Modifier for resin and resin composition containing the same

Abstract

To provide a modifier for a resin which can improve mechanical strength of a molding by being added to a general purpose resin, can be kneaded without impairing appearance, and thereby achieves thinning of the molding and long life of the molding, and a resin composition containing the same.SOLUTION: A modifier for a resin being a polyethylene polymer satisfies (1): HLMFR according to JIS K 6922-2:1997 of 0.01 to 50 g / 10 min, (2): an elution curve measured by GPC having two peaks, when the elution curve is subjected to peak resolution into two normal distributions, wherein the elution curve satisfies (2-1): Mw by a peak on a high molecular weight side of 900,000 to 5,000,000, and Mw / Mn of 2.0 to 5.0, (2-2): Mw by a peak on a low molecular weight side of 10,000 to 500,000, and Mw / Mn of more than 5.0, and (2-3): a weight ratio (wt.%) of the peak on the high molecular weight side / a weight ratio (wt.%) of the peak on the low molecular weight side of more than 5 / 95 and less than 80 / 20.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin modifier that is a specific polyethylene polymer. More specifically, the present invention relates to a resin modifier that can be added to general-purpose resins to improve the mechanical strength of molded articles and can be kneaded without impairing the appearance, making it possible to provide a raw material that is expected to thin the walls of molded articles and extend the life of molded articles, and to a resin composition containing the same. [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 transition metal 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] Therefore, the present invention provides a resin modifier that can improve the mechanical properties of general-purpose resins, particularly ethylene-based resins, without impairing the processability thereof, and a method for producing the same. [Means for solving the problem]

[0012] As a result of intensive research to solve the above problems, the present inventors discovered that by using a polyethylene polymer containing specific components in specific proportions as a resin modifier, it is possible to improve mechanical properties without impairing processability, and thus completed the present invention.

[0013] That is, the present invention relates to a resin modifier characterized by being a polyethylene polymer satisfying the following properties (1) and (2), and a resin composition containing the same. (1) The melt flow rate (hereinafter sometimes referred to as HLMFR) at a temperature of 190° C. under a load of 21.6 kg conforming to JIS K 6922-2:1997 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 (i), the following (2-1) to (2-3) are satisfied: y=a×(1 / (2π(σ 2 )) (1 / 2) ) exp(-((x-μ) 2 ) / (2(σ 2 ))) Formula (i) (Here, a is the peak intensity, σ is the standard deviation, x is the variable, and μ is x at the peak top.) (2-1): The weight average molecular weight (hereinafter sometimes referred to as Mw) calculated as linear polyethylene based on the peak on the high molecular weight side is 900,000 to 5,000,000, and the molecular weight distribution expressed as Mw / number average molecular weight (hereinafter sometimes referred to as Mn) is 2.0 to 5.0.

[0014] (2-2): Mw is 10,000 to 200,000, calculated as linear polyethylene, and Mw / Mn is greater than 5.0, based on the peak on the low molecular weight side.

[0015] (2-3): The weight ratio of the high molecular weight peak to the weight ratio of the low molecular weight peak (wt %) is greater than 5 / 95 and smaller than 80 / 20.

[0016] The present invention will be described in detail below.

[0017] The resin modifier of the present invention is composed of a polyethylene polymer, and the polyethylene polymer may be a bimodal polyethylene polymer that has a specific ultra-high molecular weight polyethylene component and a specific polyethylene component and exhibits 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 modifying effect on resins, particularly ethylene-based resins.

[0018] The polyethylene polymer (1) has an HLMFR of 0.01 to 50 g / 10 min and exhibits melt fluidity. If the HLMFR is less than 0.01 g / 10 min, the melt fluidity will be low, resulting in poor processability and poor modification effects. On the other hand, if the HLMFR exceeds 50 g / 10 min, the mechanical properties will be poor and the modification effects will be poor.

[0019] The polyethylene polymer constituting the resin modifier of the present invention is an ethylene polymer containing a specific ultra-high molecular weight polyethylene component and a specific polyethylene component with a broader molecular weight distribution as specific components, and is an ethylene polymer having a bimodal molecular weight distribution. The bimodal molecular weight distribution is an ethylene polymer whose elution curve measured by GPC is bimodal, and 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 (ultra-high molecular weight polyethylene component normal distribution and polyethylene component normal distribution) according to the above formula (i). The (2-1) ultra-high molecular weight polyethylene component (hereinafter sometimes referred to as component (A)) represented by the high molecular weight peak component has a Mw of 900,000 to 5,000,000 and a molecular weight distribution expressed as Mw / Mn of 2.0 to 5.0, and the (2-2) polyethylene component (hereinafter sometimes referred to as component (B)) represented by the low molecular weight peak component has a Mw of 10,000 to 500,000 and a Mw / Mn of greater than 5.0. Furthermore, (2-3) the ratio of component (A) / component (B) (wt%) is greater than 5 / 95 and less than 80 / 20. Here, if component (A) is 5 wt% or less, the effect of improving mechanical properties will be low. On the other hand, if it is 80 wt% or more, processability will be poor. In particular, since a good balance between molding processability and the effect of improving mechanical properties will be achieved, it is preferable that the ratio of component (A) / component (B) (wt%) is 10 / 90 to 50 / 50. Furthermore, since a resin modifier having an excellent balance between molding processability and mechanical strength improvement will be achieved, it is preferable that the Mw / Mn of component (B) is greater than 5.0 and 10.0 or less.

