Polyethylene polymer

Abstract

This invention provides a polyethylene polymer that exhibits excellent mechanical properties and processability, as well as excellent dispersibility in resins such as propylene resins, amide resins, arylene sulfide resins, and polycarbonate resins, enabling improved mechanical properties when used in resin compositions. [Solution] A polyethylene polymer that satisfies any of the following characteristics (1) to (3). (1) In accordance with JIS K6922-2:1997, the melt flow rate (HLMFR) at a temperature of 190°C and a load of 21.6 kg is 0.01 to 5 g / 10 min. (2) The elution curve measured by gel permeation chromatography (GPC) shows a bimodal shape. (3); Acid value of 1 to 10 mg KOH / g in accordance with JIS K0070:1992.

Description

Technical Field

[0001] The present invention relates to a polyethylene-based polymer having a specific acid value and a bimodal molecular weight distribution, and a resin composition containing the same. More specifically, it has excellent mechanical properties and processability, and can improve the mechanical strength of a molded body by adding it to other resins such as polypropylene, and can be kneaded without impairing the appearance. Therefore, the present invention relates to a polyethylene-based polymer that enables the provision of a raw material expected to reduce the thickness of a molded body and extend the life of a molded body, and a resin composition containing the same.

Background Art

[0002] Polypropylene-based resins have high heat resistance, high rigidity, good moldability, and are inexpensive. Therefore, they are widely used in applications such as interior and exterior parts of automobiles, such as bumpers, moldings, front grills, instrument panels, electrical equipment, exterior parts, stationery, daily necessities, containers, and films. However, even in polypropylene-based resins having such characteristics, their impact resistance may be insufficient in some applications or under special environments represented by low temperatures, and their use may be restricted.

[0003] In addition, in combination with the increasing response to global environmental problems in recent years, the demand for thinner products for polypropylene-based materials has become even stronger, and the development of materials having better moldability and impact resistance than before is desired.

[0004] To address this issue, one conventional method involves blending rubber-like elastic materials such as ethylene-propylene copolymer rubber (EPR), ethylene-butene-1 copolymer rubber (EBR), and ethylene-propylene-diene copolymer rubber (EPDM). Furthermore, ethylene-α-olefin copolymer rubber using metallocene catalysts, such as hexene-1 and octene-1, has come into use, resulting in materials with improved moldability and physical properties compared to blends of conventional rubber-like elastic materials. On the other hand, regarding the resolution of the aforementioned problems with these blending methods, conventional attempts have been made to satisfy the objective by improving them through polymerization technology, that is, by using block copolymers of propylene and α-olefins. Specifically, a moldability modifier consisting of a propylene-ethylene block copolymer having specific physical properties has been proposed, namely a propylene-ethylene block copolymer in which the MFR of the propylene homopolymer portion (crystalline component) is 500 g / 10 min or more, the MFR of the propylene-ethylene block copolymer is 100 g / 10 min or more, and the die swell ratio is 1.2 to 2.5 (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2004-18647 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, the method proposed in Patent Document 1, while fluid, required increasing the amount of expensive ethylene-based thermoplastic elastomer used to compensate for the lack of impact resistance, thus necessitating further improvement. Furthermore, while such blends of rubber-like elastic materials showed improvements in moldability and impact resistance, they resulted in a decrease in rigidity, creating a challenge in balancing impact resistance and rigidity.

[0007] Furthermore, the demands for resin modification, such as improvements in mechanical properties including impact resistance and moldability, were not limited to propylene-based resins, but were also required for amide-based resins, arylene sulfide-based resins, polycarbonate-based resins, as well as arylene ether-based resins, imide-based resins, thermosetting resins, and others.

[0008] Therefore, there has been a growing expectation for the emergence of new resins that can be used as resin modifiers, enabling improvements in the balance between impact resistance and rigidity, without compromising the processability of resins such as polypropylene resins. [Means for solving the problem]

[0009] As a result of diligent research to solve the above problems, the present inventors have found that a polyethylene polymer having a specific acid value and a bimodal molecular weight distribution exhibits excellent mechanical properties and processability, and can also be used as a modifier for resins such as propylene resins, achieving both mechanical properties such as impact resistance and rigidity without impairing processability, thus completing the present invention.

[0010] In other words, the present invention relates to a polyethylene polymer characterized by satisfying any of the following characteristics (1) to (3). (1) In accordance with JIS K6922-2:1997, the melt flow rate (hereinafter sometimes referred to as HLMFR) at a temperature of 190°C and a load of 21.6 kg is 0.01 to 5 g / 10 min. (2) The elution curve measured by gel permeation chromatography (hereinafter sometimes referred to as GPC) shows a bimodal shape. (3); Acid value of 1 to 10 mg KOH / g in accordance with JIS K0070:1992.

[0011] The details of the present invention are described below.

[0012] The polyethylene polymer of the present invention is a bimodal polyethylene polymer having a high molecular weight and acid value, and exhibiting a bimodal molecular weight distribution. Examples include ethylene homopolymers and ethylene-α-olefin copolymers. Examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene. Among these, ethylene homopolymers are preferred because they exhibit particularly excellent resin properties and modification effects.

[0013] Furthermore, the polyethylene polymer of the present invention (1) has an HLMFR of 0.01 to 5 g / 10 min and exhibits melt fluidity. Preferably, the HLMFR is 0.01 to 3 g / 10 min, and particularly preferably 0.01 to 2 g / min, as this provides an excellent balance between melt fluidity and mechanical properties. If the HLMFR is less than 0.01 g / 10 min, the melt fluidity is poor and the processability is poor. On the other hand, if it exceeds 5 g / 10 min, the molecular weight is low and the mechanical properties are poor.

[0014] Furthermore, the polyethylene polymer of the present invention has a bimodal molecular weight distribution, i.e., a bimodal elution curve measured by GPC, and this bimodal molecular weight distribution results in an excellent balance between moldability / processability, mechanical properties, and modification effect. In contrast, if the elution curve is monomodal or has three or more peaks, the balance between moldability / processability, mechanical properties, and modification effect will be inferior.

[0015] Furthermore, the polyethylene polymer of the present invention has an acid value of 1 to 10 mgKOH / g in accordance with JIS K0070:1992, and is preferably 2 to 8 mgKOH / g, or even 3 to 5 mgKOH / g, as it exhibits excellent compatibility with other resins and modification effects. Here, if the acid value is less than 1 mgKOH / g, it will have poor compatibility with other resins, such as propylene-based resins, and will have a poor modification effect. On the other hand, if the acid value exceeds 10 mgKOH / g, it will be difficult to suppress side reactions such as crosslinking during the preparation of the polyethylene polymer, resulting in poor resin properties and poor compatibility with other resins. The acid value can be measured, for example, in accordance with JIS K0070:1992.

[0016] Furthermore, since the polyethylene polymer of the present invention has a particularly good balance of moldability and mechanical property modification effect, it is preferable that the elution curve measured by GPC is expressed as a differential molecular weight distribution (x axis: Log[M], y axis: differential distribution value) and when the peak is split into two normal distributions using the following formula (i), it satisfies the following (4-1) to (4-3). f(x) = a × (1 / (2π(σ) 2 )) (1 / 2) ) exp(-((x-μ) 2 ) / (2(σ 2 ))) Equation (i) (a; peak intensity σ; standard deviation x; variable μ; mean) (4-1); The weight-average molecular weight (hereinafter sometimes referred to as Mw) in terms of linear polyethylene, based on the peak on the high molecular weight side, is between 900,000 and 5,000,000, and the molecular weight distribution (hereinafter sometimes referred to as Mw / Mn), expressed as weight-average molecular weight / number-average molecular weight, is between 2.0 and 5.0. (4-2) The Mw value due to the peak on the low molecular weight side is between 10,000 and 500,000, and the Mw / Mn ratio is between 2.0 and 5.0. (4-3) The weight ratio of the high molecular weight peak to the low molecular weight peak (weight %) is 5 / 95 to 80 / 20.

