pellet

Abstract

To provide a pellet expected to wall-thin a molded body and extend a life of the molded body, and having excellent characteristics especially for resin modifying due to enabling improving mechanical strength of the molded body by being added to a general-purpose resin, and mixing without spoiling the external appearance.SOLUTION: A pellet is such that: there is contained a polyethylene polymer which has: (1) HLMFR of 0.01-50 g / 10 min; (2) an elution curve by GPC of two peaks; (2-1) Mw at a high molecular weight side of 900,000-5,000,000, and Mw / Mn of 2.0-5.0; (2-2) Mw at a low molecular weight side of 10,000-500,000, and Mw / Mn of 2.0-5.0; and (2-3) a high molecular weight side peak / a low molecular weight side peak (wt.%) of 5 / 95-80 / 20; (I) an average weight per particle is 13 mg-31 mg; and (II) an average aspect ratio per particle is 1.2-1.6.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to specific pellets containing a specific polyethylene polymer, and more specifically, to pellets that are easy to handle and transport, and that can be added to general-purpose resins to improve the mechanical strength of molded articles, and can be kneaded without impairing the appearance, and therefore have excellent properties for resin modification, which are expected to lead to thinner molded articles and longer life of molded articles. [Background technology]

[0002] Polyethylene is a resin used in a wide range of applications, and in order to tailor it to each application, various techniques have been proposed to control the molecular weight distribution and composition by combining two or more resin components, thereby improving various physical properties and appearance. For example, increasing the amount of higher molecular weight components improves mechanical strength but decreases moldability, while increasing the amount of lower molecular weight components decreases mechanical strength but improves moldability.

[0003] Proposed methods for combining two or more polyethylene components include a method in which each component is polymerized and then blended by melt kneading or dry blending, a method in which multistage polymerization is carried out continuously, a method in which two or more polyethylene components are simultaneously produced by adding multiple polyethylene polymerization catalysts to a polymerization system, and a combination of these methods. Furthermore, a resin modifier has also been proposed (see, for example, Patent Document 1), which is blended with a target material to modify the physical properties, appearance, etc. of the target material.

[0004] In the blow molding, injection molding, inflation molding, and extrusion molding of polyethylene, materials with good moldability and physical properties are generally required. In recent years, there has been a demand for lighter weight and thinner walls to reduce costs, but at the same time, excellent mechanical strength is also required.

[0005] Ultra-high molecular weight polyethylene, which has attracted attention in recent years (see, for example, Patent Documents 2 and 3), has an extremely high molecular weight equivalent to a viscosity average molecular weight (hereinafter sometimes referred to as Mv) of 1 million or more, and therefore has excellent impact resistance, self-lubrication, abrasion resistance, weather resistance, chemical resistance, dimensional stability, etc., and has high physical properties comparable to those of engineering plastics. For this reason, attempts have been made to apply it to uses such as lining materials, food industry line parts, machine parts, artificial joints, sporting goods, microporous membranes, and separators using various molding methods.

[0006] However, due to its high molecular weight, ultra-high molecular weight polyethylene has extremely low fluidity when melted, making it difficult to mold by kneading and extrusion, as is the case with ordinary polyethylene, which has a molecular weight in the range of several tens of thousands to approximately 300,000.Therefore, ultra-high molecular weight polyethylene is molded by various methods, such as direct sintering of polymer powder obtained by polymerization, compression molding, molding using a ram extruder in which extrusion molding is performed while intermittently compressing, and extrusion molding in a state where it is dispersed in a solvent or the like, followed by removal of the solvent.

[0007] In order to improve the moldability of ultra-high molecular weight polyethylene and its kneadability with other resins, a method of adding low molecular weight polyethylene has been proposed (see, for example, Patent Documents 4 and 5), and an ultra-high molecular weight polyethylene exhibiting a specific melting behavior has also been proposed (see, for example, Patent Document 6). [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2017-179304 [Patent Document 2] Patent No. 4868853 [Patent Document 3] Patent No. 6405888 [Patent Document 4] Patent No. 4173444 [Patent Document 5] Patent No. 7071966 [Patent Document 6] Patent Publication No. 2021-172716 Summary of the Invention [Problem to be solved by the invention]

[0009] However, although the modified material proposed in Patent Document 1 was effective in improving processability to a certain extent, further improvement was required in terms of the effect of improving mechanical strength.

[0010] Furthermore, Patent Documents 2 and 3 merely propose ultra-high molecular weight polyethylene, and have problems with moldability. The proposals in Patent Documents 4 to 6 also merely improve the processability of ultra-high molecular weight polyethylene, and still have problems with versatility.

[0011] Furthermore, because ordinary ultra-high molecular weight polyethylene has extremely poor melting properties, it is handled as a powder. Such powder has problems in terms of handling and transportability, and when fed into an extruder or the like together with ordinary polyethylene pellets and mixed, the difference in mixability due to the difference in shape leads to problems such as poor mixability and uneven composition of the molded product.

[0012] Therefore, there has been a desire for the emergence of pellets that are not only easy to handle as pellets but also capable of improving the mechanical properties of general-purpose resins, particularly ethylene-based resins, without impairing their processability, and are also excellent for modifying resins. [Means for solving the problem]

[0013] As a result of intensive research to solve the above-mentioned problems, the present inventors have discovered that by containing a polyethylene polymer having specific components in specific proportions and making it into pellets with specific properties, the pellets have excellent handleability and, when used as a resin modifier, can also improve mechanical properties such as impact resistance without impairing processability, thereby completing the present invention.

[0014] That is, the present invention relates to pellets containing a polyethylene polymer, characterized in that the polyethylene polymer satisfies the following properties (1) and (2) and also satisfies the following properties (I) and (II): (1) The melt flow rate (hereinafter sometimes referred to as HLMFR) conforming to JIS K6922-2:1997 at a temperature of 190°C and a load of 21.6 kg is 0.01 to 50 g / 10 min. (2) The elution curve measured by gel permeation chromatography (hereinafter sometimes referred to as GPC) is bimodal, and when the elution curve is expressed as a differential molecular weight distribution (x-axis: Log [M], y-axis: differential distribution value), and the peak is divided into two normal distributions according to the following formula (1), the following properties (2-1) to (2-3) are satisfied. f(x)=a×(1 / (2π(σ 2 )) (1 / 2) ) exp(-((x-μ) 2 ) / (2(σ 2 ))) Formula (1) (a; peak intensity π; pi σ; standard deviation x; variable μ; average) (2-1): The weight average molecular weight (hereinafter sometimes referred to as Mw) due to the peak on the high molecular weight side is 900,000 to 5,000,000, and the molecular weight distribution (hereinafter sometimes referred to as Mw / Mn) expressed as the weight average molecular weight / number average molecular weight (hereinafter sometimes referred to as Mn) is 2.0 to 5.0. (2-2): Mw of the low molecular weight peak is 10,000 to 500,000, and Mw / Mn is 2.0 to 5.0. (2-3): The weight ratio of the high molecular weight peak to the weight ratio of the low molecular weight peak (weight %) is 5 / 95 to 80 / 20. (I): Average weight per pellet is 13mg to 31mg. (II) The aspect ratio, expressed as the ratio of the maximum and minimum lengths between the center line passing through the center point of the pellet and the two points where the pellet ends intersect, is 1.2 to 1.6 as the average aspect ratio per pellet.

[0015] The present invention will be described in detail below.

[0016] The pellets of the present invention comprise a polyethylene polymer, and the polyethylene polymer may be a bimodal polyethylene polymer having a specific ultra-high molecular weight polyethylene component and a specific polyethylene component and exhibiting a bimodal molecular weight distribution, such as an ethylene homopolymer or an ethylene-α-olefin copolymer, where the α-olefin is, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, etc., and is preferably an ethylene homopolymer because it has a particularly excellent effect of modifying resins, particularly ethylene-based resins.

[0017] The polyethylene polymer (1) has an HLMFR (according to JIS K6922-2:1997, temperature 190°C, load 21.6 kg) of 0.01 to 50 g / 10 min and exhibits melt fluidity. If the HLMFR is less than 0.01 g / 10 min, the polymer will have poor processability. On the other hand, if it exceeds 50 g / 10 min, the polymer will have poor mechanical properties.