[0020] The resin modifier 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. Therefore, when blended with a material to be modified, such as an ethylene-based resin, component (A) can be highly dispersed, making it possible to highly modify the mechanical strength of the molded body without impairing the appearance, and is particularly effective as a modifier for ethylene-based resins.

[0021] Furthermore, since this polyethylene polymer is a resin modifier that has a particularly excellent balance between dispersibility in resins and improved mechanical properties, it is preferable that the polyethylene polymer have (3) a linear polyethylene-equivalent Mw / Mn ratio measured by GPC of 4.0 or more and less than 50, and particularly preferably 4.0 or more and 30 or less.

[0022] Furthermore, since the polyethylene polymer is different from a simple blend in which components (A) and (B) are independently dispersed and is particularly excellent as a modifier, it is preferable that the polyethylene polymer (4-1) has a unimodal crystalline melting peak (hereinafter sometimes referred to as Tm1) in the first scan measured using a differential scanning calorimeter (hereinafter sometimes referred to as DSC) by heating from 0°C to 230°C at a heating rate of 10°C / min (hereinafter sometimes referred to as the first scan). Furthermore, (4-2) after the first scan, the sample is left for 5 minutes, cooled to -20°C at a rate of 10°C / min, left for 5 minutes, and then heated again from -20°C to 230°C at a rate of 10°C / min (hereinafter referred to as the second scan). The melting point of the second scan (hereinafter referred to as Tm2) is measured, and it is preferable that the difference between Tm1 and Tm2 (ΔTm = Tm1 - Tm2) is -1°C or more and less than 15°C, and the ratio (ΔH2 / ΔH1) of the heat of fusion of the first scan (hereinafter referred to as ΔH1) to the heat of fusion of the second scan (hereinafter referred to as ΔH2) is 0.94 or more.

[0023] The polyethylene polymer constituting the resin modifier 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 (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 and enables the efficient and stable production of modifiers with excellent kneadability while maintaining mechanical strength. The solvent used in the slurry polymerization method may be any commonly used organic solvent, such as benzene, toluene, xylene, pentane, hexane, and heptane. Liquefied gases such as isobutane and propane, and olefins such as 1-butene and 1-hexene can also be used as solvents.

[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 (B) modified with an aliphatic salt, 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 (B) modified with an aliphatic salt, 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. In this case, examples of the transition metal include zirconium and hafnium. Among these, zirconium compounds having a (substituted) cyclopentadienyl group and an amino group-substituted fluorenyl group and hafnium compounds having a (substituted) cyclopentadienyl group and an amino group-substituted fluorenyl group are preferred, as they enable efficient production of polyethylene polymers suitable as resin modifiers.

[0027] More specifically, for example, diphenylmethylene(1-indenyl)(9-fluorenyl)zirconium dichloride, diphenylmethylene(1-indenyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride, diphenylmethylene(4-phenyl-1-indenyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride, diphenylsilanediyl(cyclopentadienyl)(2-(dimethylamino)-9-fluorenyl)zirconium dichloride, diphenylsilanediyl(cyclopentadienyl) )(2-(diethylamino)-9-fluorenyl)zirconium dichloride, diphenylsilanediyl(cyclopentadienyl)(2-(dibenzylamino)-9-fluorenyl)zirconium dichloride, diphenylsilanediyl(cyclopentadienyl)(2,7-bis(dimethylamino)-9-fluorenyl)zirconium dichloride, diphenylsilanediyl(cyclopentadienyl)(2,7-bis(diethylamino)-9-fluorenyl)zirconium dichloride, diphenylsilanediyl(cyclopentadienyl)(2,7-bis (Dibenzylamino)-9-fluorenyl)zirconium dichloride, diphenylsilanediyl(cyclopentadienyl)(4-(dimethylamino)-9-fluorenyl)zirconium dichloride, diphenylsilanediyl(cyclopentadienyl)(4-(diethylamino)-9-fluorenyl)zirconium dichloride, diphenylsilanediyl(cyclopentadienyl)(4-(dibenzylamino)-9-fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2-(dimethylamino)-9-fluorenyl) diphenylmethylene(cyclopentadienyl)(2-(diethylamino)-9-fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2-(diisopropylamino)-9-fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2-(dibenzylamino)-9-fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2-(diethylamino)-7-ethyl-9-fluorenyl)zirconium dichloride,Diphenylmethylene(cyclopentadienyl)(2-(diisopropylamino)-7-ethyl-9-fluorenyl)zirconium dichloride, Diphenylmethylene(cyclopentadienyl)(2-(dibenzylamino)-7-ethyl-9-fluorenyl)zirconium dichloride, Diphenylmethylene(cyclopentadienyl)(2-(dimethylamino)-7-n-propyl-9-fluorenyl)zirconium dichloride, Diphenylmethylene(cyclopentadienyl)(2-(diethylamino)-7-n-propyl-9-fluorenyl)zirconium dichloride diphenylmethylene(cyclopentadienyl)(2-(diisopropylamino)-7-n-propyl-9-fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2-(dibenzylamino)-7-n-propyl-9-fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2-(dibenzylamino)-7-n-propyl-9-fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2-(dimethylamino)-7-isopropyl-9-fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2-(di Diphenylmethylene(cyclopentadienyl)(2-(diisopropylamino)-7-isopropyl-9-fluorenyl)zirconium dichloride, Diphenylmethylene(cyclopentadienyl)(2-(dibenzylamino)-7-isopropyl-9-fluorenyl)zirconium dichloride, Diphenylmethylene(cyclopentadienyl)(2-(dimethylamino)-7-n-butyl-9-fluorenyl)zirconium dichloride, Diphenyl Examples include zirconium compounds such as methylene(cyclopentadienyl)(2-(diisopropylamino)-7-t-butyl-9-fluorenyl)zirconium dichloride and diphenylmethylene(cyclopentadienyl)(2-(dibenzylamino)-7-t-butyl-9-fluorenyl)zirconium dichloride; zirconium compounds in which the dichloro form of these compounds is replaced with a dimethyl form, a diethyl form, a dihydro form, a diphenyl form, or a dibenzyl form; and hafnium compounds in which the zirconium in these compounds is replaced with hafnium.