[0017] Furthermore, as a polyethylene polymer that satisfies (4), it is preferable that the polyethylene polymer is a bimodal polyethylene polymer having an ultra-high molecular weight polyethylene component (hereinafter sometimes referred to as component (a)) (4-1) as the high molecular weight side peak component of the bimodal molecular weight distribution, with Mw being 900,000 to 5,000,000 and Mw / Mn being 2.0 to 5.0, and a polyethylene component (hereinafter sometimes referred to as component (b)) (4-2) as the low molecular weight side peak component, wherein component (a) / component (b) (weight %) is 5 / 95 or to 80 / 20 (4-3). Furthermore, a polyethylene polymer that satisfies (4) is one in which a component (a), which is an ultra-high molecular weight component, and a component (b), which is a low molecular weight component, coexist in a specific ratio within the polyethylene polymer constituting the polyethylene polymer. As a result, when blended with a material to be modified, such as a general-purpose resin, component (a) can be highly dispersed, making it possible to highly modify the mechanical strength of the molded article without impairing its appearance, and is particularly effective as a modifier for propylene-based resins.

[0018] Furthermore, the polyethylene polymer of the present invention is a modifier that is particularly excellent in balancing dispersibility in general-purpose resins and improvement of mechanical properties, so (5) it is preferable that the Mw / Mn ratio in terms of linear polyethylene, as measured by GPC, is 4.0 or more and less than 50, and particularly preferably 4.0 or more and 40 or less.

[0019] The polyethylene polymer of the present invention can be any polymer that satisfies the above-described properties. For example, a polyethylene polymer satisfying the above-described properties can be prepared by acid modification or the like. In this case, the polyethylene polymer before acid modification is preferably one produced using a metallocene catalyst, as this facilitates control of molecular weight, molecular weight distribution, and (ultra) high molecular weight. As for methods for producing a polyethylene polymer having both component (a) and component (b), examples include using a co-supported catalyst in which two or more metallocene complexes are supported on a carrier, or a multi-stage polymerization method with two or more stages.

[0020] Examples of the polymerization method of the polyethylene polymer include methods such as solution polymerization method, bulk polymerization method, gas phase polymerization method, slurry polymerization method, etc. Among them, in particular, it is possible to produce a polyethylene polymer with a regular particle shape, and while maintaining mechanical strength, it is possible to efficiently and stably produce a modifier with excellent kneadability, so the slurry polymerization method is preferable. Further, as the solvent used in the slurry polymerization method, any commonly used organic solvent may be used, for example, benzene, toluene, xylene, pentane, hexane, heptane, etc. may be mentioned, and liquefied gases such as isobutane, propane, etc., and olefins such as 1-butene, 1-hexene, etc. can also be used as solvents.

[0021] Further, as the catalyst for producing polyethylene used to produce the polyethylene polymer, any catalyst can be used as long as it can produce the polyethylene polymer. For example, in multi-stage polymerization, at least a metallocene catalyst obtained from a transition metal compound (A-1), an organically modified clay (B) modified with an aliphatic salt, and an organoaluminum compound (C) can be mentioned. For example, in the co-supported catalyst method, at least a metallocene catalyst obtained from a transition metal compound (A-1), a transition metal compound (A-2), an organically modified clay (B) modified with an aliphatic salt, and an organoaluminum compound (C) can be mentioned.

[0022] Examples of the transition metal compound (A-1) include transition metal compounds having a (substituted) cyclopentadienyl group and a (substituted) fluorenyl group, transition metal compounds having a (substituted) cyclopentadienyl group and a (substituted) indenyl group, transition metal compounds having a (substituted) indenyl group and a (substituted) fluorenyl group, etc. Examples of the transition metal in that case include zirconium, hafnium, etc. Among them, in particular, since it is possible to efficiently produce a polyethylene polymer suitable as a resin modifier, it is preferably a zirconium compound having a (substituted) cyclopentadienyl group and an amino group-substituted fluorenyl group, or a hafnium compound having a (substituted) cyclopentadienyl group and an amino group-substituted fluorenyl group.

[0023] Examples of the transition metal compound (A-2) include transition metal compounds having a (substituted) cyclopentadienyl group and a (substituted) fluorenyl group, transition metal compounds having a (substituted) cyclopentadienyl group and a (substituted) indenyl group, transition metal compounds having a (substituted) indenyl group and a (substituted) indenyl group, and the like.

[0024] Examples of the organically modified clay (B) modified with the aliphatic salt include clays modified with aliphatic salts such as aliphatic amine salts and aliphatic phosphonium salts.

[0025] The clay compound constituting the organically modified clay (B) may be any one belonging to the category of clay compounds, and may be a natural product or a synthetic product. Examples thereof include kaolinite, talc, smectite, vermiculite, mica, brittle mica, chlorite, etc. Among them, smectite, particularly hectorite or montmorillonite, is more preferable.

[0026] The organically modified clay (B) can be obtained by introducing the aliphatic salt between the layers of the clay compound to form an ion complex.

[0027] Examples of the organoaluminum compound (C) include alkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, as long as they belong to the category called organoaluminum compounds.

[0028] Regarding the method for preparing the polyethylene production catalyst using the transition metal compounds (A-1) and (A-2) (hereinafter, the transition metal compounds (A-1) and (A-2) together may be referred to as component (A)), the organically modified clay (B) (hereinafter, may be referred to as component (B)), and the organoaluminum compound (C) (hereinafter, may be referred to as component (C)), any method may be used as long as it is possible to prepare the polyethylene production catalyst containing component (A), component (B), and component (C). For example, a method may be used in which each of components (A), (B), and (C) is mixed in an inert solvent or using a monomer used for polymerization as the solvent. Furthermore, there are no restrictions on the order in which these components are reacted, nor are there any restrictions on the temperature or processing time of this treatment. It is also possible to prepare the polyethylene production catalyst using two or more types of each of components (A), (B), and (C).

[0029] The polymerization conditions for producing the polyethylene polymer, such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration, can be arbitrarily selected. Among these, polymerization is preferably carried out within the range of a polymerization temperature of 0 to 100°C, a polymerization time of 10 seconds to 20 hours, and a polymerization pressure of atmospheric pressure to 100 MPa. It is also possible to adjust the molecular weight using hydrogen or other means during polymerization. Polymerization can be carried out by batch, semi-continuous, or continuous methods, and it is also possible to carry out the polymerization in two or more stages by changing the polymerization conditions. Furthermore, the polymerized particles obtained after polymerization can be separated and recovered from the polymerization solvent by conventionally known methods and dried. The polymerized particles of the polyethylene polymer can also be formed into pellets using an extruder after drying. Additives such as antioxidants may be added when forming into pellets.

[0030] Furthermore, the polyethylene polymer of the present invention can be prepared by, for example, acid-modifying such a polyethylene polymer. There are no particular restrictions on the acid-modification method, and commonly used known methods can be used. For example, one method is to acid-modify the polyethylene polymer in an extruder in the presence of an acid modifier and an organic peroxide. Examples of acid modifiers include monomers having at least one unsaturated group, such as maleic anhydride, and at least one functional group selected from a carboxyl group, a carboxylic acid ester group, and an acid anhydride group. Examples include acrylic acid, methacrylic acid, vinyl acetate, maleic anhydride, aconitic acid, etc. These monomers can be used alone or in combination with other monomers. As organic peroxides, peroxides that can generate radicals with a hydrogen abstraction effect are preferred, and examples include hydroperoxides, dialkyl peroxides, peroxyesters, and peroxydicarbonates. These organic peroxides may be used alone or in combination with other organic peroxides. Acid modification of polyethylene polymers can be optionally performed by adding an acid modifier and an organic peroxide to the polyethylene polymer, for example, to adjust the acid value which represents the degree of modification.