[0018] The polyethylene polymer constituting the pellets of the present invention is a polyethylene polymer containing a specific ultra-high molecular weight polyethylene component as a specific component, and is a polyethylene polymer having a bimodal molecular weight distribution. In this case, the bimodal molecular weight distribution is a bimodal molecular weight distribution in which the elution curve measured by GPC is bimodal, the elution curve is expressed as a differential molecular weight distribution (x-axis: Log [M], y-axis: differential distribution value), the peak is divided into two normal distributions (ultra-high molecular weight polyethylene component normal distribution, polyethylene component normal distribution) by the above formula (1), and (2-1) the Mw of the ultra-high molecular weight polyethylene component (hereinafter sometimes referred to as component (A)) expressed as the high molecular weight peak component is 900,000 to 500,000. (2-2) The polyethylene component (hereinafter sometimes referred to as component (ii)) represented by the low molecular weight peak component has an Mw of 10,000 to 500,000 (corresponding to [η] of 0.5 to 6.0 dl / g) and an Mw / Mn of 2.0 to 5.0; (2-3) the ratio of component (i) / component (ii) (wt%) is 5 / 95 to 80 / 20. If component (i) is less than 5 wt%, the effect of improving mechanical properties is low. On the other hand, if it exceeds 80 wt%, the processability is poor. In particular, a component (i) / component (ii) (wt%) of 10 / 90 to 50 / 50 is preferred, as this provides a good balance between molding processability and the effect of improving mechanical properties.

[0019] The pellets of the present invention have a shape that allows for excellent transportability and dispersibility when mixed with other resins, particularly ethylene-based resins, using an extruder or the like. The pellet shape in this case is (I) an average weight per pellet of 13 mg to 31 mg, preferably 15 mg to 27 mg, and more preferably 17 mg to 25 mg. The average weight per pellet can be calculated, for example, by measuring the weight of 200 pellets at random. If the average weight per pellet is less than 13 mg, the pellets are too light, resulting in high transport speeds and the generation of fine powder due to friction. Furthermore, the pellets are too small, resulting in poor handleability. Furthermore, when mixed with other resins, the pellets are poorly kneaded and prone to compositional irregularities. On the other hand, if the weight exceeds 31 mg, the pellets are large in weight and shape, resulting in poor transportability, as well as particle separation during air transport and extrusion, which further increases compositional irregularities during the extrusion process.

[0020] Furthermore, the pellets of the present invention (II) have an aspect ratio, expressed as the ratio of the maximum to minimum length between two points where a center line passing through the center of the pellet intersects with the pellet end, of 1.2 to 1.6, preferably 1.3 to 1.5, as an average aspect ratio per pellet. The average aspect ratio per pellet can be determined, for example, by observing 200 pellets under a stereomicroscope, measuring the maximum and minimum length between two points where a center line passing through the center of the pellet intersects with the pellet end, and then calculating the average aspect ratio expressed as the ratio of the maximum to the minimum. If the average aspect ratio is less than 1.2, the pellets will be less easily kneaded with other resins and prone to compositional irregularities. On the other hand, if the average aspect ratio exceeds 1.6, the pellets will be prone to generating fine powder due to friction during transport, resulting in poor handling.

[0021] Furthermore, since the pellets of the present invention have excellent fluidity and are less likely to cause problems such as poor transport due to bridging during transport, (III) a funnel with a 17 mm diameter outlet is placed above a petri dish with an inner diameter of 90 mm so that the height to the outlet is 150 mm, and 200 g of pellets is filled into the funnel with the outlet blocked.The outlet is then opened to measure the height of the cone formed on the petri dish, and the angle of repose calculated using the following formula (2) is preferably 20° to 40°, particularly 22° to 35°, and more preferably 25° to 30°. Angle of repose (°)=tan -1 (height of the cone / 45)×180 / π Equation (2) (π: pi) The polyethylene polymer constituting the pellets of the present invention is a polyethylene polymer in which component (A), an ultra-high molecular weight component, and component (B), a low molecular weight component, coexist in a specific ratio. This allows, for example, component (A) to be highly dispersed when the polyethylene polymer is blended with a resin modification, more specifically, an ethylene-based resin, and makes it possible to highly modify the mechanical strength of the molded body without impairing the appearance, and the polyethylene polymer is particularly effective as a modified pellet for an ethylene-based resin.

[0022] Furthermore, since the resulting resin-modified pellets have a particularly excellent balance between dispersibility in other resins and improved mechanical properties, the polyethylene polymer preferably has (3) a Mw / Mn of 4.0 to 50, particularly 4.0 to 40, calculated as standard polyethylene, as measured by GPC.

[0023] The polyethylene polymer constituting the pellets of the present invention may be any polymer as long as it satisfies the above-mentioned properties, and is preferably produced using a metallocene catalyst, since it is particularly easy to control the molecular weight and molecular weight distribution and to achieve an (ultra)high molecular weight. Examples of methods for producing a polyethylene polymer having both component (a) and component (b) include a method using a co-supported catalyst in which two or more metallocene complexes are supported on a carrier, and a method using two or more multi-stage polymerization.

[0024] Examples of polymerization methods for the polyethylene polymer include solution polymerization, bulk polymerization, gas-phase polymerization, and slurry polymerization. Among these, slurry polymerization is preferred because it enables the production of polyethylene polymers with uniform particle shapes that are particularly easy to pelletize, and because it enables the production of polymers that are likely to efficiently and stably exhibit resin modification with excellent kneadability while maintaining mechanical strength. Furthermore, the solvent used in the slurry polymerization method may be any commonly used organic solvent, such as benzene, toluene, xylene, pentane, hexane, or heptane. Also usable solvents include liquefied gases such as isobutane and propane, and olefins such as 1-butene and 1-hexene.

[0025] Furthermore, the catalyst for polyethylene production used to produce the polyethylene polymer can be any catalyst that allows the production of the polyethylene polymer. For example, in the case of multi-stage polymerization, a metallocene catalyst obtained from at least a transition metal compound (A-1), an organically modified clay modified with an aliphatic salt (B), and an organoaluminum compound (C) can be used. For example, in the case of a co-supported catalyst method, a metallocene catalyst obtained from at least a transition metal compound (A-1), a transition metal compound (A-2), an organically modified clay modified with an aliphatic salt (B), and an organoaluminum compound (C) can be used.

[0026] 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, and transition metal compounds having a (substituted) indenyl group and a (substituted) fluorenyl group. Examples of the transition metal include zirconium and hafnium. Among these, zirconium compounds having a (substituted) cyclopentadienyl group and an amino-substituted fluorenyl group and hafnium compounds having a (substituted) cyclopentadienyl group and an amino-substituted fluorenyl group are preferred, as they enable efficient production of polyethylene polymers suitable for resin modification.

[0027] Examples of the transition metal compound (A-2) include a transition metal compound having a (substituted) cyclopentadienyl group and a (substituted) fluorenyl group, a transition metal compound having a (substituted) cyclopentadienyl group and a (substituted) indenyl group, and a transition metal compound having a (substituted) indenyl group and a (substituted) indenyl group.

[0028] The organically modified clay (B) modified with an aliphatic salt includes clays modified with an aliphatic salt such as an aliphatic amine salt or an aliphatic phosphonium salt.

[0029] The clay compound constituting the organically modified clay (B) may be any clay compound, either natural or synthetic, as long as it belongs to the category of clay compounds. Examples include kaolinite, talc, smectite, vermiculite, mica, brittle mica, and argillaceous ash. Of these, smectite, particularly hectorite or montmorillonite, is more preferred.

[0030] The organically modified clay (B) can be obtained by introducing the aliphatic salt between the layers of the clay compound to form an ionic complex.