[0028] 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.

[0029] More specifically, dimethylsilanediylbis(cyclopentadienyl)zirconium dichloride, diethylsilanediylbis(cyclopentadienyl)zirconium dichloride, dicyclohexylsilanediylbis(cyclopentadienyl)zirconium dichloride, diphenylsilanediylbis(cyclopentadienyl)zirconium dichloride, dimethylsilanediylbis(methylcyclopentadienyl)zirconium dichloride, diethylsilanediylbis(methylcyclopentadienyl)zirconium dichloride, dicyclohexylsilanediylbis(cyclopentadienyl)zirconium dichloride, Silsilanediylbis(methylcyclopentadienyl)zirconium dichloride, diphenylsilanediylbis(methylcyclopentadienyl)zirconium dichloride, dimethylsilanediylbis(2,4-dimethylcyclopentadienyl)zirconium dichloride, diethylsilanediylbis(2,4-dimethylcyclopentadienyl)zirconium dichloride, dicyclohexylsilanediylbis(2,4-dimethylcyclopentadienyl)zirconium dichloride, diphenylsilanediylbis(2,4-dimethylcyclopentadienyl) Dimethylsilanediyl[(cyclopentadienyl)(indenyl)]zirconium dichloride, Dimethylsilanediyl[(cyclopentadienyl)(indenyl)]zirconium dichloride, Diethylsilanediyl[(cyclopentadienyl)(indenyl)]zirconium dichloride, Dicyclohexylsilanediyl[(cyclopentadienyl)(indenyl)]zirconium dichloride, Diphenylsilanediyl[(cyclopentadienyl)(indenyl)]zirconium dichloride, Dimethylsilanediyl[(cyclopentadienyl)(4,7-dimethylindenyl)]zirconium dichloride silanediyl[(cyclopentadienyl)(4,7-dimethylindenyl)]zirconium dichloride, dicyclohexylsilanediyl[(cyclopentadienyl)(4,7-dimethylindenyl)]zirconium dichloride, diphenylsilanediyl[(cyclopentadienyl)(4,7-dimethylindenyl)]zirconium dichloride, dimethylsilanediyl[(cyclopentadienyl)(2,4,7-trimethylindenyl)]zirconium dichloride, diethylsilanediyl[(cyclopentadienyl)(2,4,7-trimethylindenyl)]zirconium dichloride, dicyclohexylsilanediyl[(cyclopentadienyl)(2,4,7-trimethylindenyl)]zirconium dichloride, diphenylsilanediyl[(cyclopentadienyl)(2,4,7-trimethylindenyl)]zirconium dichloride, bis(indenyl)zirconium dichloride, isopropylidenebis(indenyl)zirconium dichloride, (methyl)(phenyl)methylenebis(indenyl)zirconium dichloride, di Phenylmethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, isopropylidenebis(2-methylindenyl)zirconium dichloride, (methyl)(phenyl)methylenebis(2-methylindenyl)zirconium dichloride, diphenylmethylenebis(2-methylindenyl)zirconium dichloride, ethylenebis(2-methylindenyl)zirconium dichloride, isopropylidenebis(tetrahydroindenyl)zirconium dichloride Iodide, (methyl)(phenyl)methylenebis(tetrahydroindenyl)zirconium dichloride, diphenylmethylenebis(tetrahydroindenyl)zirconium dichloride, ethylenebis(tetrahydroindenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, (methyl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl) Zirconium dichloride, ethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride, (methyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride, ethylene(cyclopentadienyl)(2,Examples include zirconium compounds such as 7-di-t-butyl-fluorenyl)zirconium dichloride; zirconium compounds in which the dichloro form of these compounds is replaced with a dimethyl form, a diethyl form, a dihydro form, a diphenyl form, or a dibenzyl form, and hafnium compounds in which the zirconium in these compounds is replaced with hafnium.