[0031] Furthermore, there are no particular restrictions on the granulation method when forming granules of the polyethylene polymer of the present invention, and commonly used known methods can be used. Examples of granulation methods include the strand cut method, in which the resin is melted using an extruder and the molten resin is extruded in strand form, cooled with air or water, and then cut with a cutter; and the underwater cut method, in which the resin molten in an extruder is extruded into water and cut with a cutter. There are no particular restrictions on the extruder used for granulating the polyethylene polymer of the present invention, and commonly used extruders can be used. Examples of extruders include single-screw extruders and twin-screw extruders. There are no particular restrictions on the conditions for granulating the polyethylene polymer of the present invention, and granulation conditions commonly used when granulating resins can be used.

[0032] The polyethylene polymer of the present invention exhibits excellent dispersibility and compatibility with general-purpose resins due to its bimodal molecular weight distribution of a high molecular weight component (a) which is excellent in improving mechanical strength and a low molecular weight component (b) which is excellent in improving processability, as well as its acid value, thereby providing a resin composition with improved mechanical strength and suitable as a modifier. For example, it exhibits excellent modifying effects as a modifier for various resins such as olefin resins such as ethylene resins and propylene resins, vinyl chloride resins, styrene resins, ester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and LCP, amide resins such as nylon-6, nylon-6,6, nylon-4,6, and aramid, thermoplastic resins such as polyphenylene sulfide; thermosetting resins such as epoxy resins, polyurethanes, phenolic resins, and urea resins; and rubbers such as natural rubber, polybutadiene, SBS, SEBS, polychloroprene, and chlorosulfonated polyethylene. In particular, it is suitable as a modifier for olefin resins and especially for propylene resins. The propylene resin used in this case had a density of 900 kg / m³. 3 The above requirements are satisfied, and it is preferable that the material is a propylene homopolymer. An example of such a propylene resin is Novatec PP (manufactured by Nippon Polypropylene Co., Ltd.).

[0033] The amount of the modifier of the present invention to be blended into the resin is arbitrary as long as its modifying effect is achieved. In particular, it is preferable to use a resin composition containing 1 to 100 parts by weight, especially 5 to 50 parts by weight, of the modifier per 100 parts by weight of the resin, as this provides an excellent balance between mechanical properties and processability.

[0034] Furthermore, since the resin composition incorporating the polyethylene polymer of the present invention exhibits an excellent balance of mechanical properties, rigidity, and processability, it can be used not only as various structural materials such as interior and exterior parts for automobiles, exterior parts for electrical equipment, housings, and frames, but also as sheets, films, and the like. [Effects of the Invention]

[0035] By providing a polyethylene polymer that offers an excellent balance of impact resistance and rigidity, and exhibits superior kneadability, resulting in excellent durability and moldability, it becomes possible to reduce the thickness of molded bodies by improving their mechanical strength and extend the lifespan of products while maintaining conventional molding methods. [Examples]

[0036] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples as long as it does not exceed the spirit of the invention.

[0037] Unless otherwise stated, the reagents used were either commercially available or synthesized according to known methods.

[0038] A jet mill (manufactured by Seishin Corporation, product name CO-JET SYSTEM α MARK III) was used to pulverize the organically modified clay, and the particle size after pulverization was measured using a Microtrac particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., product name MT3000) with ethanol as a dispersant.

[0039] The preparation of the catalyst for polyethylene production, the production of polyethylene, and the solvent purification were all carried out under an inert gas atmosphere. A hexane solution of triisobutylaluminum (20 wt%) was provided by Tosoh Finechem Co., Ltd. Furthermore, when preparing polyethylene polymers as acid-modified polyethylene polymers, a twin-screw extruder (manufactured by Japan Steel Works, product name TEX25α) equipped with an underwater cut system was used. A predetermined amount of maleic anhydride and organic peroxide was supplied to the polyethylene polymer in the extruder, and the product was manufactured at a set extrusion temperature.

[0040] The various physical properties of polyethylene polymers were measured by the following method.

[0041] ~Measurement of intrinsic viscosity ([η])~ The viscosity was measured using an Ubbelohde viscometer with decahydronaphthalene as the solvent at 135°C at a sample concentration of 0.005 wt%.

[0042] ~Measurement of Mw and Mn~ Ultra-high temperature gel permeation chromatography (Senshu Chemicals, product name SSC-7110) equipped with a column (Tosoh Corporation, product name TSKgel GMHHR-H(S)HT) was used, with 1-chloronaphthalene as the eluent, at a column temperature of 210°C, a sample concentration of 0.5 mg / mL, and an injection volume of 0.2 mL. The molecular weight calibration curve was calibrated using standard polystyrene samples, and Mw and Mn were converted to linear polyethylene values.

[0043] ~MFR~ The melt flow rate at a temperature of 190°C and a load of 2.16 kg was measured in accordance with JIS K6922-2:1997.

[0044] ~HLMFR~ The melt flow rate at a temperature of 190°C and a load of 21.6 kg was measured in accordance with JIS K6922-2:1997.

[0045] ~Acid Value~ Measurements were taken in accordance with JIS K0070:1992.

[0046] ~Tensile Properties~ Using a materials testing machine (Orientec Co., Ltd., product name: Tensilon Universal Materials Tester RTG-1210), the yield stress and fracture strength of a dumbbell piece (compliant with ASTM-1822) were measured at 25°C and 50 mm / min.

[0047] ~Charpy Impact Strength~ Using a universal impact testing machine (manufactured by Toyo Seiki Seisakusho, product name ISO-PE-Z43), the impact strength of a 80mm x 10mm x 4.0mm rectangular test specimen with a single notch of 45° notch angle and notch tip radius of 0.25mm was measured with a pivot distance of 62mm and a pendulum load of 4J.

[0048] ~Evaluation of kneadability~ The kneadability was evaluated by the number of particles with a diameter of 0.10 mm or larger observed per 10.0 cm of strand obtained by extruding a resin composition consisting of a polyethylene polymer and a commercially available resin under the same conditions as the MFR measurement conditions.

[0049] Manufacturing Example 1 (1) Preparation of organically modified clay 300 mL of industrial alcohol (manufactured by Nippon Alcohol Sales Co., Ltd., product name: Ekinen F-3) and 300 mL of distilled water were placed in a 1-liter flask. 15.0 g of concentrated hydrochloric acid and 42.4 g (120 mmol) of dimethylbehenylamine (manufactured by Lion Specialty Chemicals, product name: Lipomin DM22D) were added. The mixture was heated to 45°C to disperse 100 g of synthetic hectorite (manufactured by BYK Additives Limited, product name: Laponite RDS). The temperature was then raised to 60°C and the mixture was stirred for 1 hour while maintaining that temperature. After filtering the slurry, it was washed twice with 600 mL of 60°C warm water and dried in an oven at 85°C for 12 hours to obtain 125 g of organically modified clay. This organically modified clay was pulverized using a jet mill to a median diameter of 10 μm.

[0050] (2) Preparation of a suspension of the catalyst for polyethylene production After purging a 300 mL flask equipped with a thermometer and reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, followed by 0.669 g of diphenylmethylene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride and 142 mL of a hexane solution of 20 wt% triisobutylaluminum. The mixture was stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed, washed twice with 200 mL of hexane, and then 200 mL of hexane was added to obtain a suspension of the catalyst for polyethylene production (solid weight: 12.5 wt%).

[0051] Manufacturing Example 2 (1) Preparation of organically modified clay The process was carried out in the same manner as in Manufacturing Example 1.