[0031] As the organoaluminum compound (C), any compound that falls into the category of organoaluminum compounds can be used, including, for example, alkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[0032] Regarding the method for preparing the catalyst for polyethylene production using the transition metal compounds (A-1) and (A-2) (hereinafter, the transition metal compounds (A-1) and (A-2) are sometimes collectively referred to as component (A)), the organo-modified clay (B) (hereinafter, sometimes referred to as component (B)), and the organoaluminum compound (C) (hereinafter, sometimes referred to as component (C)) that constitute the catalyst for polyethylene production, any method may be used as long as it is possible to prepare a catalyst for polyethylene production containing component (A), component (B), and component (C). Examples of such methods include mixing components (A), (B), and (C) in an inert solvent or using the monomer to be polymerized as a solvent. There are no limitations on the order in which these components are reacted, nor on the temperature or time at which the reaction is carried out. It is also possible to prepare a catalyst for polyethylene production using two or more types of each of component (A), component (B), and component (C).

[0033] The polymerization conditions for producing the polyethylene polymer, such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration, can be selected arbitrarily. Among these, it is preferable to carry out the polymerization at a temperature of 0 to 100°C, for a polymerization time of 10 seconds to 20 hours, and at a polymerization pressure in the range of atmospheric pressure to 100 MPa. It is also possible to adjust the molecular weight using hydrogen or the like during the polymerization. The polymerization can be carried out by any of batch, semi-continuous, and continuous methods, and can also be carried out in two or more stages by changing the polymerization conditions. The polymer particles obtained after the polymerization are separated and recovered from the polymerization solvent by a conventionally known method, and then dried.

[0034] After drying, the polyethylene polymer can be formed into pellets of a specific shape using an extruder, and in this case, the pellets may be blended with additives such as antioxidants, stabilizers, lubricants, and ultraviolet absorbers.

[0035] The method for producing the pellets of the present invention is not particularly limited, and commonly used known methods can be used. Examples of pellet production methods, i.e., granulation methods, include a strand-cut method in which a polyethylene polymer is melted using an extruder, the molten resin is extruded in the form of strands, and then cooled with air or water and cut with a cutter; and an underwater-cut method in which the resin molten in the extruder is extruded into water and cut with a cutter. The extruder used is not particularly limited, and commonly used extruders can be used, such as single-screw extruders and twin-screw extruders. The conditions for pelletization are not particularly limited, and granulation conditions generally used for granulating resins can be used. When granulating the pellets of the present invention, it is preferable to perform the granulation at the lowest possible temperature within the granulation temperature range, for example, 150 to 230°C. The discharge rate is optional, and a rate of 1 to 10,000 kg / h is preferred because it facilitates the stable production of pellets with a regular shape.

[0036] The pellets of the present invention have excellent handleability and transportability, and can be subjected to common molding methods such as injection molding, compression molding, and extrusion molding to form various molded articles having an excellent balance between mechanical properties and processability, and can be used to form various structural materials such as sheets, films, housings, and frames.

[0037] Furthermore, when the pellets of the present invention are blended or mixed with other resins, the pellet shape allows for excellent dispersibility of component (A), an ultra-high molecular weight polyethylene component with excellent mechanical properties, and component (B), a polyethylene component with excellent processability, resulting in excellent resin modification. Examples of other resins that can be used include olefin resins such as ethylene-based resins and propylene-based resins; vinyl chloride resins, styrene-based 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; and 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. The pellets of the present invention are particularly suitable for modifying olefin-based resins and even ethylene-based resins. The ethylene-based resins used in this case include those having a density of 920 kg / m or more. 3 High density polyethylene is preferred to satisfy the above requirements, and an example of such polyethylene is Nipolon Hard (manufactured by Tosoh Corporation).

[0038] The amount of the pellets of the present invention to be blended with other resins may be any amount as long as the modifying effect is exhibited. In particular, since this provides an excellent balance between the mechanical properties and processability, it is preferable to use 5 to 50 parts by weight per 100 parts by weight of the resin.

[0039] Furthermore, a resin composition containing the pellets of the present invention has an excellent balance between mechanical properties and processability, and can therefore be used as various structural materials such as not only sheets and films but also housings and frames. [Effects of the Invention]

[0040] The pellets of the present invention are not only excellent in handling and transportability, but also, when added to general-purpose resins, can improve the mechanical strength of molded articles, can be kneaded without impairing the appearance, are expected to thin the walls of molded articles, and have a long lifespan, and are particularly excellent in terms of resin modification effects. [Example]

[0041] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to these examples as long as they do not depart from the gist of the invention.

[0042] Unless otherwise specified, the reagents used were commercially available products or those synthesized according to known methods.

[0043] The organically modified clay was pulverized using a jet mill (Seishin Enterprise Co., Ltd., product name CO-JET SYSTEM α MARK III), and the particle size after pulverization was measured using a Microtrac particle size distribution analyzer (Nikkiso Co., Ltd., product name MT3000) using ethanol as a dispersant.

[0044] The preparation of the catalyst for polyethylene production, the production of polyethylene polymer, and the solvent purification were all carried out under an inert gas atmosphere. The hexane solution (20 wt%) of triisobutylaluminum manufactured by Tosoh Finechem Co., Ltd. was used.

[0045] The physical properties of the pellets, polyethylene polymer, resin composition, etc. were measured by the following methods.

[0046] ~Measurement of intrinsic viscosity ([η])~ The measurement was carried out using an Ubbelohde viscometer at 135°C with decahydronaphthalene as a solvent and a polyethylene polymer concentration of 0.005 wt%.

[0047] ~Measurement of Mw and Mn~ Measurements were performed using an ultra-high temperature gel permeation chromatography (Senshu Scientific, SSC-7110) equipped with a column (Tosoh, TSKgel GMHHR-H(S)HT) using 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.

[0048] ~MFR~ The melt flow rate was measured at a temperature of 190°C under a load of 2.16 kg in accordance with JIS K6922-2:1997.

[0049] ~HLMFR~ The melt flow rate was measured at a temperature of 190°C under a load of 21.6 kg in accordance with JIS K6922-2:1997.

[0050] ~Pellet weight~ 200 randomly selected pellets were extracted, and the weight of each pellet was measured to calculate the average weight, which was taken as the pellet weight.

[0051] ~Aspect Ratio~ Twenty randomly selected pellets were extracted, and the maximum and minimum values ​​of the length between the two points where the center line passing through the center point of the pellet intersects with the end of the pellet were measured using a stereomicroscope (Nikon (trade name) SMZ1500). The average of the maximum and minimum values ​​was used to calculate the average aspect ratio as the average maximum / average minimum value.

[0052] ~Angle of repose~ A funnel with a 17 mm diameter outlet was placed above a 90 mm inner diameter petri dish so that the height to the outlet was 150 mm. With the outlet blocked, 200 g of pellets was filled into the funnel, and then the outlet was opened to deposit the pellets in a cone shape on the petri dish. The height of the cone was measured, and the angle of repose was calculated using (2) above.

[0053] ~Tensile properties~ Using (trade name) RTG-1210 (manufactured by Orientec Co., Ltd.), the yield stress, nominal breaking strain, and breaking strength of the dumbbell specimen (ATMS-1822) were measured at 25°C and 50 mm / min.

[0054] ~Charpy impact strength~ Using a universal impact tester (manufactured by Toyo Seiki Seisakusho, product name ISO-PE-Z43), the impact strength of 80 mm × 10 mm × 4.0 mm rectangular test pieces with a single notch (notch angle 45°, notch tip radius 0.25 mm) was measured at a support distance of 62 mm and a pendulum load of 4 J.

[0055] ~Mixability evaluation~ The kneadability was evaluated by the number of particles with a diameter of 0.10 mm or more observed on the surface per 10.0 cm of a strand obtained by HLMFR measurement.

[0056] Manufacturing Example 1 (1) Preparation of organically modified clay A 1-liter flask was charged with 300 ml of industrial alcohol (Equinene F-3, manufactured by Japan Alcohol Sales Co., Ltd.) and 300 ml of distilled water. 15.0 g of concentrated hydrochloric acid and 42.4 g (120 mmol) of dimethylbehenylamine (Lipomin DM22D, manufactured by Lion Specialty Chemicals Co., Ltd.) were added, and the mixture was heated to 45°C to disperse 100 g of synthetic hectorite (Laponite RDS, manufactured by BYK Additives Limited). The mixture was then heated to 60°C and stirred for 1 hour while maintaining the temperature. The resulting slurry was filtered, washed twice with 600 ml of hot water at 60°C, and dried in a dryer at 85°C for 12 hours to obtain 125 g of organically modified clay. This organically modified clay was then jet-milled to a median diameter of 10 μm.

