene polymer (D) is the following method. That is, this is a method for producing a polymer by using a chromium catalyst and a single tank or a multi-tank reactor and introducing ethylene and α-olefin into the reactor.
In the case of multistage polymerization, the amount of ethylene-based polymer produced in the second and subsequent polymerization zones and its properties are determined by determining the amount of polymer produced in each stage (which can be determined by analysis of unreacted gas, etc.) The physical properties of the polymer extracted after each stage can be measured, and the physical properties of the polymer produced at each stage can be determined based on the additivity.

3. Ethylene-based polymer composition (1) blending ratio As described above, the ethylene-based polymer composition of the present invention needs to contain an ethylene-based polymer (C) and an ethylene-based polymer (D). It is.
The blending ratio of the ethylene polymer (C) and the ethylene polymer (D) is 10 (C) based on the total amount of the ethylene polymer (C) and the ethylene polymer (D). It is necessary that (D) is 10 to 90% by weight with respect to -90% by weight. Preferably, (C) is 20 to 80% by weight, (D) is 20 to 80% by weight, more preferably (C) is 30 to 70% by weight, and (D) is 30 to 70% by weight. It is. When (C) is less than 10% by weight, the content of the high molecular weight component in the ethylene polymer composition is lowered, and the mechanical strength becomes insufficient, which is not preferable. On the other hand, when (C) is more than 90% by weight, the fluidity is lowered and the extrudability becomes insufficient.

(2) Characteristics The ethylene polymer composition of the present invention preferably has the following characteristics.
(Wi) The density (W) is preferably 0.910 to 0.965 g / cm ³ . More preferably, 0.920~0.962g / cm ^3, particularly preferably 0.925~0.960g / cm ^3. When the density (W) is less than 0.910 g / cm ³ , the rigidity becomes insufficient, which is not preferable. On the other hand, if it is larger than 0.965 g / cm ³ , the durability becomes insufficient, which is not preferable. In addition, the density (W) of an ethylene-type polymer composition can be adjusted with the amount of each (alpha) -olefin at the time of manufacture of a component (C) and (D), and the compounding quantity of a component (C) and (D). it can.

(W-ii) The melt flow rate (MFR (W)) is preferably 0.02 to 1 g / 10 min. More preferably, it is 0.05-0.8 g / 10min, Most preferably, it is 0.1-0.6g / 10min. An MFR (W) of less than 0.02 g / 10 minutes is not preferable because the fluidity is lowered and the extrudability becomes insufficient. On the other hand, if it is larger than 1 g / 10 minutes, the durability becomes insufficient, which is not preferable. In addition, MFR (W) of an ethylene-type polymer composition can be adjusted with the compounding quantity of each hydrogen amount at the time of manufacture of component (C) and (D), and component (C) and (D).

(W-iii) It is preferable that HLMFR (W) / MFR (W) which is a ratio of a melt flow rate and a high load melt flow rate is 50-150. More preferably, it is 60-140, Most preferably, it is 70-130. When HLMFR (W) / MFR (W) is smaller than 50, the melt tension is lowered, and the swell during extrusion becomes small, so that the moldability becomes insufficient, which is not preferable. On the other hand, if it is larger than 150, unstable flow during extrusion, which is called melt fracture, is liable to occur, and the surface of the molded product becomes rough. In addition, HLMFR (W) / MFR (W) of the ethylene-based polymer composition is adjusted by the respective hydrogen amounts at the time of producing the components (C) and (D) and the blending amounts of the components (C) and (D). can do.

(3) Other components The ethylene polymer (C), the ethylene polymer (D), or the ethylene polymer composition of the present invention is an ordinary polymer as long as it does not impair the purpose of the present invention. You may contain the additive added to polyolefin. These additives can be used alone or in combination of two or more.
Examples of the additive include a stabilizer such as a heat stabilizer, a weather stabilizer, a crosslinking agent, a crosslinking aid, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a filler, Examples include mineral oil softeners, petroleum resins, and waxes.

(4) Manufacturing method There is no restriction | limiting in particular as a manufacturing method of the ethylene-type polymer composition of this invention, A well-known method is applicable. For example, ethylene-based polymer (C) and ethylene-based polymer (D) are produced separately, and these are mixed in the above proportions in ordinary kneading such as an extruder, Banbury mixer, roll, Brabender plastograph, kneader, etc. It can be manufactured by melt-kneading using a machine. The temperature for melting and kneading is not particularly limited as long as the ethylene polymer (C) and the ethylene polymer (D) are melted, but it can be usually produced by kneading in the range of 180 to 350 ° C. Among these kneaders, a single-screw or twin-screw extruder or a continuous kneader can be used, and it is particularly preferable to manufacture using a twin-screw extruder, and a machine using a pelletizer or a homogenizer according to a conventional method. After being pelletized by typical melt mixing, it can be molded by various molding machines to obtain a desired molded product.