[0052] (2) Preparation of a suspension of the catalyst for polyethylene production After purging a 300 mL flask equipped with a thermometer and reflux tubing with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, followed by 0.628 g of diphenylmethylene (cyclopentadienyl)(2-diethylamino-9-fluorenyl) zirconium dichloride and 142 mL of a hexane solution of 20 wt% triisobutylaluminum. The mixture was stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed, washed twice with 200 mL of hexane, and then 200 mL of hexane was added to obtain a suspension of the catalyst for polyethylene production (solid weight: 12.5 wt%).

[0053] Manufacturing Example 3 (1) Preparation of organically modified clay The process was carried out in the same manner as in Manufacturing Example 1.

[0054] (2) Preparation of a suspension of the catalyst for polyethylene production After purging a 300 mL flask equipped with a thermometer and reflux tubing with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, followed by 0.628 g of diphenylmethylene (cyclopentadienyl)(2-diethylamino-9-fluorenyl)hafnium dichloride and 142 mL of a hexane solution of 20 wt% triisobutylaluminum. The mixture was stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed, washed twice with 200 mL of hexane, and then 200 mL of hexane was added to obtain a suspension of the catalyst for polyethylene production (solid weight: 12.5 wt%).

[0055] Manufacturing Example 4 (1) Preparation of organically modified clay The process was carried out in the same manner as in Manufacturing Example 1.

[0056] (2) Preparation of a suspension of metallocene complex co-supported catalyst for polyethylene production After purging a 300 mL flask equipped with a thermometer and reflux tubing with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added. Then, 0.182 g of bis(n-butylcyclopentadienyl)zirconium dichloride, 0.067 g of diphenylmethylene(cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride, and 142 mL of a hexane solution of 20 wt% triisobutylaluminum were added, and the mixture was stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed, washed twice with 200 mL of hexane, and then 200 mL of hexane was added to obtain a suspension of metallocene complex co-supported catalyst for polyethylene production (solid weight: 12.5 wt%).

[0057] Manufacturing Example 5 (1) Preparation of organically modified clay The process was carried out in the same manner as in Manufacturing Example 1.

[0058] (2) Preparation of a suspension of metallocene complex co-supported catalyst for polyethylene production After purging a 300 mL flask equipped with a thermometer and reflux tubing with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added. Then, 0.142 g of bis(n-butylcyclopentadienyl)zirconium dichloride, 0.201 g of diphenylmethylene(cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride, and 142 mL of a hexane solution of 20 wt% triisobutylaluminum were added, and the mixture was stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed, washed twice with 200 mL of hexane, and then 200 mL of hexane was added to obtain a suspension of metallocene complex co-supported catalyst for polyethylene production (solid weight: 12.5 wt%). Manufacturing Example 6 (1) Organic modified clay The process was carried out in the same manner as in Manufacturing Example 1.

[0059] (2) Preparation of a suspension of the catalyst for polyethylene production After purging a 300 mL flask equipped with a thermometer and reflux tubing with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added. Then, 0.365 g of bis(n-butylcyclopentadienyl)zirconium dichloride, 0.063 g of diphenylmethylene(cyclopentadienyl)(2-diethylamino-7-t-butyl-9-fluorenyl)zirconium dichloride, and 142 mL of a hexane solution of 20 wt% triisobutylaluminum were added, and the mixture was stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed, washed twice with 200 mL of hexane, and then 200 mL of hexane was added to obtain a suspension of the catalyst for polyethylene production (solid weight: 12.5 wt%).

[0060] Manufacturing example 7 (1) Preparation of organically modified clay The process was carried out in the same manner as in Manufacturing Example 1.

[0061] (2) Preparation of a suspension of metallocene complex co-supported catalyst for polyethylene production After purging a 300 mL flask equipped with a thermometer and reflux tubing with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added. Then, 0.361 g of diphenylmethylene (cyclopentadienyl)(9-fluorenyl)hafnium dichloride, 0.043 g of diphenylmethylene (cyclopentadienyl)(2-diethylamino-9-fluorenyl)hafnium dichloride, and 142 mL of a hexane solution of 20 wt% triisobutylaluminum were added, and the mixture was stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed, washed twice with 200 mL of hexane, and then 200 mL of hexane was added to obtain a suspension of metallocene complex co-supported catalyst for polyethylene production (solid weight: 12.5 wt%).

[0062] Example 1 Manufacturing of ingredient (I-1) In a 10-liter autoclave, 6 liters of hexane, 5.5 mL of a hexane solution of 20 wt% triisobutylaluminum, and 2.50 g (equivalent to 310 mg of solids) of the polyethylene production catalyst obtained in Production Example 1 were added. After heating to 70°C, ethylene was continuously supplied to maintain an ethylene partial pressure of 0.80 MPa, and slurry polymerization was carried out. During polymerization, 500 g of ethylene (in polyethylene equivalent) was consumed.

[0063] Manufacturing of component (L-1) and polyethylene polymer (H-1) After polymerizing component (a-1), ethylene was continuously supplied to maintain a temperature of 60°C and an ethylene partial pressure of 0.87 MPa. Furthermore, hydrogen was intermittently added to maintain a hydrogen concentration of 4500 ppm in the autoclave's gas phase, and slurry polymerization was carried out to polymerize component (b-1), thereby producing polyethylene polymer (c-1), which is an ethylene homopolymer. 500 g of ethylene, in polyethylene equivalent, was consumed.

[0064] To obtain polyethylene polymer (Ni-1-1), 100 parts by weight of the above polyethylene polymer (Ha-1) was extruded at 220°C in the presence of 1 part by weight of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.09 parts by weight of organic peroxide (manufactured by NOF Corporation, trade name Perhexa 25B).

[0065] The obtained polyethylene polymer (Ni-1-1) had an HLMFR of 2.52 g / 10 min, a bimodal elution curve by GPC, and an acid value of 3.3 mg KOH / g. Furthermore, using peak separation software, the peaks of the polyethylene polymer (Ni-1-1) were separated according to the Gauss distribution, and the calculated Mw of component (I-1) was 1 million, with an Mw / Mn ratio of 3.3. Similarly, the calculated Mw of component (Ro-1) was 100,000, with an Mw / Mn ratio of 4.2, and component (I-1) / component (Ro-1) = 10 / 90 (weight%). The physical properties of the obtained polyethylene polymer (Ni-1-1) are shown in Table 1.

[0066] Example 2 A polyethylene polymer (Ni-1-2) was obtained in the same manner as in Example 1, except that 100 parts by weight of polyethylene polymer (Ha-1) was acid-modified with 0.5 parts by weight of maleic anhydride and 0.05 parts by weight of organic peroxide (manufactured by NOF Corporation, trade name Perhexa 25B). The physical properties of the obtained polyethylene polymer are shown in Table 1.

[0067] Example 3 A polyethylene polymer (Ni-1-3) was obtained in the same manner as in Example 1, except that 3 parts by weight of maleic anhydride and 0.15 parts by weight of organic peroxide (manufactured by NOF Corporation, trade name Perhexa 25B) were used per 100 parts by weight of polyethylene polymer (Ha-1). The physical properties of the obtained polyethylene polymer are shown in Table 1.

[0068] Examples 4-6 Manufacturing of ingredients (I-2~4) The procedure was carried out in the same manner as in Example 1, except that the polymerization time for component (i-1) was set to 1.5 hours, 2.5 hours, and 3.75 hours for components (i-2), (i-3), and (i-4), respectively.

[0069] The procedure was carried out in the same manner as in Example 1, except that the polymerization time for component (L-1) was set to 3.5 hours, 2.5 hours, and 1.25 hours for components (L-2), (L-3), and (L-4), respectively, to obtain polyethylene polymers (H-2 to H-4) which are bimodal polyethylene.