[0057] (2) Preparation of catalyst suspension for polyethylene production A 300 ml flask equipped with a thermometer and reflux condenser was purged with nitrogen, and then 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 20 wt % hexane solution of triisobutylaluminum, and the mixture was stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed and washed twice with 200 ml of hexane, and then 200 ml of hexane was added to obtain a suspension of a catalyst for polyethylene production (solids content: 12.5 wt %).

[0058] Manufacturing Example 2 (1) Preparation of organically modified clay The same procedure as in Production Example 1 was carried out.

[0059] (2) Preparation of catalyst suspension for polyethylene production After replacing the air in a 300 ml flask equipped with a thermometer and reflux condenser 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 20 wt % hexane solution of triisobutylaluminum, and the mixture was stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed and washed twice with 200 ml of hexane, and then 200 ml of hexane was added to obtain a suspension of a catalyst for polyethylene production (solids content: 12.5 wt %).

[0060] Manufacturing Example 3 (1) Preparation of organically modified clay The same procedure as in Production Example 1 was carried out.

[0061] (2) Preparation of catalyst suspension for polyethylene production After replacing the air in a 300 ml flask equipped with a thermometer and reflux condenser 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 20 wt % hexane solution of triisobutylaluminum, and the mixture was stirred for 3 hours at 60°C. After cooling to 45°C, the supernatant was removed and washed twice with 200 ml of hexane, and then 200 ml of hexane was added to obtain a suspension of a catalyst for polyethylene production (solids content: 12.5 wt %).

[0062] Manufacturing Example 4 (1) Preparation of organically modified clay The same procedure as in Production Example 1 was carried out.

[0063] (2) Preparation of suspensions of metallocene complex co-supported catalysts for polyethylene production A 300 ml flask equipped with a thermometer and reflux condenser was purged with nitrogen and then charged with 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane. 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 20 wt% hexane solution of triisobutylaluminum were added and stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed and washed twice with 200 ml of hexane. 200 ml of hexane was added to obtain a suspension of a metallocene complex co-supported catalyst for polyethylene production (solids content: 12.5 wt%).

[0064] Production Example 5 (1) Preparation of organically modified clay The same procedure as in Production Example 1 was carried out.

[0065] (2) Preparation of suspensions of metallocene complex co-supported catalysts for polyethylene production After replacing the air in a 300 ml flask equipped with a thermometer and reflux condenser with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane were added, followed by 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 20 wt% hexane solution of triisobutylaluminum, and the mixture was stirred at 60 ° C for 3 hours. After cooling to 45 ° C, the supernatant was removed and washed twice with 200 ml of hexane, and 200 ml of hexane was added to obtain a suspension of a metallocene complex co-supported catalyst for polyethylene production (solids content: 12.5 wt%). Manufacturing Example 6 (1) Preparation of organically modified clay The same procedure as in Production Example 1 was carried out.

[0066] (2) Preparation of suspensions of metallocene complex co-supported catalysts for polyethylene production A 300 ml flask equipped with a thermometer and reflux condenser was purged with nitrogen and then charged with 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane. Then, 0.135 g of bis(n-butylcyclopentadienyl)zirconium dichloride, 0.446 g of diphenylmethylene(cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride, and 142 ml of a 20 wt% hexane solution of triisobutylaluminum were added and stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed and washed twice with 200 ml of hexane. An additional 200 ml of hexane was added to obtain a suspension of a metallocene complex co-supported catalyst for polyethylene production (solids content: 12.5 wt%).

[0067] Manufacturing Example 7 (1) Preparation of organically modified clay The same procedure as in Production Example 1 was carried out.

[0068] (2) Preparation of suspensions of metallocene complex co-supported catalysts for polyethylene production A 300 ml flask equipped with a thermometer and reflux condenser was purged with nitrogen, and then charged with 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane. Next, 0.051 g of bis(n-butylcyclopentadienyl)zirconium dichloride, 0.502 g of diphenylmethylene(cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride, and 142 ml of a 20 wt% hexane solution of triisobutylaluminum were added and stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed and washed twice with 200 ml of hexane. 200 ml of hexane was added to obtain a suspension of a metallocene complex co-supported catalyst for polyethylene production (solids content: 12.5 wt%).

[0069] Manufacturing Example 8 (1) Preparation of organically modified clay The same procedure as in Production Example 1 was carried out.

[0070] (2) Preparation of suspensions of metallocene complex co-supported catalysts for polyethylene production A 300 ml flask equipped with a thermometer and reflux condenser was purged with nitrogen, and then charged with 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane. Next, 0.101 g of bis(n-butylcyclopentadienyl)zirconium dichloride, 0.471 g of diphenylmethylene(cyclopentadienyl)(2-diethylamino-9-fluorenyl)zirconium dichloride, and 142 ml of a 20 wt % hexane solution of triisobutylaluminum were added and stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed and washed twice with 200 ml of hexane. 200 ml of hexane was added to obtain a suspension of a metallocene complex co-supported catalyst for polyethylene production (solids content: 12.5 wt %).

[0071] Manufacturing Example 9 (1) Preparation of organically modified clay The same procedure as in Production Example 1 was carried out.

[0072] (2) Preparation of suspensions of metallocene complex co-supported catalysts for polyethylene production A 300 ml flask equipped with a thermometer and reflux condenser was purged with nitrogen and then charged with 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane. Next, 0.376 g of diphenylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, 0.033 g of diphenylmethylene(cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride, and 142 ml of a 20 wt% hexane solution of triisobutylaluminum were added and stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed and washed twice with 200 ml of hexane. 200 ml of hexane was added to obtain a suspension of a metallocene complex co-supported catalyst for polyethylene production (solids content: 12.5 wt%).

[0073] Manufacturing Example 10 (1) Preparation of organically modified clay The same procedure as in Production Example 1 was carried out.

[0074] (2) Preparation of suspensions of metallocene complex co-supported catalysts for polyethylene production A 300 ml flask equipped with a thermometer and reflux condenser was purged with nitrogen and then charged with 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane. Then, 0.142 g of bis(n-butylcyclopentadienyl)zirconium dichloride, 0.188 g of diphenylmethylene(cyclopentadienyl)(2-diethylamino-7-t-butyl-9-fluorenyl)zirconium dichloride, and 142 ml of a 20 wt% hexane solution of triisobutylaluminum were added and stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed and washed twice with 200 ml of hexane. 200 ml of hexane was added to obtain a suspension of a metallocene complex co-supported catalyst for polyethylene production (solids content: 12.5 wt%).

[0075] Manufacturing Example 11 (1) Preparation of organically modified clay The same procedure as in Production Example 1 was carried out.

[0076] (2) Preparation of suspensions of metallocene complex co-supported catalysts for polyethylene production A 300ml flask equipped with a thermometer and reflux condenser was purged with nitrogen and then charged with 25.0g of the organically modified clay obtained in (1) and 108ml of hexane. 0.361g of diphenylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dichloride, 0.043g of diphenylmethylene(cyclopentadienyl)(2-diethylamino-9-fluorenyl)hafnium dichloride, and 142ml of a 20wt% hexane solution of triisobutylaluminum were then added and stirred at 60°C for 3 hours. After cooling to 45°C, the supernatant was removed and washed twice with 200ml of hexane. 200ml of hexane was added to obtain a suspension of a metallocene complex co-supported catalyst for polyethylene production (solids content: 12.5wt%).

[0077] Manufacturing Example 12 (1) Organically modified clay The same procedure as in Production Example 1 was carried out.

[0078] (2) Preparation of catalyst suspension for polyethylene production A 300 ml flask equipped with a thermometer and reflux condenser was purged with nitrogen, and then charged with 25.0 g of the organically modified clay obtained in (1) and 108 ml of hexane. Next, 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 20 wt % hexane solution of triisobutylaluminum were added and stirred for 3 hours at 60°C. After cooling to 45°C, the supernatant was removed and washed twice with 200 ml of hexane. 200 ml of hexane was added to obtain a suspension of a catalyst for polyethylene production (solids content: 12.5 wt %).