Since the ethylene-based polymer composition of the present invention produces a molded product, other olefinic polymer contained in a molded product made of a normal polyolefin as necessary, as long as the object of the present invention is not impaired. In addition to coalescence and rubber, antioxidants (phenolic, phosphorus, sulfur), UV absorbers, light stabilizers, lubricants, antistatic agents, antifogging agents, antiblocking agents, processing aids, color pigments, One or more known additives such as a pearl pigment, a polarizing pearl pigment, a crosslinking agent, a foaming agent, a neutralizing agent, a heat stabilizer, a crystal nucleating agent, an inorganic or organic filler, and a flame retardant may be blended. it can.
Examples of the organic filler include carbon fiber, carbon black, and carbon nanotube. Examples of the inorganic filler include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, water. Aluminum oxide, magnesium hydroxide, dolomite, calcium sulfate, potassium titanate, barium sulfate, talc, clay, mica, glass flake, glass beads, glass fiber, aluminum silicate, calcium silicate, montmorillonite, bentonite, molybdenum sulfide, graphite , Calcium carbonate, metal powder (aluminum, copper, iron, lead, etc.), silica and the like.
In any case, various additives may be blended with the ethylene polymer as necessary, and the mixture may be kneaded with a kneading extruder, a Banbury mixer, or the like to obtain a molding material.

4). Molded article The molded article of the present invention is characterized by molding the ethylene polymer composition of the present invention. In the present invention, an arbitrary molded body can be obtained by molding the above ethylene polymer composition by a known molding method.
The molding method is not particularly limited and can be molded by various molding methods according to the purpose. For example, injection molding method, extrusion molding method, hollow molding method, pipe molding method, tube molding method, heterogeneous molding Examples thereof include body coating molding methods, injection blow molding methods, direct blow molding methods, T-die sheets, film molding methods, inflation molding methods, and press molding methods. By these forming methods, it can be formed into a container shape, a tray shape, a sheet shape, a rod shape, a film shape, various machine element shapes, various coverings, or the like.
In particular, the resin composition modified with the resin modifier of the present invention is characterized by improved mechanical properties and less polymer gel formation, so it is molded by sheet molding. Is preferred. Specifically, when molded into various tray-type containers for food trays, medical trays, etc., and deep-drawn sheet containers such as yogurt, jelly, and tofu, manufactured products with excellent fish eyes and excellent appearance can do.

The ethylene polymer composition of the present invention is excellent in moldability, durability, and impact strength, and also has an ethylene-based weight capable of producing a molded product having excellent appearance with less unevenness due to high molecular weight gel. Since it is a united composition, it is particularly preferably a sheet molded body that requires smoothness on both the inner and outer surfaces of the product.
The sheet molded article of the present invention can be preferably obtained by a single-layer or multilayer extrusion sheet molding method usually used for molding polyolefin. The single layer extrusion sheet forming method is a method of extruding from a single or biaxial screw extruder into a sheet shape from a T die such as a coat hanger die, and a method of extruding from a circular circular die into a cylindrical shape and dividing into a sheet shape. is there. The multilayer extrusion sheet forming method is a method of extruding from two or more single-screw or twin-screw extruders through a feed block or a multi-manifold. The extruded sheet is cooled and solidified by pressing with an air knife, an air chamber, a hard rubber roll, a steel belt, and a metal roll on the surface of the metal roll (in which cooling water and oil are circulated). It is also possible to cool and solidify both sides of the sheet with a steel belt.
The multilayer sheet may be added with other layers such as candles, gas barriers, oxygen adsorption, light blocking, and regeneration treatment as long as the effects of the present invention are not impaired.
Furthermore, the extruded sheet-formed sheet is processed into various thermoformed bodies by thermoforming such as hot platen pressure forming, vacuum forming, vacuum pressure forming, and solid phase pressure forming.
Since the sheet molded product of the present invention is extremely excellent in extrusion sheet moldability and thermoforming processability, various tray-type containers for food trays, medical trays and the like that particularly require shape retention and surface smoothness, yogurt, Ideal for packaging containers such as deep-drawn sheet containers such as jelly and tofu.
The shape and size of the packaging container are not particularly limited, and the planar shape can be various shapes such as a quadrilateral, a circle, and an ellipse, and the three-dimensional shape is also a box shape (particularly a lunch box shape), a tray. Various shapes such as a shape and a bowl shape can be used.
In addition, the sheet plastic molded product of the present invention includes an antistatic agent, an antioxidant, a neutralizing agent, a lubricant, an antiblocking agent, an antifogging agent, an organic or inorganic pigment, as long as the purpose is not impaired as necessary. Well-known additives such as fillers, inorganic fillers, UV inhibitors, dispersants, weathering agents, crosslinking agents, foaming agents, flame retardants, and the like can be added.