[0030] Examples of the organically modified clay (B) modified with an aliphatic salt include N,N-dimethyl-behenylamine hydrochloride, N-methyl-N-ethyl-behenylamine hydrochloride, N-methyl-Nn-propyl-behenylamine hydrochloride, N,N-dioleyl-methylamine hydrochloride, N,N-dimethyl-behenylamine hydrofluoride, N-methyl-N-ethyl-behenylamine hydrofluoride, N-methyl-Nn-propyl-behenylamine hydrofluoride, N,N-dioleyl-methylamine hydrofluoride, N,N-dimethyl-behenylamine N-methyl-N-ethyl-behenylamine hydrobromide, N-methyl-Nn-propyl-behenylamine hydrobromide, N,N-dioleyl-methylamine hydrobromide, N,N-dimethyl-behenylamine hydroiodide, N-methyl-N-ethyl-behenylamine hydroiodide, N-methyl-Nn-propyl-behenylamine hydroiodide, N,N-dioleyl-methylamine hydroiodide, N,N-dimethyl-behenylamine sulfate, N-methyl-N-ethyl-behenylamine sulfate aliphatic amine salts such as N-methyl-Nn-propyl-behenylamine sulfate, N,N-dioleyl-methylamine sulfate; P,P-dimethyl-behenylphosphine hydrochloride, P,P-diethyl-behenylphosphine hydrochloride, P,P-dipropyl-behenylphosphine hydrochloride, P,P-dimethyl-behenylphosphine hydrofluoride, P,P-diethyl-behenylphosphine hydrofluoride, P,P-dipropyl-behenylphosphine hydrofluoride, P,P-dimethyl-behenylphosphine hydrobromide, P,P- Examples of clays modified with aliphatic salts include aliphatic phosphonium salts such as diethyl-behenylphosphine hydrobromide, P,P-dipropyl-behenylphosphine hydrobromide, P,P-dimethyl-behenylphosphine hydroiodide, P,P-diethyl-behenylphosphine hydroiodide, P,P-dipropyl-behenylphosphine hydroiodide, P,P-dimethyl-behenylphosphine sulfate, P,P-diethyl-behenylphosphine sulfate, and P,P-dipropyl-behenylphosphine sulfate.

[0031] The clay compound constituting the organically modified clay (B) may be any compound as long as it belongs to the category of clay compounds. In general, the organically modified clay (B) is formed by stacking many layers called silicate layers, which are composed of a tetrahedral sheet of silica tetrahedra connected in two dimensions and an octahedral sheet of alumina octahedrons or magnesia octahedrons connected in two dimensions in a 1:1 or 2:1 ratio. The Si in some of the silica tetrahedra is replaced by Al, the Al in the alumina octahedron by Mg, and the Mg in the magnesia octahedron by Li, etc., resulting in a lack of positive charge within the layer, and the layer as a whole is negatively charged. To compensate for this negative charge, Na is introduced between the layers. + Ya Ca 2+ The clay compounds are known to contain cations such as kaolinite, talc, smectite, vermiculite, mica, brittle mica, and mercury, both natural and synthetic, and these can be used, with smectite being preferred because of its ease of availability and ease of organic modification, and hectorite or montmorillonite being even more preferred among smectites.

[0032] 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. When preparing the organically modified clay (B), it is preferable to select conditions for a clay compound concentration of 0.1 to 30% by weight and a treatment temperature of 0 to 150°C. The aliphatic salt may be prepared as a solid and dissolved in a solvent for use, or a solution of the aliphatic salt may be prepared by chemical reaction in a solvent and used as is. Regarding the reaction ratio of the clay compound to the aliphatic salt, it is preferable to use an equivalent or greater amount of aliphatic salt relative to the exchangeable cations of the clay compound. Examples of suitable treatment solvents include aliphatic hydrocarbons such as pentane, hexane, and heptane; aromatic hydrocarbons such as benzene and toluene; alcohols such as ethyl alcohol and methyl alcohol; ethers such as ethyl ether and n-butyl ether; halogenated hydrocarbons such as methylene chloride and chloroform; acetone; 1,4-dioxane; tetrahydrofuran; and water. Preferably, alcohols or water are used alone or as one of the solvent components.

[0033] Furthermore, there is no limitation on the particle size of the organo-modified clay (B) constituting the catalyst for polyethylene production, but a particle size of 1 to 100 μm is preferred because this results in excellent efficiency during catalyst preparation and polyethylene production. The method for adjusting the particle size is also not limited; large particles may be pulverized to an appropriate particle size, small particles may be granulated to an appropriate particle size, or pulverization and granulation may be combined. Furthermore, particle size adjustment may be performed on the clay before organo-modification or on the organo-modified clay after modification.

[0034] 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.