[0079] Preparation Example 1 A bimodal polyethylene, polyethylene polymer (III-1), was produced by two-stage polymerization in which component (III-1) was polymerized in succession after component (III-1), as follows: The polyethylene polymer (III-1) had an HLMFR of 2.74 g / 10 min and an [η] of 3.2 dL / g.

[0080] Manufacturing of ingredient (A-1) A 10-liter autoclave was charged with 6 liters of hexane, 5.5 ml of a 20 wt % hexane solution of triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solids) of the suspension of the catalyst for polyethylene production obtained in Production Example 1, and the temperature was raised to 70°C. After that, ethylene was continuously fed so that the ethylene partial pressure could be maintained at 0.80 MPa, and slurry polymerization was carried out. 500 g of ethylene, calculated as polyethylene, was consumed during the polymerization, and the [η] of component (A-1) calculated in relation to the hydrogen concentration in the system during the polymerization reaction was 10.1 dL / g.

[0081] Manufacture of component (Ro-1) and polyethylene polymer (Ha-1) After polymerizing component (A-1), ethylene was continuously supplied so as to maintain the ethylene partial pressure at 0.87 MPa at 60°C, and hydrogen was intermittently added so that the hydrogen concentration in the gas phase of the autoclave was 4500 ppm, and slurry polymerization was carried out to polymerize component (B-1), thereby producing polyethylene polymer (C-1), an ethylene homopolymer. 500 g of ethylene was consumed in terms of polyethylene, and the [η] of component (B-1), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 2.0 dL / g.

[0082] Using peak separation software, the peaks of polyethylene polymer (III-1) were separated according to a Gaussian distribution and the calculated Mw of component (III-1) was 1,000,000, with an Mw / Mn of 3.2. Similarly, the Mw of component (III-1) was calculated to be 100,000, with an Mw / Mn of 4.1, and component (III-1) / component (III-1) = 10 / 90 (wt%).

[0083] Preparation Examples 2 to 4 Manufacturing of ingredients (A-2 to A-4) The same procedures as in Example 1 were carried out, except that the polymerization time of component (a-1) was 1.5, 2.5, and 3.75 hours for component (a-2), component (a-3), and component (a-4), respectively.

[0084] The polymerization time of component (R-1) was The same procedure as in Example 1 was carried out except that the times for the reaction mixtures (-4) were 3.5, 2.5, and 1.25 hours, respectively.

[0085] For the polyethylene polymers (H-2 to H-4) obtained in Preparation Examples 2 to 4, which were bimodal polyethylenes, the intrinsic viscosity ([η]), Mw, and Mw / Mn were calculated in the same manner as in Production Example 1.

[0086] For the polyethylene polymers (C-2 to C-4), which are bimodal polyethylenes obtained in Preparation Examples 2 to 4, peaks of the polyethylene polymers (C-2 to C-4) were separated according to Gaussian distribution using peak separation software in the same manner as in Production Example 1, and the Mw and Mw / Mn of components (A-2 to A-4), the Mw and Mw / Mn of components (B-2 to B-4), and the ratio of components (A-2 to A-4) / component (B-2 to B-4) were calculated.

[0087] Preparation Example 5 A bimodal polyethylene, polyethylene polymer (III-5), was produced by two-stage polymerization in which component (III-5) was polymerized in succession after component (III-5) was polymerized as follows: The polyethylene polymer (III-5) had an HLMFR of 0.49 g / 10 min and an [η] of 6.1 dL / g.

[0088] Manufacturing of ingredient (A-5) Produced in the same manner as component (A-1) in Preparation Example 1.

[0089] Manufacture of component (Ro-5) and polyethylene polymer (Har-5) After polymerization of component (A-5), ethylene was continuously supplied to maintain the ethylene partial pressure at 0.87 MPa at 60°C, and hydrogen was intermittently added to maintain the hydrogen concentration in the gas phase of the autoclave at 10,500 ppm, followed by slurry polymerization to polymerize component (B-5), producing polyethylene polymer (C-5), an ethylene homopolymer. 500 g of ethylene was consumed in polyethylene equivalent, and the [η] of component (B-5), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 0.7 dL / g.

[0090] Using peak separation software, the peaks of polyethylene polymer (III-5) were separated according to Gaussian distribution and the calculated Mw of component (III-5) was 1,000,000, with an Mw / Mn of 3.2. Similarly, the Mw of component (III-5) was calculated to be 20,000, with an Mw / Mn of 4.5, and component (III-5) / component (III-5) = 50 / 50 (wt%).

[0091] Preparation Example 6 A bimodal polyethylene, polyethylene polymer (III-6), was produced by two-stage polymerization in which component (III-6) was polymerized followed by component (III-6) as follows: The polyethylene polymer (III-6) had an HLMFR of 0.02 g / 10 min and an [η] of 8.6 dL / g.

[0092] Manufacturing of ingredient (A-6) It was produced in the same manner as in Component (A-1) of Preparation Example 1, except that the amount of ethylene consumed in terms of polyethylene was 300 g.

[0093] Manufacture of component (Ro-6) and polyethylene polymer (Ha-6) After polymerization of component (A-6), ethylene was continuously supplied to maintain the ethylene partial pressure at 0.40 MPa at 60°C, and hydrogen was intermittently added to maintain the hydrogen concentration in the gas phase of the autoclave at 600 ppm, followed by slurry polymerization to polymerize component (B-6), producing polyethylene polymer (C-6), an ethylene homopolymer. 700 g of ethylene was consumed in polyethylene equivalent, and the [η] of component (B-6), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 5.6 dL / g.

[0094] Using peak separation software, the peaks of polyethylene polymer (III-6) were separated according to a Gaussian distribution, and the calculated Mw of component (III-6) was 1,000,000, with an Mw / Mn of 3.2. Similarly, the Mw of component (III-6) was calculated to be 400,000, with an Mw / Mn of 3.2, and component (III-6) / component (III-6) = 30 / 70 (wt%).

[0095] Preparation Example 7 A bimodal polyethylene, polyethylene polymer (III-7), was produced by two-stage polymerization in which component (III-7) was polymerized in succession after component (III-7) was polymerized as follows: The polyethylene polymer (III-7) had an HLMFR of 0.01 g / 10 min, but was meltable and had an [η] of 16.9 dL / g.

[0096] Manufacturing of ingredient (A-7) A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solids) of the suspension of the catalyst for polyethylene production obtained in Production Example 2, and the temperature was then raised to 60°C. Ethylene was continuously supplied so that the ethylene partial pressure could be maintained at 0.80 MPa, and slurry polymerization was carried out; 300 g of ethylene, calculated as polyethylene, was consumed in the reaction, and the [η] of component (A-7) calculated in relation to the hydrogen concentration in the system during the polymerization reaction was 22 dL / g.

[0097] Manufacture of component (Ro-7) and polyethylene polymer (Ha-7) After polymerizing component (A-7), ethylene was continuously fed so that the ethylene partial pressure was maintained at 0.80 MPa at 60°C, and hydrogen was intermittently added so that the hydrogen concentration in the gas phase of the autoclave was 4500 ppm, and slurry polymerization was carried out to polymerize component (B-7), producing polyethylene polymer (C-7), an ethylene homopolymer. 700 g of ethylene was consumed in terms of polyethylene, and the [η] of component (B-7), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 2 dL / g.

[0098] Using peak separation software, the peaks of polyethylene polymer (III-7) were separated according to a Gaussian distribution, and the calculated Mw of component (III-7) was 3,000,000, with an Mw / Mn ratio of 2.8. Similarly, the Mw of component (III-7) was calculated to be 100,000, with an Mw / Mn ratio of 4.5, and component (III-7) / component (III-7) = 30 / 70 (wt%).

[0099] Preparation Example 8 A bimodal polyethylene, polyethylene polymer (III-8), was produced by two-stage polymerization in which component (III-8) was polymerized followed by component (III-8) as follows: The polyethylene polymer (III-8) had an HLMFR of 1.0 g / 10 min and an [η] of 22.3.