  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 (HLMFR) at a temperature of 190 ° C. and a load of 21.60 kg:
It measured based on JISK7210: 1999.
The HLMFR of the component (A) or the component (B) was obtained by correlating the hydrogen concentration during the production of the ethylene polymer with the HLMFR of the ethylene polymer in the case of a small amount of batch polymerization.
On the other hand, when superposing | polymerizing in large quantities, the ethylene polymer was extracted from the reaction container of a 1st reaction process, and HLMFR of the ethylene polymer of a component (A) was measured. Next, the ethylene polymer is withdrawn from the reaction vessel of the second reaction step, the HLMFR of the ethylene polymer of component (C) is measured, and between the HLMFR after the second reaction step and the HLMFR after the first reaction step. It was sought that additivity with respect to% by weight was established.
(2) Melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg:
It measured based on JISK7210: 1999.
(3) Density:
JIS K7112 (1999): Measured by method A (submersion method in water).
In addition, the density of the component (A) or the component (B) was obtained by correlating the α-olefin concentration during the production of the ethylene polymer with the density of the ethylene polymer in the case of a small batch polymerization.
On the other hand, when superposing | polymerizing in large quantities, the ethylene polymer was extracted from the reaction container of a 1st reaction process, and the density of the ethylene polymer of a component (A) was measured. Next, the ethylene polymer is withdrawn from the reaction vessel of the second reaction step, the density of the ethylene polymer of component (C) is measured, and between the density after the second reaction step and the density after the first reaction step. It was sought that additivity with respect to% by weight was established.

(4) Rupture time in full notch creep test (FNCT) (measured at 80 ° C., 3.7 MPa):
The measurement was performed at 80 ° C. and 3.7 MPa in accordance with the all-around notch tensile creep test of JIS K6774 (1995) Appendix 1. The test piece was cut out from a 6 mm thick compression-molded sheet prepared under the conditions of JIS K6922-2 (1997) Table 2, and notched all around (test piece thickness 6 mm, notch depth 1 mm, full circumference). It was used. As a test solution for immersing the sample, a 1% aqueous solution of sodium alkyl sulfate was used.

(5) Measurement of molecular weight by gel permeation chromatography (GPC) (weight average molecular weight Mw, number average molecular weight Mn):
It measured by the gel permeation chromatography (GPC) of the following conditions.
Apparatus: WATERS 150C
Column: 3 AD80M / S manufactured by Showa Denko KK Measurement temperature: 140 ° C
Concentration: 1 mg / 1 ml
Solvent: o-dichlorobenzene Calculation of molecular weight and column calibration were performed according to the following method.
GPC chromatographic data was loaded into a computer at a frequency of 1 point / second, and data processing was performed according to the description in Chapter 4 of “Size Exclusion Chromatography” published by Sadao Mori and Kyoritsu Publishing Co., and Mw and Mn values were calculated.

(6) Tensile impact strength:
In accordance with JIS K7160-1996 “Plastics—Test Method for Tensile Impact Strength”, the test was performed under the conditions of a test piece thickness of 1.0 mm and a temperature of 23 ° C.

(7) Mixability evaluation (mixing evaluation rate):
The mixing property was evaluated by the method described in <Mixability evaluation method> described above.
At that time, the resolution of the scanner was 4800 dpi, and a score of 1 to 6 was assigned according to the area ratio of fish eyes in the image.

2. Materials Used (1) Synthesis of Metallocene Catalyst A cylindrical flask fully equipped with nitrogen and equipped with an induction stirrer was charged with silica having an average particle diameter of 11 μm (average particle diameter of 11 μm, surface area of 313 m ² / g, pore volume of 1. 6 g ³ / g) was charged, 3 ml of toluene was added, and the mixture was 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 silica-supported metallocene catalyst A.