[0035] 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 organically 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 may be used in any proportions as long as they are usable as a catalyst for polyethylene production. In particular, in order to obtain a catalyst for polyethylene production that is capable of efficiently producing a modifier for polyethylene resins, the molar ratio per metal atom of component (A) to component (C) is preferably component (A):component (C) = 100:1 to 1:100,000, and particularly preferably 1:1 to 1:10,000. The weight ratio of component (A) to component (B) is preferably component (A):component (B)=10:1 to 1:10000, and more preferably 3:1 to 1:1000.

[0036] The catalyst for polyethylene production may be prepared by any method that allows for the preparation of a catalyst for polyethylene production containing the component (A), the component (B), and the component (C). For example, components (A), (B), and (C) may be mixed in a solvent that is inert to them, or using the monomer to be polymerized as the solvent. There are no limitations on the order in which these components are reacted, nor on the temperature or time at which this treatment is carried out. It is also possible to prepare a catalyst for polyethylene production using two or more types of each of the component (A), component (B), and component (C).

[0037] The polymerization conditions, such as polymerization temperature, polymerization time, and polymerization pressure, used in producing the polyethylene polymer 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 normal 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.

[0038] Among these, two-stage polymerization is preferred because different polymerization conditions for component (A) and component (B) enable efficient production of the ethylene polymer of the present invention having different molecular weight distributions for component (A) and component (B). Two-stage batch polymerization is particularly preferred because it allows easier control of the polymerization conditions. In this case, polymerization termination mechanisms in polymerization, particularly coordination polymerization, include a β-hydrogen elimination reaction in which hydrogen bonded to the carbon at the β-position from the growing end is eliminated to produce an alkene and a metal hydride, and a chain transfer reaction to the monomer, hydrogen, and organoaluminum compound in the polymerization system. Lower monomer pressure conditions enable lower molecular weight and broader molecular weight distribution, so it is preferred to relatively lower the monomer pressure during polymerization of component (B). For example, by setting the ethylene pressure during polymerization of component (B) to 0.35 MPa or less, particularly 0.25 MPa or less, component (B) having Mw = 10,000 to 500,000 and Mw / Mn exceeding 5.0, preferably 10.0 or less, can be efficiently produced. The ethylene pressure during polymerization of component (A) can be selected to exceed 0.35 MPa if it is possible to produce component (B) having an Mw of 900,000 to 5,000,000 and an Mw / Mn of 2.0 to 5.0, and to polymerize an ethylene polymer more efficiently, it is preferable to set each ethylene pressure to 0.35 MPa or less, or even 0.25 MPa or less. Furthermore, when polymerization is carried out by the co-supported catalyst method, polymerization can be easily carried out by setting the ethylene pressure to 0.35 MPa or less, or even 0.25 MPa or less.

[0039] The form of the resin modifier of the present invention is not limited, and for example, the polymer obtained by the above production method may be used as is, or may be formed into pellets using an extruder, etc. Furthermore, additives such as antioxidants may be added to the resin modifier.

[0040] The resin modifier of the present invention exhibits excellent dispersibility of both component (A), an ultra-high molecular weight polyethylene component with excellent mechanical properties, and component (B), a polyethylene component with excellent processability. Therefore, it exhibits excellent modifying effects as a modifier for various resins, such as olefin resins such as ethylene-based resins and propylene-based resins, vinyl chloride resins, styrene-based resins, ester-based resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and LCP, amide-based 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 ethylene-based resins used in this study have a density of 920 g / cm or more. 3 High density polyethylene is preferred to satisfy the above requirements, and an example of such polyethylene is Nipolon Hard (trade name, manufactured by Tosoh Corporation).

[0041] The amount of resin modifier of the present invention to be blended is arbitrary as long as the modifying effect is exhibited. In particular, since this results in an excellent balance between mechanical properties and processability, it is preferable for the resin composition to contain 1 to 100 parts by weight of the modifier, and particularly 5 to 50 parts by weight, per 100 parts by weight of resin.

[0042] The resin composition containing the resin modifier 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]

[0043] By providing a resin modifier that has high mechanical strength and excellent kneadability, and therefore is excellent in durability and moldability, it is possible to reduce the thickness of molded products and extend the product life by improving the mechanical strength of the molded products using conventional molding methods. [Example]

[0044] 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.

[0045] Unless otherwise specified, the reagents used were commercially available products or those synthesized according to known methods.

[0046] 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.

[0047] The production of the catalyst for polyethylene production, the preparation of the 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.

[0048] Furthermore, the physical properties of the polyethylene were measured by the following methods.

[0049] ~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%.

[0050] ~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.

[0051] ~MFR~ The melt flow rate was measured at a temperature of 190°C under a load of 2.16 kg in accordance with JIS6922-2:1997.

[0052] ~HLMFR~ The melt flow rate was measured at a temperature of 190°C under a load of 21.6 kg in accordance with JIS6922-2:1997.

[0053] ~Measurement of thermal melting~ Using a differential scanning calorimeter (DSC) (DSC6220, manufactured by SII NanoTechnology, Inc.), the sample was heated from 0°C to 230°C at a heating rate of 10°C / min (first scan), and the crystalline melting peak (Tm1) and heat of fusion (ΔH1) were measured. After allowing the sample to stand for 5 minutes, it was cooled to -20°C at a heating rate of 10°C / min, and then allowed to stand for 5 minutes. The sample was then heated again from -20°C to 230°C at a heating rate of 10°C / min (second scan), and the crystalline melting peak (Tm2) and heat of fusion (ΔH2) were measured. The polyethylene sample weight was 6 mg.