[0070] To obtain polyethylene polymers (Ni-2 to Ni-4), 100 parts by weight of the obtained polyethylene polymer (Ha-2 to Ni-4) was extruded at 220°C in the presence of 1 part by weight of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.09 parts by weight of organic peroxide (manufactured by NOF Corporation, trade name Perhexa 25B). The physical properties of polyethylene polymers (Ni-2 to Ni-4) are shown in Table 1.

[0071] Example 7 Manufacturing of ingredient (I-5) It was manufactured in the same manner as component (i-1) of Example 1.

[0072] Production of component (L-5) and polyethylene polymer (H-5) After polymerizing component (a-5), ethylene was continuously supplied to maintain a temperature of 60°C and an ethylene partial pressure of 0.87 MPa. Furthermore, hydrogen was intermittently added to maintain a hydrogen concentration of 10,500 ppm in the autoclave's gas phase, and slurry polymerization was carried out to polymerize component (b-5), thereby producing polyethylene polymer (c-5), which is an ethylene homopolymer. 500 g of ethylene, in polyethylene equivalent, was consumed.

[0073] The obtained polyethylene polymer (Ha-5) was subjected to acid modification in the same manner as in Example 1 to obtain polyethylene polymer (Ni-5). Polyethylene polymer (Ni-5) had an HLMFR of 0.46 g / 10 min, a bimodal elution curve by GPC, and an acid value of 2.6 mg KOH / g. Furthermore, using peak separation software, the peaks of polyethylene polymer (Ni-5) were separated according to the Gauss distribution, and the calculated Mw of component (I-5) was 1 million, with an Mw / Mn ratio of 3.1. Similarly, the calculated Mw of component (Ro-5) was 20,000, with an Mw / Mn ratio of 4.4, and component (I-5) / component (Ro-5) = 50 / 50 (weight%). The physical properties of the obtained polyethylene polymer (Ni-5) are shown in Table 1.

[0074] Example 8 Manufacturing of ingredient (I-6) Except for using 300g of ethylene in polyethylene equivalent, the product was manufactured in the same manner as the components (i-1) of Example 1.

[0075] Production of component (L-6) and polyethylene polymer (H-6) After polymerizing component (a-6), ethylene was continuously supplied to maintain a temperature of 60°C and an ethylene partial pressure of 0.40 MPa. Hydrogen was then intermittently added to maintain a hydrogen concentration of 600 ppm in the autoclave's gas phase, and slurry polymerization was carried out to polymerize component (b-6), thereby producing polyethylene polymer (c-6), which is an ethylene homopolymer. 700 g of ethylene, in polyethylene equivalent, was consumed.

[0076] The obtained polyethylene polymer (Ha-6) was subjected to acid modification in the same manner as in Example 1 to obtain polyethylene polymer (Ni-6). The obtained polyethylene polymer (Ni-6) had an HLMFR of 0.02 g / 10 min, and the elution curve by GPC showed a bimodal shape, indicating an acid value of 2.8 mg KOH / g. Furthermore, using peak separation software, the peaks of the polyethylene polymer (Ni-6) were separated according to the Gauss distribution, and the calculated Mw of component (I-6) was 1 million, with an Mw / Mn ratio of 3.6. Similarly, the calculated Mw of component (Ro-6) was 400,000, with an Mw / Mn ratio of 3.3, and component (I-6) / component (Ro-6) = 30 / 70 (weight%). The physical properties of the obtained polyethylene polymer (Ni-6) are shown in Table 1.

[0077] Example 9 Manufacturing of ingredient (I-7) In a 10-liter autoclave, 6.0 liters of hexane, 5.5 mL of a hexane solution of 20 wt% triisobutylaluminum, and 2.50 g (equivalent to 310 mg of solids) of the polyethylene production catalyst obtained in Production Example 2 were added. After heating to 60°C, ethylene was continuously supplied to maintain an ethylene partial pressure of 0.80 MPa, and slurry polymerization was carried out. Approximately 300 g of ethylene, in polyethylene equivalent, was consumed by the reaction.

[0078] Manufacturing of component (Ro-7) and polyethylene polymer (Ha-7) After polymerizing component (a-7), ethylene was continuously supplied to maintain a temperature of 60°C and an ethylene partial pressure of 0.80 MPa. Hydrogen was then intermittently added to maintain a hydrogen concentration of 4500 ppm in the autoclave's gas phase, and slurry polymerization was carried out to polymerize component (b-7), thereby producing polyethylene polymer (c-7), which is an ethylene homopolymer. 700 g of ethylene, in polyethylene equivalent, was consumed.

[0079] The obtained polyethylene polymer (Ha-7) was subjected to acid modification in the same manner as in Example 1 to obtain polyethylene polymer (Ni-7). The obtained polyethylene polymer (Ni-7) had an HLMFR of 0.01 g / 10 min, a bimodal elution curve by GPC, and an acid value of 3.5 mg KOH / g. Furthermore, using peak separation software, the peaks of the polyethylene polymer (Ni-7) were separated according to the Gauss distribution, and the calculated Mw of component (A-7) was 3 million, with an Mw / Mn ratio of 2.9. Similarly, the calculated Mw of component (Ro-7) was 100,000, with an Mw / Mn ratio of 4.4, and component (A-7) / component (Ro-7) = 30 / 70 (weight%). The physical properties of the obtained polyethylene polymer (Ni-7) are shown in Table 1.

[0080] Example 10 Manufacturing of ingredient (I-8) In a 10-liter autoclave, 6.0 liters of hexane, 5.5 mL of a hexane solution of 20 wt% triisobutylaluminum, and 2.50 g (equivalent to 310 mg of solids) of the polyethylene production catalyst obtained in Production Example 3 were added. After heating to 70°C, ethylene was continuously supplied to maintain an ethylene partial pressure of 0.50 MPa, and slurry polymerization was carried out. Approximately 300 g of ethylene, in polyethylene equivalent, was consumed by the reaction.

[0081] Production of component (Ro-8) and polyethylene polymer (Ha-8) After polymerizing component (a-8), ethylene was continuously supplied to maintain a temperature of 60°C and an ethylene partial pressure of 0.50 MPa. Furthermore, hydrogen was intermittently added to maintain a hydrogen concentration of 3000 ppm in the autoclave's gas phase, and slurry polymerization was carried out to polymerize component (b-8), thereby producing polyethylene polymer (c-8), which is an ethylene homopolymer. 700 g of ethylene, in polyethylene equivalent, was consumed.

[0082] The obtained polyethylene polymer (Ha-8) was subjected to acid modification in the same manner as in Example 1 to obtain polyethylene polymer (Ni-8). The obtained polyethylene polymer (Ni-8) had an HLMFR of 0.01 g / 10 min, a bimodal elution curve by GPC, and an acid value of 2.5 mg KOH / g. Furthermore, using peak separation software, the peaks of the polyethylene polymer (Ni-8) were separated according to the Gauss distribution, and the calculated Mw of component (I-8) was 4.5 million, with an Mw / Mn ratio of 3.1. Similarly, the calculated Mw of component (Ro-8) was 100,000, with an Mw / Mn ratio of 3.3, and component (I-8) / component (Ro-8) = 30 / 70 (weight%). The physical properties of the obtained polyethylene polymer (Ni-8) are shown in Table 1.

[0083] [Table 1]

[0084] Example 11 In a 10-liter autoclave, 6.0 liters of hexane, 5.5 mL of a hexane solution of 20 wt% triisobutylaluminum, and 2.50 g (equivalent to 310 mg of solids) of the metallocene complex co-supported polyethylene production catalyst obtained in Production Example 4 were added. After heating to 70°C, ethylene was continuously supplied to maintain an ethylene partial pressure of 0.80 MPa, and slurry polymerization was carried out. 950 g of ethylene, in polyethylene equivalent, was consumed by the reaction, producing polyethylene polymer (Ha-9), which is an ethylene homopolymer.