(2) Synthesis of Chromium Catalyst A detailed description of the synthesis of the chromium catalyst can be found in publicly known documents including, for example, Japanese Patent Publication No. 2011-190437.
For example, an example is shown below. That is, 50 g of silica gel (for example, product name C-952 manufactured by Grace; trade name C-952) and 200 mL of ion-exchanged water were added to a 1 L flask equipped with a stirrer, and an aqueous solution in which 2.2 g of chromium (III) acetate was dissolved in 70 mL of ion-exchanged water was added. Then, the silica compound was thoroughly impregnated into the silica gel. Next, heating was performed to distill off the entire amount of water to obtain a greenish-white fluidity chromium catalyst precursor particle. By performing calcination activation (activation) in a calcination electric furnace in a fluidized state by a dry air stream, the chrome catalyst precursor particles can obtain an orange chrome catalyst indicating that hexavalent chromium is contained. . The firing temperature for activation is generally 350 ° C. to 850 ° C.

(3) Production of Component (D) A polymerization apparatus having a polymerization liquid-filled loop reactor is continuously supplied with dehydrated and purified isobutane, the chromium catalyst obtained in (2) above, and ethylene. The components (D) ((D-1) to (D-5) and (CD-1) to (CD-3)) were produced by polymerization. The HLMFR of component (D) was adjusted by supplying an appropriate amount of hydrogen.

(4) Production conditions for component (A) and component (B) Table 3 shows the polymerization conditions for producing component (A) and component (B).

[Example 1]
Component (A-1) and component (B-1) were produced as follows, and 247 g of an ethylene polymer (C-1) as a two-stage polymer was produced by continuous polymerization. The polymer (C-1) had an HLMFR of 2.3 g / 10 min and a density of 0.944 g / cm ³ .

Production of component (A-1);
Component (A-1) was produced by carrying out ethylene / 1-hexene copolymerization using the silica-supported metallocene catalyst A. That is, 800 mL of isobutane, 1.0 mL of 1-hexene, 0.10 mmol of triisobutylaluminum, Stadis450 (a mixture of polysulfone copolymer, polymer polyamine, and oil-soluble sulfonic acid) manufactured by The Associated Octel, in a 2 L autoclave with an induction stirrer Toluene dilution (2 g / L) 0.8 ml was added, the temperature was raised to 80 ° C., 50 mL of hydrogen was added, and ethylene was further introduced to keep the ethylene partial pressure at 1.0 MPa. Next, 24 mg of the catalyst A was injected with nitrogen, and polymerization was continued for 32 minutes while maintaining an ethylene partial pressure of 1.0 MPa and a temperature of 80 ° C. During the polymerization reaction, H ₂ and 1-hexene were additionally supplied at a supply rate proportional to the ethylene consumption rate. As a result, 96 g of ethylene was consumed by the reaction, and the H ₂ / C ₂ (hydrogen / ethylene) molar ratio in the gas phase part of the autoclave 10 minutes after the start of polymerization and at the end of the polymerization was 0.132% and 0.187%, respectively. The amount of 1-hexene supplied additionally was 1.0 mL. The HLMFR of component (A-1) obtained at this time was 0.78 g / 10 min, and the density was 0.936 g / cm ³ .

Production of component (B-1);
After the production of component (A-1) as described above, 130 mL of hydrogen was quickly added while maintaining the temperature and pressure, and ethylene / 1-hexene copolymerization was continued for another 88 minutes to produce component (B-1). Manufactured. During the polymerization reaction, H ₂ and 1-hexene were additionally supplied at a supply rate proportional to the ethylene consumption rate. As a result, 124 g of ethylene was consumed by the reaction, and the H ₂ / C ₂ molar ratios at 10 minutes after addition of hydrogen and at the end of the polymerization were 0.617% and 0.244%, respectively. -The amount of hexene was 1.5 mL. The HLMFR of component (B-1) obtained at this time was 18.0 / 10 minutes.

An ethylene polymer composition was produced by blending the component (C-1) and the component (D-1) shown in Table 1 by melt kneading. The composition had an HLMFR of 17.8 g / 10 min and a density of 0.957 g / cm ³ , and the result of the evaluation of mixing was good.

[Example 2]
Component (A-2) and component (B-2) were produced as follows, and continuous polymerization was carried out to produce 303 g of an ethylene polymer (C-2) as a two-stage polymer. The polymer (C-2) had an HLMFR of 1.9 g / 10 min and a density of 0.932 g / cm ³ .