[0054] ~Tensile properties~ Using (trade name) RTG-1210 (manufactured by Orientec Co., Ltd.), the tensile stress at break, yield stress, and nominal strain at break of a dumbbell specimen (ATMS-1822) were measured at 25°C and 50 mm / min. ~Charpy impact strength~ Using a universal impact testing machine (Toyo Seiki Seisakusho, ISO-PE-Z43), the impact strength of 80 mm x 10 mm x 4.0 mm strip-shaped 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] ~Flexural modulus~ Using an AG-2000B (product name, manufactured by Shimadzu Corporation), test pieces were cut into strips with a width of 10 mm and a length of 80 mm, and a bending test was carried out at 23°C at a bending speed of 2 mm / min in accordance with JIS6922-2 to measure the flexural modulus.

[0056] ~Mixability evaluation~ The kneadability was evaluated by the number of particles with a diameter of 0.05 mm or more observed on the surface per 10.0 cm of a strand obtained by HLMFR measurement.

[0057] Manufacturing Example 1 (1) Manufacturing 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.

[0058] (2) Production of suspensions of catalysts for polyethylene production A 5L flask equipped with a thermometer and reflux condenser was purged with nitrogen, and then 450g of the organically modified clay obtained in (1) and 1000ml of hexane were added, followed by 11.30g of diphenylmethylene(cyclopentadienyl)(2-dimethylamino-9-fluorenyl)dichloride and 1280ml of a 20wt% 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 3735ml of hexane, and then 3735ml of hexane was added to obtain a suspension of a catalyst for polyethylene production (solids content: 12.5wt%).

[0059] Manufacturing Example 2 (1) Manufacturing of organically modified clay The same procedure as in Production Example 1 was carried out.

[0060] (2) Production of suspensions of catalysts for polyethylene production After replacing the air in a 5L flask equipped with a thermometer and reflux condenser with nitrogen, 450g of the organically modified clay obtained in (1) and 1000ml of hexane were added, followed by 12.87g of diphenylmethylene(cyclopentadienyl)(2-diethylamino-9-fluorenyl)hafnium dichloride and 1280ml of a 20wt% 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 3735ml of hexane, and then 3735ml of hexane was added to obtain a suspension of a catalyst for polyethylene production (solids content: 12.5wt%).

[0061] Manufacturing Example 3 (1) Manufacturing 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 63.7 g (120 mmol) of dioleylmethylamine ((C18H35)2(CH3)N, manufactured by Lion Specialty Chemicals Co., Ltd., product name Lipomin MO) were added, heated to 45°C, and 100 g of synthetic hectorite (Laponite RD, manufactured by BYK) was dispersed in the flask. 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 water at 60°C, and dried in a dryer at 85°C for 12 hours to obtain 130 g of organically modified clay. This organically modified clay was then jet-milled to a median diameter of 15 μm.

[0062] (2) Production of suspensions of 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 the addition of 0.392 g (1 mmol) of bis(indenyl)zirconium dichloride and 142 ml of 20% triisobutylaluminum, and stirring for 3 hours at 60°C. After cooling to room temperature, the supernatant was removed and washed twice with 220 ml of hexane, and then 220 ml of hexane was added to obtain a catalyst suspension (solid weight content: 12.0 wt%).

[0063] Production Example 4 A 2-liter autoclave was charged with 1.2 liters of hexane, 1.1 ml of 20% triisobutylaluminum, and 200 mg (equivalent to 24 mg of solids) of the catalyst suspension obtained in Production Example 3, and the temperature was raised to 85°C. After that, an ethylene / hydrogen mixed gas equivalent to a pressure of 0.90 MPa was continuously fed (hydrogen concentration in the ethylene / hydrogen mixed gas: 450 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain a monomodal polyethylene polymer (H-5). The obtained polyethylene polymer (H-5) had a Mw of 111,000 and a density of 950 kg / m 3 It was.

[0064] Example 1 As shown below, a bimodal polyethylene, polyethylene polymer (III-1), was prepared by two-stage polymerization in which component (III-1) was polymerized in succession after component (III-1), and a resin modifier was obtained. The resin modifier polyethylene polymer (III-1) had an HLMFR of 2.4 g / 10 min and an [η] of 4.6.

[0065] Preparation of component (A-1) 1m 3 A reactor was charged with 600 L of hexane, 1.8 kg of a 20 wt % triisobutylaluminum hexane solution, and 1.62 kg (equivalent to 196 g of solids) of the suspension of the polyethylene production catalyst obtained in Production Example 1. The temperature was then raised to 60°C. Ethylene was continuously supplied to maintain the ethylene pressure at 0.20 MPa, and hydrogen was intermittently added to maintain the hydrogen concentration in the gas phase of the reactor at 390 ppm, thereby conducting slurry polymerization. During the polymerization, 15 kg of ethylene was consumed in terms of polyethylene, and the polymerization time was 46 minutes. The [η] of component (A-1), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 10.1.