[0085] To obtain polyethylene polymer (Ni-9-1), 100 parts by weight of the above polyethylene polymer (Ha-9) was extruded at 220°C in the presence of 1 part by weight of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.09 parts by weight of organic peroxide (manufactured by NOF Corporation, trade name Perhexa 25B). The obtained polyethylene polymer (Ni-9-1) had an HLMFR of 2.61 g / 10 min, a bimodal elution curve by GPC, and an acid value of 3.3 mg KOH / g. Furthermore, using peak separation software, the peaks of the polyethylene polymer (Ni-9-1) were separated according to the Gauss distribution, and the Mw of component (I-9) was calculated to be 1 million, with an Mw / Mn ratio of 3.2. Similarly, the Mw of component (Ro-9) was calculated to be 130,000, with an Mw / Mn ratio of 3.9, and component (I-9) / component (Ro-9) = 10 / 90 (weight%). The physical properties of the obtained polyethylene polymer (Ni-9-1) are shown in Table 2.

[0086] Example 12 A polyethylene polymer (Ni-9-2) was obtained in the same manner as in Example 11, except that 0.5 parts by weight of maleic anhydride and 0.05 parts by weight of organic peroxide (manufactured by NOF Corporation, trade name Perhexa 25B) were added to 100 parts by weight of the polyethylene polymer (Ha-9) produced in Example 11. The physical properties of the obtained polyethylene polymer are shown in Table 2.

[0087] Example 13 A polyethylene polymer (Ni-9-3) was obtained in the same manner as in Example 11, except that 3 parts by weight of maleic anhydride and 0.15 parts by weight of organic peroxide (manufactured by NOF Corporation, trade name Perhexa 25B) were added to 100 parts by weight of the polyethylene polymer (Ha-9) produced in Example 11. The physical properties of the obtained polyethylene polymer are shown in Table 2.

[0088] Example 14 Bimodal polyethylene (Ha-10) was produced by polymerization using a metallocene complex co-supported catalyst for polyethylene production, as described below.

[0089] In a 10-liter autoclave, 6.0 liters of hexane, 5.5 mL of a hexane solution of 20 wt% triisobutylaluminum, and 2.50 g (equivalent to 310 mg of solids) of the metallocene complex co-supported polyethylene production catalyst obtained in Production Example 5 were added. After heating to 70°C, ethylene was continuously supplied to maintain an ethylene partial pressure of 0.80 MPa, and slurry polymerization was carried out. 950 g of ethylene, in polyethylene equivalent, was consumed by the reaction, producing polyethylene polymer (Ha-10), which is an ethylene homopolymer.

[0090] To obtain polyethylene polymer (Ni-10), 100 parts by weight of the above polyethylene polymer (Ha-10) was extruded at 220°C in the presence of 1 part by weight of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.09 parts by weight of organic peroxide (manufactured by NOF Corporation, product name Perhexa 25B). The obtained polyethylene polymer (Ni-10) had an HLMFR of 0.81 g / 10 min, a bimodal elution curve by GPC, and an acid value of 3.1 mg KOH / g. Furthermore, using peak separation software, the peaks of the polyethylene polymer (Ni-10) were separated according to the Gauss distribution, and the Mw of component (I-10) was calculated to be 1 million, with an Mw / Mn ratio of 3.3. Similarly, the Mw of component (Ro-10) was calculated to be 130,000, with an Mw / Mn ratio of 3.9, and component (I-10) / component (Ro-10) = 30 / 70 (by weight). The physical properties of the obtained polyethylene polymer (Ni-10) are shown in Table 2.

[0091] [Table 2]

[0092] Comparative Example 1 A polyethylene polymer (c-17) was obtained by the same method as in Example 1, except that only component (i-1) in Example 1 was polymerized.

[0093] An attempt was made to produce polyethylene polymer (Ni-17) at 220°C in the presence of 1 part by weight of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.09 parts by weight of organic peroxide (manufactured by NOF Corporation, product name Perhexa 25B) per 100 parts by weight of the above polyethylene polymer (Ha-17), but it could not be extruded.

[0094] Comparative Example 2 A polyethylene polymer (Ha-18), which is bimodal polyethylene, was produced by polymerization in the following manner.

[0095] In a 10-liter autoclave, 6.0 liters of hexane, 5.5 mL of a hexane solution of 20 wt% triisobutylaluminum, and 2.50 g (equivalent to 310 mg of solids) of the polyethylene production catalyst suspension obtained in Production Example 6 were added. After heating to 70°C, ethylene was continuously supplied to maintain an ethylene partial pressure of 0.80 MPa, and slurry polymerization was carried out. 950 g of ethylene, in polyethylene equivalent, was consumed by the reaction. A polyethylene polymer (Ha-18) with [η] = 8.3 dL / g was produced.

[0096] An attempt was made to produce polyethylene polymer (Ni-18) at 220°C in the presence of 1 part by weight of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.09 parts by weight of organic peroxide (manufactured by NOF Corporation, product name Perhexa 25B) per 100 parts by weight of the above polyethylene polymer (Ha-18), but it could not be extruded. Incidentally, using peak separation software, the peak separation of the polyethylene polymer (Ha-18) before acid modification according to the Gauss distribution was calculated, and the Mw of component (I-18) was 7 million, with an Mw / Mn ratio of 2.8. Similarly, the Mw of component (Ro-18) was calculated to be 100,000, with an Mw / Mn ratio of 4.3, and component (I-18) / component (Ro-18) = 10 / 90 (weight%).

[0097] Comparative Example 3 Manufacturing of ingredient (I-19) In a 10-liter autoclave, 6.0 liters of hexane, 5.5 mL of a hexane solution of 20 wt% triisobutylaluminum, and 2.50 g (equivalent to 310 mg of solids) of the polyethylene production catalyst suspension obtained in Production Example 1 were added. After heating to 60°C, ethylene was continuously supplied to maintain an ethylene partial pressure of 0.37 MPa, and hydrogen was intermittently added to maintain a hydrogen concentration of 6400 ppm in the gas phase of the autoclave. Slurry polymerization was carried out, and 500 g of ethylene, in terms of polyethylene, was consumed by the reaction.

[0098] Manufacturing of component (Ro-19) and polyethylene polymer (Ha-19) After polymerizing component (a-19), component (b-19) was manufactured in the same manner as component (b-1) described in Example 1, and polyethylene polymer (c-19) was produced.

[0099] Polyethylene polymer (Ni-19) was produced by extruding 100 parts by weight of the above polyethylene polymer (Ha-19) at 220°C in the presence of 1 part by weight of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.09 parts by weight of organic peroxide (manufactured by NOF Corporation, product name Perhexa 25B). The obtained polyethylene polymer (Ni-19) had an HLMFR of 4.9 g / 10 min, and the elution curve by GPC showed a unimodal peak and an acid value of 6.6 mg KOH / g. Furthermore, using peak separation software, the peaks of the polyethylene polymer (Ni-19) were separated according to the Gauss distribution, and the Mw of component (I-19) was calculated to be 500,000, with an Mw / Mn ratio of 3.1. Similarly, the Mw of component (Ro-19) was calculated to be 100,000, with an Mw / Mn ratio of 4.4, and component (I-19) / component (Ro-19) = 50 / 50 (weight%).