Production of component (A-2);
In the same manner as in component (A-1) of Example 1, component (A-2) was produced. However, hydrogen was 45 mL, the catalyst amount was 23 mg, and the polymerization time was 50 minutes. As a result, 144 g of ethylene was consumed by the reaction, and the H ₂ / C ₂ ratios at 10 minutes after the start of polymerization and at the end of the polymerization were 0.135% and 0.180%, respectively, and the amount of 1-hexene supplied additionally was It was 6.1 mL. The HLMFR of the component (A-2) obtained at this time was 0.77 g / 10 min, and the density was 0.930 g / cm ³ .

Production of component (B-2);
After manufacturing a component (A-2), it carried out similarly to the component (B-1) of the said Example 1, and manufactured the component (B-2). However, the added hydrogen was 135 mL, and the polymerization time was 130 minutes. As a result, 120 g of ethylene was consumed by the reaction, and the H ₂ / C ₂ molar ratios at 10 minutes after addition of hydrogen and at the end of polymerization were 0.191% and 0.272%, respectively. -The amount of hexene was 5.1 mL. The HLMFR of the component (B-2) obtained at this time was 3.2 g / 10 minutes.

The ethylene-based polymer composition was produced by blending the component (C-2) and the component (D-2) shown in Table 1 by melt kneading. The composition had an HLMFR of 18.0 g / 10 min and a density of 0.954 g / cm ³ , and the result of the evaluation of mixing was good.

[Example 3]
Component (A-3) and component (B-3) were produced as follows, and continuous polymerization was carried out to produce 212 g of an ethylene polymer (C-3) as a two-stage polymer. The polymer (C-3) had an HLMFR of 6.2 g / 10 min and a density of 0.939 g / cm ³ .

Production of component (A-3);
In the same manner as in component (A-1) of Example 1, component (A-3) was produced. However, hydrogen was 45 mL, the catalyst amount was 23 mg, and the polymerization time was 30 minutes. As a result, 66 g of ethylene was consumed by the reaction, and the H ₂ / C ₂ ratios at 10 minutes after the start of polymerization and at the end of the polymerization were 0.104% and 0.146%, respectively, and the amount of 1-hexene supplied additionally was It was 2.7 mL. The HLMFR of the component (A-3) obtained at this time was 0.46 g / 10 min, and the density was 0.934 g / cm ³ .

Production of component (B-3);
After manufacturing a component (A-3), it carried out similarly to the component (B-1) of the said Example 1, and manufactured the component (B-3). However, the added hydrogen was 200 mL, and the polymerization time was 91 minutes. As a result, 101 g of ethylene was consumed by the reaction, and after adding hydrogen for 10 minutes and at the end of the polymerization, the H ₂ / C ₂ molar ratios were 0.991% and 0.268%, respectively. -The amount of hexene was 4.5 mL. The HLMFR of the component (B-3) obtained at this time was 90 g / 10 minutes.

The ethylene-based polymer composition was produced by blending the component (C-3) and the component (D-3) shown in Table 1 by melt kneading. The composition had an HLMFR of 25.6 g / 10 min and a density of 0.955 g / cm ³ , and the results of the evaluation of mixing were good.

[Example 4]
Component (A-4) and component (B-4) were produced as follows, and continuous polymerization was conducted to produce 242 g of an ethylene polymer (C-4) as a two-stage polymer. The HLMFR of the polymer (C-4) was 1.3 g / 10 min, and the density was 0.934 g / cm ³ .

Production of component (A-4);
In the same manner as in component (A-1) of Example 1, component (A-4) was produced. However, hydrogen was 40 mL, the catalyst amount was 24 mg, and the polymerization time was 50 minutes. As a result, 148 g of ethylene was consumed by the reaction, and the H ₂ / C ₂ ratio 10 minutes after the start of polymerization and at the end of the polymerization were 0.117% and 0.228%, respectively, and the amount of 1-hexene supplied additionally was It was 6.3 mL. The HLMFR of component (A-4) obtained at this time was 0.93 g / 10 min, and the density was 0.932 g / cm ³ .

Production of component (B-4);
After manufacturing a component (A-4), it carried out similarly to the component (B-1) of the said Example 1, and manufactured the component (B-4). However, the added hydrogen was 140 mL, and the polymerization time was 25 minutes. As a result, 68 g of ethylene was consumed by the reaction, and after adding hydrogen for 10 minutes and at the end of polymerization, the H ₂ / C ₂ molar ratios were 0.411% and 0.414%, respectively. -The amount of hexene was 2.9 mL. The HLMFR of the component (B-4) obtained at this time was 15 g / 10 minutes.