[0066] Preparation of component (B-1) and polyethylene polymer (B-1) After polymerizing component (A-1), ethylene was continuously supplied to maintain the ethylene pressure at 0.20 MPa at 60°C. Hydrogen was intermittently added to maintain the hydrogen concentration in the gas phase of the reactor at 31,600 ppm. Slurry polymerization was then performed to polymerize component (B-1), producing polyethylene polymer (H-1), an ethylene homopolymer used as a resin modifier. 61 kg of ethylene was consumed in polyethylene equivalents, and the polymerization time was 230 minutes. The [η] of component (B-1), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 2.0.

[0067] Using peak separation software, the peaks of polyethylene polymer (Ha-1) were separated according to a Gaussian distribution, and the calculated Mw of component (A-1) was 1 million, with an Mw / Mn of 3.5. Similarly, the Mw of component (B-1) was calculated to be 100,000, with an Mw / Mn of 6.1. Furthermore, component (A-1) / component (B-1) = 20 / 80 (wt%). DSC measurement showed a single peak at Tm1 = 136.6°C. The measurement results for polyethylene polymer (Ha-1), a resin modifier, are shown in Table 1.

[0068] The obtained polyethylene polymer (H-1) was melt-kneaded using a twin-screw extruder (manufactured by Toyo Seiki Seisakusho, (trade name) Labo Plastomill parallel twin-screw extruder 2D25S) at 160 ° C, 30 rpm, and a discharge rate of 0.8 kg / h to obtain resin modifier pellets. At this time, the stick-slip phenomenon did not occur.

[0069] 10 g of the resulting resin modifier pellets, 30 g of the polyethylene polymer (H-5) obtained in Production Example 4, and 0.04 g of an antioxidant (product name Irganox 1010, manufactured by BASF) were placed in a 70 ml batch mixer (manufactured by Toyo Seiki Seisakusho, Ltd., product name Labo Plastomill 4C150) and mixed at a mixing temperature of 190°C and a rotation speed of 30 rpm for 5 minutes to obtain a resin composition. The evaluation results of the obtained resin composition are shown in Table 2.

[0070] Example 2 As shown below, a bimodal polyethylene polyethylene polymer (H-2) was prepared as a resin modifier by two-stage polymerization, in which component (A-2) was polymerized followed by component (B-2). The resin modifier polyethylene polymer (H-2) had an HLMFR of 1.50 g / 10 min and an [η] of 7.3.

[0071] Preparation of component (A-2) 1m 3A reactor was charged with 600 L of hexane, 1.8 kg of a hexane solution of 20 wt % triisobutylaluminum, and 1.87 kg (equivalent to 230 g of solids) of the suspension of the polyethylene production catalyst obtained in Production Example 2. The temperature was then raised to 60°C. Ethylene was continuously supplied to maintain the ethylene pressure at 0.25 MPa, and hydrogen was intermittently added to maintain the hydrogen concentration in the gas phase of the reactor at 420 ppm, thereby conducting slurry polymerization. During the polymerization, 13 kg of ethylene was consumed in terms of polyethylene, and the polymerization time was 38 minutes. The [η] of component (A-2), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 21.0.

[0072] Preparation of component (Ro-2) and polyethylene polymer (Ha-2) After polymerizing component (A-2), ethylene was continuously supplied to maintain the ethylene pressure at 0.25 MPa at 60°C. Hydrogen was intermittently added to maintain the hydrogen concentration in the gas phase of the reactor at 66,700 ppm. Slurry polymerization was then performed to polymerize component (B-2), producing polyethylene polymer (C-2), an ethylene homopolymer used as a resin modifier. 47 kg of ethylene was consumed in polyethylene equivalents, and the polymerization time was 290 minutes. The [η] of component (B-2), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 2.0.

[0073] Using peak separation software, the peaks of polyethylene polymer (Ha-2) were separated according to a Gaussian distribution, and the calculated Mw of component (A-2) was 3 million, with an Mw / Mn of 3.3. Similarly, the Mw of component (B-2) was calculated to be 100,000, with an Mw / Mn of 6.1. Similarly, the component ratio (A-2) / component (B-2) was calculated to be 20 / 80 (wt%). DSC measurement showed a single peak at Tm1 = 137.1°C. The measurement results for polyethylene polymer (Ha-2), a resin modifier, are shown in Table 1.

[0074] Resin modifier pellets and a resin composition were obtained in the same manner as in Example 1, except that polyethylene polymer (H-2), a resin modifier, was used instead of polyethylene polymer (H-1). No stick-slip phenomenon occurred when obtaining the resin modifier pellets. The evaluation results of the obtained resin composition are shown in Table 2.

[0075] Comparative Example 1 A bimodal polyethylene, polyethylene polymer (III-3), was prepared by two-stage polymerization in which component (III-3) was polymerized followed by component (III-3) as follows: The polyethylene polymer (III-3) had an HLMFR of 2.74 g / 10 min and an [η] of 3.2.