[0100] Manufacturing of ingredient (A-8) A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solids) of the suspension of the catalyst for polyethylene production obtained in Production Example 3, and the temperature was then raised to 70°C. Ethylene was continuously supplied so that the ethylene partial pressure could be maintained at 0.50 MPa, and slurry polymerization was carried out; 300 g of ethylene, calculated as polyethylene, was consumed in the reaction, and the [η] of component (A-8) calculated in relation to the hydrogen concentration in the system during the polymerization reaction was 29 dL / g.

[0101] Manufacture of component (Ro-8) and polyethylene polymer (Ha-8) After polymerizing component (A-8), ethylene was continuously fed so that the ethylene partial pressure was maintained at 0.50 MPa at 60°C, and hydrogen was intermittently added so that the hydrogen concentration in the gas phase of the autoclave was 3000 ppm, and slurry polymerization was carried out to polymerize component (B-8), producing polyethylene polymer (C-8), an ethylene homopolymer. 700 g of ethylene was consumed in terms of polyethylene, and the [η] of component (B-8), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 2 dL / g.

[0102] Using peak separation software, the peaks of polyethylene polymer (III-8) were separated according to Gaussian distribution and calculated to give component (III-8) with a Mw of 4,500,000 and a Mw / Mn of 3. Similarly, component (III-8) was calculated to have a Mw of 100,000, a Mw / Mn of 3.2, and component (III-8) / component (III-8) = 30 / 70 (wt%).

[0103] Preparation Example 9 A bimodal polyethylene (H-9) was produced by polymerization using a metallocene complex co-supported catalyst for polyethylene production as follows: The polyethylene (H-9) had an HLMFR of 2.67 g / 10 min and an [η] of 3.2 dL / g.

[0104] A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solid content) of the suspension of the metallocene complex-co-supported catalyst for polyethylene production obtained in Production Example 4, and the temperature was then raised to 70°C. Ethylene was continuously supplied so that the ethylene partial pressure could be maintained at 0.80 MPa, and slurry polymerization was carried out; 950 g of ethylene, calculated as polyethylene, was consumed in the reaction, and a polyethylene polymer (H-9), which was an ethylene homopolymer, was produced.

[0105] Using peak separation software, the peaks of polyethylene polymer (III-9) were separated according to Gaussian distribution and calculated to give component (IV-9) with a Mw of 1,000,000 and a Mw / Mn of 1. Similarly, component (IV-9) was calculated to have a Mw of 130,000, a Mw / Mn of 3.9, and component (IV-9) / component (IV-9) = 10 / 90 (wt%).

[0106] Preparation Example 10 A bimodal polyethylene (H-10) was produced by polymerization using a metallocene complex co-supported catalyst for polyethylene production as follows: The polyethylene (H-10) had an HLMFR of 0.82 g / 10 min and an [η] of 5.1 dL / g.

[0107] A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solid content) of the suspension of the metallocene complex-co-supported polyethylene catalyst obtained in Production Example 5, and the temperature was then raised to 70°C. Ethylene was continuously supplied so that the ethylene partial pressure could be maintained at 0.80 MPa, and slurry polymerization was carried out; 950 g of ethylene, calculated as polyethylene, was consumed in the reaction, and a polyethylene polymer (H-10), which was an ethylene homopolymer, was produced.

[0108] Using peak separation software, the peaks of polyethylene (H-10) were separated according to a Gaussian distribution, and the calculated Mw of component (A-10) was 1,000,000, with an Mw / Mn ratio of 3.1. Similarly, the Mw of component (B-10) was calculated to be 130,000, with an Mw / Mn ratio of 3.9, and component (A-10) / component (B-10) = 30 / 70 (wt%).

[0109] Preparation Example 11 A bimodal polyethylene (H-11) was produced by polymerization using a metallocene complex co-supported catalyst for polyethylene production as follows: The polyethylene (H-11) had an HLMFR of 0.22 g / 10 min and an [η] of 6.6 dL / g.

[0110] A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solid content) of the suspension of the metallocene complex co-supported catalyst for polyethylene production obtained in Production Example 6, and the temperature was raised to 70°C. Ethylene was then continuously supplied so that the ethylene partial pressure could be maintained at 0.80 MPa, and slurry polymerization was carried out; 950 g of ethylene, calculated as polyethylene, was consumed in the reaction, and a polyethylene polymer (H-11), which was an ethylene homopolymer, was produced.

[0111] Using peak separation software, the peaks of polyethylene (H-11) were separated according to a Gaussian distribution, and the calculated Mw of component (A-11) was 1,000,000, with an Mw / Mn ratio of 3.1. Similarly, the Mw of component (B-11) was calculated to be 130,000, with an Mw / Mn ratio of 3.9, and component (A-11) / component (B-11) = 50 / 50 (wt %).

[0112] Preparation Example 12 A bimodal polyethylene, polyethylene polymer (H-12), was produced by polymerization using a metallocene complex co-supported catalyst for polyethylene production as follows: The polyethylene polymer (H-12) had an HLMFR of 0.03 g / 10 min and an [η] of 8.6 dL / g.

[0113] A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solid content) of the suspension of the metallocene complex co-supported catalyst for polyethylene production obtained in Production Example 7, and the temperature was then raised to 70°C. Ethylene was continuously supplied so that the ethylene partial pressure could be maintained at 0.80 MPa, and slurry polymerization was carried out; 950 g of ethylene, calculated as polyethylene, was consumed in the reaction, and a polyethylene polymer (H-12), which was an ethylene homopolymer, was produced.

[0114] Using peak separation software, the peaks of polyethylene (H-12) were separated according to a Gaussian distribution and the calculated Mw of component (A-12) was 1,000,000, with an Mw / Mn ratio of 3.1. Similarly, the Mw of component (B-12) was calculated to be 130,000, with an Mw / Mn ratio of 3.9, and component (A-12) / component (B-12) = 75 / 25 (wt%).

[0115] Preparation Example 13 A bimodal polyethylene, polyethylene polymer (H-13), was produced by polymerization using a metallocene complex co-supported catalyst for polyethylene production as follows. The polyethylene polymer (H-13) had an HLMFR of 0.46 g / 10 min and an [η] of 6.1 dL / g.

[0116] A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a 20 wt % hexane solution of triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solid content) of the suspension of the catalyst for polyethylene production obtained in Production Example 8, and the temperature was raised to 70°C. Ethylene was then continuously supplied so that the ethylene partial pressure could be maintained at 0.80 MPa, and slurry polymerization was carried out. 950 g of ethylene, calculated as polyethylene, was consumed in the reaction, and a polyethylene polymer (H-13), which was an ethylene homopolymer, was produced.

[0117] Using peak separation software, the peaks of polyethylene (H-13) were separated according to a Gaussian distribution, and the calculated Mw of component (A-13) was 1,000,000, with an Mw / Mn ratio of 4.1. Similarly, the Mw of component (B-13) was calculated to be 20,000, with an Mw / Mn ratio of 4.4, and component (A-13) / component (B-13) = 50 / 50 (wt%).

[0118] Preparation Example 14 A bimodal polyethylene, polyethylene polymer (H-14), was produced by polymerization using a metallocene complex co-supported catalyst for polyethylene production as follows. The polyethylene polymer (H-14) had an HLMFR of 0.01 g / 10 min and an [η] of 8.6 dL / g.

[0119] A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solid content) of the suspension of the metallocene complex co-supported catalyst for polyethylene production obtained in Production Example 9, and the temperature was raised to 70°C. Ethylene was then continuously supplied so that the ethylene partial pressure could be maintained at 0.80 MPa, and slurry polymerization was carried out; 950 g of ethylene, calculated as polyethylene, was consumed in the reaction, and a polyethylene polymer (H-14), which was an ethylene homopolymer, was produced.

[0120] Using peak separation software, the peaks of polyethylene (H-14) were separated according to a Gaussian distribution, and the calculated Mw of component (A-14) was 1,000,000, with an Mw / Mn ratio of 3.3. Similarly, the Mw of component (B-14) was calculated to be 400,000, with an Mw / Mn ratio of 3.5, and component (A-14) / component (B-14) = 30 / 70 (wt%).