An ethylene polymer composition was produced by blending the component (C-4) and the two components (D-4) shown in Table 1 by melt kneading. The composition had an HLMFR of 13.2 g / 10 min and a density of 0.953 g / cm ³ , and the result of the evaluation of mixing was good.

[Example 5]
According to the conditions of the above-mentioned Examples, the component (A-5) and the component (B-5) listed in Table 1 are subjected to continuous multistage polymerization in that order, and the component (C-5) which is an ethylene polymer Manufactured in large quantities. An ethylene polymer composition was produced by blending the component (C-5) and the component (D-5) shown in Table 1 by melt kneading. The composition had an HLMFR of 11.1 g / 10 min and a density of 0.954 g / cm ³ , and the results of the evaluation of mixing were good.

[Comparative Example 1]
The components (CA-1) and (CB-1) were produced separately as follows. The HLMFR of the ethylene polymer composition obtained by blending these two components by melt kneading was 2.7 g / 10 min, and the density was 0.939 g / cm ³ .

Production of component (CA-1);
In the same manner as in the component (A-1) in Example 1, the component (CA-1) was produced. However, hydrogen was 30 mL, the catalyst amount was 23 mg, and the polymerization time was 120 minutes. As a result, 142 g of ethylene was consumed by the reaction, and the H ₂ / C ₂ ratios at 10 minutes after the start of polymerization and at the end of the polymerization were 0.16% and 0.16%, respectively, and the amount of 1-hexene supplied additionally was 2.0 mL. The component (CA-1) obtained at this time was 162 g, HLMFR was 0.42 g / 10 min, and the density was 0.932 g / cm ³ .

Production of component (CB-1);
In the same manner as in component (A-1) of Example 1, component (CB-1) was produced. However, hydrogen was 180 mL, the catalyst amount was 23 mg, and the polymerization time was 30 minutes. As a result, 96 g of ethylene was consumed by the reaction, and the H ₂ / C ₂ ratio 10 minutes after the start of polymerization and at the end of the polymerization were 0.438% and 0.415%, respectively, and the amount of 1-hexene supplied additionally was 1.0 mL. The component (CB-1) obtained at this time was 105 g, HLMFR was 17.7 g / 10 min, and the density was 0.947 g / cm ³ .

An ethylene polymer composition was produced by blending the three components of component (CA-1), component (CB-1) and component (CD-1) shown in Table 12 by melt kneading. The composition had an HLMFR of 15.3 g / 10 min, a density of 0.956 g / cm ³ , and the result of the evaluation of mixing was poor.

[Comparative Example 2]
In the same manner as in the Examples, the component (CA-2) and the component (CB-2) were produced and continuously polymerized to produce an ethylene polymer (CC-2) as a two-stage polymer. The polymer (CC-2) had an HLMFR of 3.2 g / 10 min and a density of 0.938 g / cm ³ .
The HLMFR of the component (CA-2) obtained at this time was 0.38 g / 10 min, and the density was 0.925 g / cm ³ .
Moreover, HLMFR of the component (CB-2) obtained at this time was 124.3 g / 10min.

An ethylene polymer composition was produced by blending the component (CC-2) and the two components (CD-2) shown in Table 2 by melt kneading. The composition had an HLMFR of 24.2 g / 10 min and a density of 0.958 g / cm ³ , and the result of the evaluation of mixing was poor.

[Comparative Example 3]
According to the conditions of Comparative Example 1, the temperature in the polymerization apparatus was maintained at 70 ° C., and the component (CA-3) and the component (CB-3) that were ethylene polymers were separately polymerized. An ethylene polymer composition was produced by blending the three components of component (CA-3), component (CB-3) and component (CD-3) shown in Table 2 by melt kneading. The composition had an HLMFR of 11.5 g / 10 min and a density of 0.953 g / cm ³ , and the result of the evaluation of mixing was poor.

<Mixing with component to be modified>
The melt-mixing of the ethylene polymer produced with the above-mentioned metallocene catalyst and the ethylene polymer produced with the chromium catalyst was kneaded by a laboratory plast mill manufactured by Toyo Seiki Seisakusho. Using a roller blade R100, after filling a sample of 70 g, after heating for 5 minutes at a test temperature of 170 ° C., kneading was performed for 1 minute at a rotation speed of 40 rpm. The obtained sample was subjected to MFR, HLMFR, density, mixing, tensile impact test, and full notch creep test.