[0100] Comparative Example 4 Manufacturing of ingredient (I-20) In a 10-liter autoclave, 6.0 liters of hexane, 5.5 mL of a hexane solution of 20 wt% triisobutylaluminum, and 2.5 g (equivalent to 310 mg of solids) of the polyethylene production catalyst obtained in Production Example 7 were added. After heating to 60°C, ethylene was continuously supplied to maintain an ethylene partial pressure of 0.87 MPa, and hydrogen was intermittently added to maintain a hydrogen concentration of 2100 ppm in the gas phase of the autoclave. Slurry polymerization was carried out, and 500 g of ethylene, equivalent to polyethylene, was consumed by the reaction.

[0101] Manufacturing of component (Ro-20) and polyethylene polymer (Ha-20) After polymerizing component (I-20), ethylene was continuously supplied to maintain a temperature of 60°C and an ethylene partial pressure of 0.87 MPa. Hydrogen was also added intermittently to maintain a hydrogen concentration of 2600 ppm in the autoclave's gas phase, and slurry polymerization was carried out. Approximately 500 g of ethylene, equivalent to polyethylene, was consumed by the reaction, and polyethylene polymer (H-20) was produced.

[0102] Polyethylene polymer (Ni-20) was produced by extruding 100 parts by weight of the above polyethylene polymer (Ha-20) at 220°C in the presence of 1 part by weight of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.09 parts by weight of organic peroxide (manufactured by NOF Corporation, product name Perhexa 25B). The obtained polyethylene polymer (Ni-20) had an HLMFR of 0.05 g / 10 min, a unimodal elution curve by GPC, and an acid value of 3.1 mg KOH / g. Furthermore, using peak separation software, the peaks of the polyethylene polymer (Ni-20) were separated according to the Gauss distribution, and the Mw of component (I-20) was calculated to be 1 million, with an Mw / Mn ratio of 3.4. Similarly, the Mw of component (Ro-20) was calculated to be 700,000, with an Mw / Mn ratio of 4.3, and component (I-20) / component (Ro-20) = 50 / 50 (weight%).

[0103] Comparative Example 5 Manufacturing of ingredient (I-21) In a 10-liter autoclave, 6.0 liters of hexane, 5.5 mL of a hexane solution of 20 wt% triisobutylaluminum, and 2.5 g (equivalent to 310 mg of solids) of the polyethylene production catalyst obtained in Production Example 1 were added. After heating to 60°C, ethylene was continuously supplied to maintain an ethylene partial pressure of 0.87 MPa, and hydrogen was intermittently added to maintain a hydrogen concentration of 2100 ppm in the gas phase of the autoclave. Slurry polymerization was carried out, and 900 g of ethylene, in terms of polyethylene, was consumed by the reaction.

[0104] Manufacturing of component (Ro-21) and polyethylene polymer (Ha-21) After polymerizing component (I-21), ethylene was continuously supplied to maintain a temperature of 60°C and an ethylene partial pressure of 0.87 MPa. Hydrogen was also added intermittently to maintain a hydrogen concentration of 4500 ppm in the autoclave's gas phase, and slurry polymerization was carried out. 100 g of ethylene, equivalent to polyethylene, was consumed in the reaction, producing polyethylene polymer (H-21).

[0105] Polyethylene polymer (Ni-21) was produced by extruding 100 parts by weight of the above polyethylene polymer (Ha-21) at 220°C in the presence of 1 part by weight of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.09 parts by weight of organic peroxide (manufactured by NOF Corporation, product name Perhexa 25B). HLMFR measurement was not possible for the obtained polyethylene polymer (Ni-21). The elution curve by GPC showed a unimodal peak and an acid value of 2.8 mgKOH / g. Furthermore, using peak separation software, the peaks of the polyethylene polymer (Ni-21) were separated according to the Gauss distribution, and the Mw of component (I-21) was calculated to be 1 million, with an Mw / Mn ratio of 3.1. Similarly, the Mw of component (Ro-26) was calculated to be 100,000, with an Mw / Mn ratio of 4.5, and component (I-21) / component (Ro-21) = 90 / 10 (weight%).

[0106] [Table 3]

[0107] Example 15 8 g of the polyethylene polymer (Ni-1-1) produced in Example 1, 32 g of commercially available propylene resin (Nippon Polypropylene Co., Ltd., product name Novatec PP MFR=2.5), and 0.04 g of antioxidant (BASF, product name Irganox 1010) were placed in a 70 mL batch-type kneader (Toyo Seiki Seisakusho Co., Ltd., product name Laboplastmill 4C150), and kneaded for 5 minutes at a kneading temperature of 230 °C and a rotation speed of 30 rpm to obtain a resin composition, which was then evaluated. The results are shown in Table 4.

[0108] Example 16 A resin composition was prepared and evaluated in the same manner as in Example 15, except that the polyethylene polymer (Ni-1-2) produced in Example 2 was used instead of the polyethylene polymer (Ni-1-1). The results are shown in Table 4.

[0109] Example 17 A resin composition was prepared and evaluated in the same manner as in Example 15, except that the polyethylene polymer (Ni-1-3) produced in Example 3 was used instead of the polyethylene polymer (Ni-1-1). The results are shown in Table 4.

[0110] Examples 18-24 Resin compositions were prepared and evaluated in the same manner as in Example 15, except that polyethylene polymers (Ni-2) to (Ni-8) produced in Examples 4 to 10 were used instead of polyethylene polymer (Ni-1-1). The results are shown in Table 4.

[0111] [Table 4]

[0112] Example 25 8 g of the polyethylene polymer (Ni-9-1) produced in Example 11, 32 g of commercially available propylene resin (Nippon Polypropylene Co., Ltd., product name Novatec PP MFR=2.5), and 0.04 g of antioxidant (BASF, product name Irganox 1010) were placed in a 70 mL batch-type kneader (Toyo Seiki Seisakusho Co., Ltd., product name Laboplastmill 4C150), and kneaded for 5 minutes at a kneading temperature of 230 °C and a rotation speed of 30 rpm to obtain a resin composition, which was then evaluated. The results are shown in Table 5.

[0113] Example 26 A resin composition was prepared and evaluated in the same manner as in Example 25, except that the polyethylene polymer (Ni-9-2) produced in Example 12 was used instead of the polyethylene polymer (Ni-9-1). The results are shown in Table 5.

[0114] Example 27 A resin composition was prepared and evaluated in the same manner as in Example 25, except that the polyethylene polymer (Ni-9-3) produced in Example 13 was used instead of the polyethylene polymer (Ni-9-1). The results are shown in Table 5.

[0115] Example 28 The resin composition was prepared and evaluated in the same manner as in Example 25, except that the polyethylene polymer (Ni-10) produced in Example 14 was used instead of the polyethylene polymer (Ni-9-1). The results are shown in Table 5.

[0116] [Table 5]

[0117] Comparative Example 6 The evaluation was performed using commercially available polypropylene resin (manufactured by Nippon Polypropylene Co., Ltd., product name Novatec PP, MFR=0.4). The results are shown in Table 6.

[0118] Comparative Example 7 The evaluation was performed using commercially available polypropylene resin (manufactured by Nippon Polypropylene Co., Ltd., product name Novatec PP, MFR=2.5). The results are shown in Table 6.

[0119] Comparative Example 8 A resin composition was obtained and evaluated using the same method as in Example 1, except that the polyethylene polymer (Ni-19) produced in Comparative Example 3 was used instead of the polyethylene polymer (Ni-1). The results are shown in Table 6.

[0120] Comparative Example 9 8g of polyethylene polymer (H-1), 32g of commercially available polypropylene resin (manufactured by Nippon Polypropylene Co., Ltd., product name Novatec PP MFR=2.5), and 0.04g of antioxidant (manufactured by BASF, product name Irganox 1010) were placed in a 70mL batch-type kneader (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name Laboplastmill 4C150), and kneaded for 5 minutes at a kneading temperature of 230°C and a rotation speed of 30 rpm to obtain a resin composition. However, the dispersibility of polyethylene polymer (H-1) in the commercially available polypropylene resin was poor, and furthermore, the mechanical strength of the composition with the commercially available polypropylene resin did not improve.