[0121] Preparation Example 15 A bimodal polyethylene, polyethylene polymer (H-15), was produced by polymerization using a metallocene complex co-supported catalyst for polyethylene production as follows. The polyethylene polymer (H-15) had an HLMFR of 0.01 g / 10 min and an [η] of 16.9 dL / g.

[0122] A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solid content) of the suspension of the metallocene complex co-supported catalyst for polyethylene production obtained in Production Example 10, and the temperature was raised to 70°C. Ethylene was then continuously supplied so that the ethylene partial pressure could be maintained at 0.80 MPa, and slurry polymerization was carried out. 950 g of ethylene, calculated as polyethylene, was consumed in the reaction, and a polyethylene polymer (H-15), which was an ethylene homopolymer, was produced.

[0123] Using peak separation software, the peaks of polyethylene (H-15) were separated according to a Gaussian distribution and the calculated Mw of component (A-15) was 3,150,000, with an Mw / Mn of 3.8. Similarly, the Mw of component (B-15) was calculated to be 90,000, with an Mw / Mn of 4.1, and component (A-15) / component (B-15) = 30 / 70 (wt%).

[0124] Preparation Example 16 A bimodal polyethylene, polyethylene polymer (H-16), was produced by polymerization using a metallocene complex co-supported catalyst for polyethylene production as follows. The polyethylene polymer (H-16) had an HLMFR of 0.01 g / 10 min and an [η] of 22.3 dL / g.

[0125] A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solid content) of the suspension of the metallocene complex co-supported catalyst for polyethylene production obtained in Production Example 11, and the temperature was raised to 70°C. Ethylene was then continuously supplied so that the ethylene partial pressure could be maintained at 0.50 MPa, and slurry polymerization was carried out; 950 g of ethylene, calculated as polyethylene, was consumed in the reaction, and a polyethylene polymer (H-16), which was an ethylene homopolymer, was produced.

[0126] Using peak separation software, the peaks of polyethylene (H-16) were separated according to a Gaussian distribution and the calculated Mw of component (A-16) was 4,400,000, with an Mw / Mn ratio of 3.5. Similarly, the Mw of component (B-16) was calculated to be 100,000, with an Mw / Mn ratio of 4.6, and component (A-16) / component (B-16) = 30 / 70 (wt%).

[0127] [Table 1]

[0128] [Table 2]

[0129] Preparation Example 17 A polyethylene polymer (III-17) was obtained in the same manner as in Preparation Example 1, except that only the component (III-1) in Preparation Example 1 was polymerized.

[0130] The obtained polyethylene polymer (Ha-17) had an [η] of 10.1 dl / g, and a Mw of 1,000,000 and a Mw / Mn of 3.2 as determined by GPC.

[0131] Preparation Example 18 A bimodal polyethylene, polyethylene polymer (H-18), was produced by polymerization as follows. The HLMFR of the polyethylene polymer (H-18) could not be measured, and [η] was 8.3 dL / g.

[0132] A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solids content) of the suspension of the catalyst for polyethylene production obtained in Production Example 12, and the temperature was raised to 70°C. Ethylene was then continuously supplied so that the ethylene partial pressure could be maintained at 0.80 MPa, and slurry polymerization was carried out; 950 g of ethylene, calculated as polyethylene, was consumed in the reaction, and a polyethylene polymer (H-18) was produced.

[0133] Using peak separation software, the peaks of polyethylene polymer (H-18) were separated according to a Gaussian distribution, and the calculated Mw of component (A-18) was 7,000,000, with an Mw / Mn ratio of 2.8. Similarly, the Mw of component (B-18) was calculated to be 100,000, with an Mw / Mn ratio of 4.4, and component (A-18) / component (B-18) = 10 / 90 (wt%).

[0134] Preparation Example 19 A bimodal polyethylene, polyethylene homopolymer (H-19), was produced by continuously polymerizing component (A-19) and component (B-19) as follows. The polyethylene polymer (H-19) had an HLMFR of 5.19 g / 10 min and an [η] of 4.1 dL / g.

[0135] Manufacturing of ingredient (I-19) A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a 20 wt % hexane solution of triisobutylaluminum, and 2.50 g (corresponding to 310 mg of solids content) of the suspension of the catalyst for polyethylene production obtained in Production Example 1, and the temperature was then raised to 60°C. Ethylene was continuously supplied so as to maintain the ethylene partial pressure at 0.37 MPa, and hydrogen was further added intermittently so that the hydrogen concentration in the gas phase of the autoclave became 6,400 ppm, to carry out slurry polymerization, and 500 g of ethylene, calculated as polyethylene, was consumed in the reaction.

[0136] Manufacture of component (Ro-19) and polyethylene polymer (Ha-19) After polymerizing component (A-19), component (B-19) was produced in the same manner as component (B-1) described in Preparation Example 1, and polyethylene polymer (C-19) was produced.

[0137] Using peak separation software, the peaks of polyethylene polymer (H-19) were separated according to a Gaussian distribution, and the calculated Mw of component (A-19) was 500,000, with an Mw / Mn of 2.8. Similarly, the Mw of component (B-19) was calculated to be 100,000, with an Mw / Mn of 4.4, and component (A-19) / component (B-19) = 50 / 50 (wt%).

[0138] Preparation Example 20 A bimodal polyethylene, polyethylene polymer (III-20), was produced by continuously polymerizing component (III-20) and component (III-20) as follows. The HLMFR of the polyethylene polymer (III-20) could not be measured, and [η] was 8.9 dL / g.

[0139] Manufacturing of ingredient (I-20) A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.5 g (corresponding to 310 mg of solids) of the suspension of the catalyst for polyethylene production obtained in Production Example 13, and the temperature was then raised to 60°C. Ethylene was continuously supplied so as to maintain the ethylene partial pressure at 0.87 MPa, and hydrogen was further added intermittently so that the hydrogen concentration in the gas phase of the autoclave became 2100 ppm, thereby carrying out slurry polymerization; 500 g of ethylene, calculated as polyethylene, was consumed in the reaction.

[0140] Manufacture of component (Ro-20) and polyethylene polymer (Ha-20) After polymerizing component (A-20), ethylene was continuously supplied so as to maintain the ethylene partial pressure at 0.87 MPa at 60°C, and hydrogen was intermittently added so that the hydrogen concentration in the gas phase of the autoclave became 2600 ppm, thereby carrying out slurry polymerization. 500 g of ethylene, calculated as polyethylene, was consumed in the reaction, and polyethylene polymer (C-20) was produced.

[0141] Using peak separation software, the peaks of polyethylene polymer (H-20) were separated according to a Gaussian distribution, and the calculated Mw of component (A-20) was 1,000,000, with an Mw / Mn of 3.2. Similarly, the Mw of component (B-20) was calculated to be 700,000, with an Mw / Mn of 4.4, and component (A-20) / component (B-20) = 50 / 50 (wt%).

[0142] Preparation Example 21 A bimodal polyethylene, polyethylene polymer (III-21), was produced by continuously polymerizing component (III-21) and component (III-21) as follows. The HLMFR of the polyethylene polymer (III-21) could not be measured, and [η] was 9.3 dL / g.

[0143] Manufacturing of ingredient (A-21) A 10-liter autoclave was charged with 6.0 liters of hexane, 5.5 ml of a hexane solution of 20 wt % triisobutylaluminum, and 2.5 g (corresponding to 310 mg of solids) of the suspension of the catalyst for polyethylene production obtained in Production Example 1, and the temperature was then raised to 60°C. Ethylene was continuously supplied so as to maintain the ethylene partial pressure at 0.87 MPa, and hydrogen was further added intermittently so that the hydrogen concentration in the gas phase of the autoclave became 2100 ppm, thereby carrying out slurry polymerization; 900 g of ethylene, calculated as polyethylene, was consumed in the reaction.

[0144] Manufacture of component (Ro-21) and polyethylene polymer (Ha-21) After polymerizing component (A-21), ethylene was continuously supplied so as to maintain the ethylene partial pressure at 0.87 MPa at 60°C, and hydrogen was intermittently added so that the hydrogen concentration in the gas phase of the autoclave became 4500 ppm, thereby carrying out slurry polymerization. 100 g of ethylene, calculated as polyethylene, was consumed in the reaction, and polyethylene polymer (C-21) was produced.