1) In the case of a small amount of batch polymerization, the HLMFR of the component (A) or the component (B) was determined from the correlation between the hydrogen concentration during the production of the ethylene polymer and the HLMFR (Examples 1 to 4).
2) In the case of small batch polymerization, the density of the component (A) or the component (B) was determined from the correlation between the α-olefin comonomer concentration and the density during the production of the ethylene polymer (Examples 1 to 4).
3) When polymerized in a large amount, the HLMFR of the component (B) is determined based on the additivity from the HLMFR of the component (A) and the component (C) and the weight ratio of the component (A) and the component (B). (Example 5).
4) When polymerized in large quantities, the density of component (B) is determined based on additivity from the density of component (A) and component (C) and the weight ratio of component (A) and component (B). (Example 5).
5) The polymerization ratio of component (A) and component (B) was determined from the amount of ethylene consumed by the reaction when each component was polymerized (Examples 1 to 5).

[Example 6]
<Manufacture of sheet compact>
The pellet resin of the ethylene polymer composition obtained in Example 5 was extruded with a T-die single layer extrusion sheet molding machine having a screw diameter 40 mm extruder heated to 230 ° C., width 600 mm, die lip interval 0.8 mm. The sheet was extruded from a coat hanger die in the horizontal direction and cooled and solidified by sandwiching it with a mirror-finished hard chrome-plated metal roll in which water at 40 ° C. was circulated, thereby producing a sheet having a thickness of 0.5 mm. The obtained sheet had few fish eyes and was smooth and excellent in appearance, and no other problems were found. Furthermore, the laminated sheet is heated from above and below with a ceramic heater at 450 ° C. using an indirectly heated vacuum / pressure forming machine (manufactured by Asano Laboratories, Cosmic forming machine), so that the first layer of the sheet is on the inside, A round container molded body was vacuum formed using a mold having a diameter of 10 cm and a depth of 3 cm. The obtained container molded body was a smooth container with few fish eyes and excellent in appearance, and no other problems were found.

[Evaluation]
As described above, from the results shown in Tables 1 and 2, when Examples 1 to 5 and Comparative Examples 1 to 3 are compared, those that do not satisfy the specific requirements for the ethylene polymer composition of the present invention are evaluated for mixing. It is inferior to the polyethylene of the examples.
When Example 1 and Comparative Example 1 are compared, the ethylene polymer produced by multi-stage polymerization is used for the components of each ethylene polymer constituting the blend material, although the blending ratio and viscosity are almost equal. The miscibility of the used Example 1 is remarkably improved as compared with Comparative Example 1 in which each component was polymerized separately.

  When Example 5 and Comparative Example 3 are compared, the ethylene polymer produced by multi-stage polymerization is used for each ethylene polymer component constituting the blend material, although the blending ratio and viscosity are almost equal. The miscibility of Example 5 used was significantly improved over Comparative Example 3 where each component was polymerized separately. Furthermore, with respect to tensile impact strength, Example 5 is significantly improved over Comparative Example 3. This indicates that the mechanical strength was improved because the mixing property of Example 5 was superior to that of Comparative Example 3.

It turns out that the mixing property is improving also about Examples 2-4 compared with Comparative Examples 1-3.
As shown in these examples, it was confirmed that the ethylene-based polymer composition according to the present invention has high mixing evaluation while improving mechanical strength as shown in Examples 1 to 5. .

The ethylene-based polymer composition of the present invention and the molded product comprising the same are, for example, the center of the particle of the component (C) even when the high molecular weight component (A) has a high viscosity and the molecular weight distribution is relatively narrow. The component (B) present in the part is an ethylene polymer composition that is excellent in compatibility with each other because it promotes dispersion of the component (A) when melt kneaded with the material to be modified. Therefore, the ethylene polymer composition has relatively low molecular weight components with a relatively narrow molecular weight distribution and can be highly dispersed without increasing the viscosity after blending, moldability, durability and impact strength. In addition, it is an ethylene polymer composition that is particularly suitable for a sheet molded product because it can hardly produce irregularities derived from a high molecular weight gel and can produce a molded product with an excellent appearance. The ethylene polymer composition of the present invention and a molded article comprising the same can provide a molded article having excellent physical properties and appearance, and can be used in fields where high physical properties and appearance are required. Since it can be used suitably, it is very useful industrially.