[0121] Comparative Example 10 100 parts by weight of the polyethylene polymer (Ha-1) obtained in Example 1 was extruded at 210°C in the presence of 0.2 parts by weight of maleic anhydride and 0.02 parts by weight of peroxide to obtain polyethylene polymer (Ni-22). The acid value was 0.5 mg KOH / g.

[0122] 8 g of polyethylene polymer (Ni-22), 32 g of commercially available propylene resin (manufactured by Nippon Polypropylene Co., Ltd., product name Novatec PP MFR=2.5), and 0.04 g of antioxidant (manufactured by BASF, product name Irganox 1010) were placed in a 70 mL batch-type kneader (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name Laboplastmill 4C150), and kneaded for 5 minutes at a kneading temperature of 230 °C and a rotation speed of 30 rpm to obtain a resin composition, which was then evaluated. The results are shown in Table 6.

[0123] Comparative Example 11 100 parts by weight of the polyethylene polymer (Ha-1) produced in Example 1 was extruded at 210°C in the presence of 10 parts by weight of maleic anhydride and 0.1 parts by weight of peroxide to obtain polyethylene polymer (Ni-23). ​​The acid value of the obtained polyethylene polymer (Ni-24) was 12 mgKOH / g.

[0124] 8 g of polyethylene polymer (Ni-23), 32 g of commercially available propylene resin (manufactured by Nippon Polypropylene Co., Ltd., product name Novatec PP MFR=2.5), and 0.04 g of antioxidant (manufactured by BASF, product name Irganox 1010) were placed in a 70 mL batch-type kneader (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name Laboplastmill 4C150), and kneaded for 5 minutes at a kneading temperature of 230 °C and a rotation speed of 30 rpm to obtain a resin composition, which was then evaluated. The results are shown in Table 6.

[0125] [Table 6]

[0126] Example 29 8 g of the polyethylene polymer (Ni-1-1) produced in Example 1, 32 g of commercially available nylon resin (UBE Corporation, product name 1024JI MFR=7.1), and 0.04 g of antioxidant (BASF, product name Irganox1010) were placed in a 70 mL batch-type kneader (Toyo Seiki Seisakusho Co., Ltd., product name Laboplastmill 4C150), and kneaded for 5 minutes at a kneading temperature of 270 °C and a rotation speed of 30 rpm to obtain a resin composition, which was then evaluated. The results are shown in Table 7.

[0127] Example 30 A resin composition was prepared and evaluated in the same manner as in Example 29, except that the polyethylene polymer (Ni-1-2) produced in Example 2 was used instead of the polyethylene polymer (Ni-1-1). The results are shown in Table 7.

[0128] Example 31 A resin composition was prepared and evaluated in the same manner as in Example 29, except that the polyethylene polymer (Ni-1-3) produced in Example 3 was used instead of the polyethylene polymer (Ni-1-1). The results are shown in Table 7.

[0129] Examples 32, 33 The resin composition was prepared and evaluated in the same manner as in Example 29, except that polyethylene polymers (Ni-2) and (Ni-3) produced in Examples 4 and 5 were used instead of polyethylene polymer (Ni-1-1). The results are shown in Table 7.

[0130] Comparative Example 12 The evaluation was performed using commercially available nylon resin (manufactured by UBE Corporation, product name 1024JI, MFR=7.1). The results are shown in Table 7.

[0131] [Table 7]

[0132] Example 34 8 g of the polyethylene polymer (Ni-1-1) produced in Example 1, 32 g of commercially available polycarbonate resin (Idemitsu Kosan Co., Ltd., product name: Toughlon #1700, MFR=22.5), and 0.04 g of antioxidant (BASF, product name: Irganox 1010) were placed in a 70 mL batch-type kneader (Toyo Seiki Seisakusho Co., Ltd., product name: Laboplastmill 4C150), and kneaded for 5 minutes at a kneading temperature of 280 °C and a rotation speed of 30 rpm to obtain a resin composition, which was then evaluated. The results are shown in Table 8.

[0133] Example 35 A resin composition was prepared and evaluated in the same manner as in Example 34, except that the polyethylene polymer (Ni-1-2) produced in Example 2 was used instead of the polyethylene polymer (Ni-1-1). The results are shown in Table 8.

[0134] Example 36 A resin composition was prepared and evaluated in the same manner as in Example 34, except that the polyethylene polymer (Ni-1-3) produced in Example 3 was used instead of the polyethylene polymer (Ni-1-1). The results are shown in Table 8.

[0135] Examples 37, 38 A resin composition was prepared and evaluated in the same manner as in Example 34, except that polyethylene polymers (Ni-2) and (Ni-3) produced in Examples 4 and 5 were used instead of polyethylene polymer (Ni-1-1). The results are shown in Table 8.

[0136] Comparative Example 13 The evaluation was performed using commercially available polycarbonate resin (manufactured by Idemitsu Kosan Co., Ltd., product name: Toughlon #1700, MFR=22.5). The results are shown in Table 8.

[0137] [Table 8] [Industrial applicability]

[0138] The polyethylene polymer of the present invention has an excellent balance of impact resistance and rigidity, Because it possesses a specific acid value and a bimodal molecular weight distribution, it can be added to other resins such as polypropylene to improve the mechanical strength of molded articles. Furthermore, it can be mixed without impairing the appearance, making it a resin composition that is expected to enable thinner molded articles and extend their lifespan, thus possessing high industrial value.

Claims

1. A polyethylene polymer characterized by satisfying all of the following characteristics (1) to (3). (1) In accordance with JIS K6922-2:1997, the melt flow rate (HLMFR) at a temperature of 190°C and a load of 21.6 kg is 0.01 to 5 g / 10 min. (2) The elution curve measured by gel permeation chromatography (GPC) shows a bimodal peak. (3) Acid value of 1 to 10 mg KOH / g in accordance with JIS K0070:1992.

2. Furthermore, the polyethylene polymer according to claim 1 is characterized by also satisfying the following characteristic (4). (4) The elution curve measured by GPC is expressed as a differential molecular weight distribution (x axis: Log [M], y axis: differential distribution value), and when the peak is split into two normal distributions using the following formula (i), the following conditions (4-1) to (4-3) are satisfied. f(x)=a×(1 / (2π(σ ２ )) （１／２） ) exp(-((x-μ) ２ ) / (2(s ２ ))) formula (i) (a; peak intensity σ; standard deviation x; variable μ; average) (4-1); The weight-average molecular weight (Mw) in terms of linear polyethylene, based on the peak on the high molecular weight side, is 900,000 to 5,000,000, and the molecular weight distribution (Mw / Mn), expressed as weight-average molecular weight / number-average molecular weight, is 2.0 to 5.

0. (4-2); The Mw due to the peak on the low molecular weight side is between 10,000 and 500,000, and the Mw / Mn ratio is between 2.0 and 5.

0. (4-3); The weight ratio (weight%) of the high molecular weight peak / low molecular weight peak is 5 / 95 to 80 / 20.

3. The polyethylene polymer according to claim 1, characterized in that it also satisfies (5) below. (5) The linear polyethylene equivalent Mw / Mn measured by GPC is 4.0 or more and less than 50.

4. The polyethylene polymer according to claim 1, characterized in that it is an acid-modified ethylene homopolymer.

5. A modifier characterized by containing the polyethylene polymer described in any one of claims 1 to 4.

6. A resin composition characterized by comprising 1 to 100 parts by weight of the polyethylene polymer described in any one of claims 1 to 4 per 100 parts by weight of the resin.

Images