[0145] Using peak separation software, the peaks of polyethylene polymer (H-21) were separated according to Gaussian distribution and the calculated Mw of component (A-21) was 1,000,000, with an Mw / Mn of 3.2. Similarly, the Mw of component (B-26) was calculated to be 100,000, with an Mw / Mn of 4.4, and component (A-21) / component (B-21) = 90 / 10 (wt%).

[0146] [Table 3]

[0147] Example 1 The polyethylene polymer (III) produced in Preparation Example 1 was blended with 1,000 ppm of an antioxidant (product name Irganox 1010, manufactured by BASF), and extruded using a twin-screw extruder (manufactured by The Japan Steel Works, Ltd., product name TEX25α) equipped with an underwater cutter and set at an extrusion temperature of 190°C, a screw rotation speed of 30 rpm, and a discharge rate of 10 kg / h. 40 kg of pellets were obtained, each having an average weight of 17.5 mg, an average aspect ratio of 1.3, and an angle of repose of 25°. The physical properties of the resulting pellets are shown in Table 4.

[0148] 8 g of the obtained pellets, 32 g of a commercially available ethylene-based resin (manufactured by Tosoh Corporation, product name: Nipolonhard 8D01A), and 0.04 g of an antioxidant (manufactured by BASF, product name: Irganox 1010) were placed in a 70 ml batch mixer (manufactured by Toyo Seiki Seisaku-sho, Ltd., product name: Labo Plastomill 4C150) and mixed for 5 minutes at a mixing temperature of 190°C and a rotation speed of 30 rpm to obtain a resin composition. Test pieces were prepared from the resin composition and evaluated. The results are shown in Table 4.

[0149] Examples 2 to 5 Pellets were obtained in the same manner as in Example 1, except that the polyethylene polymers (Ha-2) to (Ha-5) produced in Preparation Examples 2 to 5 were used instead of the polyethylene polymer (Ha-1). The pellet properties and evaluation results are shown in Table 4.

[0150] Examples 6 to 8 Pellets were obtained in the same manner as in Example 1, except that the polyethylene polymers (H-6) to (H-8) produced in Preparation Examples 6 to 8 were used instead of the polyethylene polymer (H-1), and the physical properties of the pellets are shown in Table 4. The resin compositions were evaluated using a commercially available ethylene-based resin (manufactured by Tosoh Corporation, product name Nipolon Hard HD5110).

[0151] [Table 4]

[0152] Examples 9 to 13 Pellets were obtained in the same manner as in Example 1, except that the polyethylene polymers (H-9) to (H-13) produced in Preparation Examples 9 to 13 were used instead of the polyethylene polymer (H-1). The pellet properties and evaluation results are shown in Table 5.

[0153] Examples 14 to 16 Pellets were obtained in the same manner as in Example 6, except that polyethylene polymers (H-14) to (H-16) produced in Preparation Examples 14 to 16 were used instead of polyethylene polymer (H-6). The pellet properties and evaluation results are shown in Table 5.

[0154] [Table 5]

[0155] The pellets obtained in Examples 1 to 16 all provided resin compositions excellent in Charpy impact strength and kneadability.

[0156] Comparative Example 1 Evaluation was carried out using commercially available polyethylene (manufactured by Tosoh Corporation, product name Nipolon Hard 8D01A, MFR=0.10, Mw=200,000, Mw / Mn=11). The Charpy impact strength was poor.

[0157] Comparative Example 2 Evaluation was carried out using commercially available polyethylene (manufactured by Tosoh Corporation, product name Nipolon Hard 5110, MFR=0.93, Mw=100,000, Mw / Mn=8.5). The Charpy impact strength was poor.

[0158] Comparative Examples 3 and 4 Pelletization was attempted in the same manner as in Example 1 (extrusion at 190°C), except that the polyethylene polymers (Ha-17) and (Ha-18) produced in Preparation Examples 17 and 18 were used instead of the polyethylene polymer (Ha-1). However, the melt viscosity was high and pellets could not be obtained.

[0159] Comparative Example 5 Pellets were obtained in the same manner as in Example 1, except that the polyethylene polymer (H-19) produced in Preparation Example 19 was used instead of the polyethylene polymer (H-1). The pellet properties and evaluation results are shown in Table 6.

[0160] Comparative Examples 6 and 7 Pelletization was attempted in the same manner as in Example 1 (extrusion at 190°C), except that the polyethylene polymers (Ha-21, 22) produced in Preparation Examples 20 and 21 were used instead of the polyethylene polymer (Ha-1). However, the melt viscosity was high and pellets could not be obtained. Comparative Examples 8-9 Pellets were obtained in the same manner as in Examples 1 and 2, except that the extrusion temperature was set to 240° C. The pellet properties and evaluation results are shown in Table 6.

[0161] [Table 6]

[0162] In Comparative Example 5, the molecular weight of component (A-19) in the pellets was low, and no improvement in mechanical strength was observed when the composition was made. In Comparative Examples 8 and 9, the pellets had poor shape, and the dispersibility was poor when the composition was made into a resin composition, and no improvement in mechanical strength was observed. [Industrial Applicability]

[0163] The pellets of the present invention can be added to general-purpose resins to improve the mechanical strength of the molded body, and can be kneaded without damaging the appearance, so they are expected to make the molded body thinner and extend its lifespan.They are pellets with excellent properties, especially for resin modification, and their industrial value is extremely high.

Claims

1. A pellet containing a polyethylene polymer, characterized in that the polyethylene polymer is a polyethylene polymer that satisfies the following properties (1) and (2) and also satisfies the following properties (I) and (II). (1): A melt flow rate of 0.01 to 50 g / 10 min at a temperature of 190° C. and a load of 21.6 kg in accordance with JIS K6922-2:1997. (2) The elution curve measured by gel permeation chromatography is bimodal, and when the elution curve is expressed as a differential molecular weight distribution (x-axis: Log [M], y-axis: differential distribution value), and the peak is divided into two normal distributions according to the following formula (1), the following properties (2-1) to (2-3) are satisfied: f(x)=a×(1 / (2π(σ ２ )) （１／２） ) exp(-((8-μ) ２ ) / (2(σ ２ ))) formula (1) (a; peak intensity π; pi σ; standard deviation x; variable μ; average) (2-1): The weight average molecular weight due to the peak on the high molecular weight side is 900,000 to 5,000,000, and the molecular weight distribution expressed as weight average molecular weight / number average molecular weight is 2.0 to 5.

0. (2-2): The weight average molecular weight based on the peak on the low molecular weight side is 10,000 to 500,000, and the molecular weight distribution is 2.0 to 5.

0. (2-3): The weight ratio of the high molecular weight peak to the weight ratio of the low molecular weight peak (wt %) is 5 / 95 to 80 / 20. (I): Average weight per pellet is 13 mg to 31 mg. (II): The aspect ratio, expressed as the ratio of the maximum value to the minimum value of the length between two points where a center line passing through the center point of the pellet and an end of the pellet intersect, is 1.2 to 1.6 as an average aspect ratio per pellet.

2. 2. The pellet according to claim 1, wherein the polyethylene polymer is a polyethylene polymer that also satisfies the following property (3): (3): Molecular weight distribution measured by gel permeation chromatography is 4.0 to 50.

3. 2. The pellet of claim 1, wherein the polyethylene polymer is an ethylene homopolymer.

4. 2. The pellet according to claim 1, further satisfying the following characteristic (III): (III): A funnel having a discharge outlet with a diameter of 17 mm was placed above a petri dish with an inner diameter of 90 mm so that the height to the discharge outlet was 150 mm. 200 g of pellets were filled into the funnel with the discharge outlet blocked, and the discharge outlet was then opened to measure the height of the cone formed on the petri dish. The angle of repose calculated by the following formula (2) was 20° to 40°. Angle of repose (°) = tan －１ (height of the cone / 45) x 180 / π Equation (2) (π: Pi)

5. 2. The pellet according to claim 1, which is for modifying a resin.

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