Claims (13)

10 to 90% by weight of ethylene polymer (C) satisfying the following characteristics (I) to (IV) and 10 to 90 ethylene polymer (D) satisfying the following characteristics (i) to (iii): An ethylene polymer composition comprising: wt%.
Characteristic (I): formed by multistage polymerization of the following component (A) and component (B).
Component (A): Density (A) is 0.900 to 0.950 g / cm ³ , high load melt flow rate (in accordance with HLMFR (A), JIS K7210, temperature 190 ° C., load 21.60 kg) Is an ethylene polymer having a molecular weight of 0.1 to 10 g / 10 min.
Component (B): Ethylene-based weight having a density (B) of 0.900 to 0.970 g / cm ³ and a high load melt flow rate (HLMFR (B)) of 0.5 to 100 g / 10 min Coalescence.
Characteristic (II): Density (C) is 0.900 to 0.968 g / cm ³ .
Characteristic (III): High load melt flow rate (HLMFR (C)) is 0.14 to 70 g / 10 min.
Characteristic (IV): The ratio of HLMFR (B) to HLMFR (A) (HLMFR (B) / HLMFR (A)) is 1.5 to 200.
Characteristic (i): produced with a chromium catalyst.
Characteristic (ii): The density (D) is 0.920 to 0.965 g / cm ³ .
Characteristic (iii): High load melt flow rate (HLMFR (D)) is 1 to 100 g / 10 min.   The ethylene-based polymer composition according to claim 1, wherein the component (A) and the component (B) are subjected to multistage polymerization in this order. The ethylene polymer composition according to claim 1 or 2, wherein the component (A) and the component (B) satisfy the following property (V).
Characteristic (V): Component (A) content weight ratio (X (A)) to component (B) content weight ratio (X (B)) on the basis of the sum of component (A) and component (B) The ratio (X (A) / X (B)) is 0.11-4. The density (W) is 0.910 to 0.965 g / cm ³ , and the melt flow rate (measured at a temperature of 190 ° C. and a load of 2.16 kg according to MFR (W), JIS K7210) It is 0.02-1 g / 10min, The ethylene-type polymer composition of any one of Claims 1-3 characterized by the above-mentioned.   The HLMFR (W) / MFR (W), which is the ratio of the melt flow rate (MFR (W)) and the high-load melt flow rate (HLMFR (W)), is 50 to 150. The ethylene polymer composition according to any one of the above.   The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) of the component (A) is 2 or more and less than 5. The ethylene polymer composition according to any one of 1 to 5.   The ethylene polymer composition according to any one of claims 1 to 6, wherein the component (A) and the component (B) are an ethylene polymer polymerized by a metallocene catalyst.   The ethylene polymer composition according to any one of claims 1 to 6, wherein the component (A) and the component (B) are ethylene polymers polymerized by a Ziegler catalyst.   The ethylene-based polymer composition according to any one of claims 1 to 8, wherein the component (A) and the component (B) are polymerized by a gas phase polymerization method or a slurry polymerization method. .   The ethylene-based polymer composition according to any one of claims 1 to 9, wherein the component (A) and / or the component (B) is obtained by multistage polymerization of two or more stages. .   The molded object formed by shape | molding the ethylene-type polymer composition of any one of Claims 1-10.   The molded body according to claim 11, which is formed by sheet molding. 10 to 90% by weight of ethylene polymer (C) satisfying the following characteristics (I) to (IV), and 10 to 90 ethylene polymer (D) satisfying the following characteristics (i) to (iii): A method for producing an ethylene-based polymer composition, comprising melt-mixing with wt%.
Characteristic (I): formed by multistage polymerization of the following component (A) and component (B).
Component (A): Density (A) is 0.900 to 0.950 g / cm ³ , high load melt flow rate (in accordance with HLMFR (A), JIS K7210, temperature 190 ° C., load 21.60 kg) Is an ethylene polymer having a molecular weight of 0.1 to 10 g / 10 min.
Component (B): Ethylene-based weight having a density (B) of 0.900 to 0.970 g / cm ³ and a high load melt flow rate (HLMFR (B)) of 0.5 to 100 g / 10 min Coalescence.
Characteristic (II): Density (C) is 0.900 to 0.968 g / cm ³ .
Characteristic (III): High load melt flow rate (HLMFR (C)) is 0.14 to 70 g / 10 min.
Characteristic (IV): The ratio of HLMFR (B) to HLMFR (A) (HLMFR (B) / HLMFR (A)) is 1.5 to 200.
Characteristic (i): produced with a chromium catalyst.
Characteristic (ii): The density (D) is 0.920 to 0.965 g / cm ³ .
Characteristic (iii): High load melt flow rate (HLMFR (D)) is 1 to 100 g / 10 min.

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