[0076] Preparation of component (A-3) A 10-liter autoclave was charged with 6 liters of hexane, 5.5 ml of a 20 wt % triisobutylaluminum hexane solution, and 2.50 g (equivalent to 310 mg of solids) of the suspension of the polyethylene production catalyst obtained in Production Example 1. The temperature was then raised to 60°C. Ethylene was continuously supplied to maintain the ethylene pressure at 0.87 MPa, and hydrogen was intermittently added to maintain a hydrogen concentration of 1000 ppm in the gas phase of the autoclave. Slurry polymerization was carried out. During the polymerization, 200 g of ethylene was consumed in polyethylene equivalent terms, and the polymerization time was 1 hour. The [η] of component (A-3), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 10.1.

[0077] Preparation of component (B-3) and polyethylene polymer (B-3) After polymerization of component (A-3), ethylene was continuously supplied to maintain the ethylene pressure at 0.87 MPa at 60°C. Hydrogen was intermittently added to maintain the hydrogen concentration in the gas phase of the autoclave at 30,000 ppm. Slurry polymerization was then performed to polymerize component (B-3), producing polyethylene polymer (C-3), an ethylene homopolymer. Eight hundred grams of ethylene, calculated as polyethylene, was consumed, and the polymerization time was 4.5 hours. The [η] of component (B-3), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 2.0.

[0078] Using peak separation software, the peaks of polyethylene polymer (III-3) were separated according to a Gaussian distribution, and the calculated Mw of component (III-3) was 1 million, with an Mw / Mn of 3.2. Similarly, the Mw of component (III-3) was calculated to be 100,000, with an Mw / Mn of 4.1. Furthermore, component (III-3) / component (III-3) ratio was 20 / 80 (wt%), and DSC measurement showed a single peak at Tm1 = 138.5°C. The measurement results are shown in Table 1.

[0079] An attempt was made to prepare pellets of polyethylene polymer (III-3) and a resin composition in the same manner as in Example 1, except that polyethylene polymer (III-3) was used instead of polyethylene polymer (III-1). During pelletization, a stick-slip phenomenon occurred, making discharge unstable and continuous production difficult. The evaluation results of a resin composition using some of the pellets that could be produced stably are shown in Table 2.

[0080] Comparative Example 2 A bimodal polyethylene, polyethylene polymer (III-4), was prepared by two-stage polymerization in which component (III-4) was polymerized in succession after component (III-4) was polymerized as follows: The polyethylene polymer (III-4) had an HLMFR of 0.01 g / 10 min, but was meltable, and its [η] was 16.9.

[0081] Preparation of component (A-4) 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) of the suspension of the catalyst for polyethylene production obtained in Production Example 1, and the temperature was raised to 60°C. Ethylene was continuously supplied so that the ethylene pressure could be maintained at 0.80 MPa, and hydrogen was added intermittently so that the hydrogen concentration in the gas phase of the autoclave became 300 ppm, thereby carrying out slurry polymerization. 200 g of ethylene, calculated as polyethylene, was consumed in the reaction, and the [η] of component (A-4) calculated from the relationship with the hydrogen concentration in the system during the polymerization reaction was 22.

[0082] Preparation of component (B-4) and polyethylene polymer (B-4) After polymerization of component (A-4), ethylene was continuously supplied to maintain the ethylene pressure at 0.80 MPa at 60°C, and hydrogen was intermittently added to maintain the hydrogen concentration in the gas phase of the autoclave at 30,000 ppm, followed by slurry polymerization to polymerize component (B-4), producing polyethylene polymer (C-4), an ethylene homopolymer. Ethylene was consumed in an amount of 800 g, calculated as polyethylene, and the [η] of component (B-4), calculated in relation to the hydrogen concentration in the system during the polymerization reaction, was 2.

[0083] Using peak separation software, the peaks of polyethylene polymer (III-4) were separated according to a Gaussian distribution, and the calculated Mw of component (III-4) was 3 million, with an Mw / Mn ratio of 2.8. Similarly, the Mw of component (III-4) was calculated to be 100,000, with an Mw / Mn ratio of 4.5. Furthermore, component (III-4) / component (III-4) ratio was 30 / 70 (wt%), and DSC measurement showed a single peak at Tm1 = 138.9°C. The measurement results are shown in Table 1.

[0084] An attempt was made to prepare pellets of polyethylene polymer (Ha-4) and a resin composition in the same manner as in Example 1, except that polyethylene polymer (Ha-4) was used instead of polyethylene polymer (Ha-1). During pelletization, a stick-slip phenomenon occurred, making discharge unstable and continuous production difficult. The evaluation results of a resin composition using some of the pellets that could be produced stably are shown in Table 2.

[0085] Comparative Example 3 The polyethylene polymer (H-5) prepared in Production Example 4 was melt-kneaded using a twin-screw extruder (manufactured by Toyo Seiki Seisakusho, Ltd., (trade name) Labo Plastomill parallel twin-screw extruder 2D25S) at 160°C, 30 rpm, and a discharge rate of 0.8 kg / h to obtain polyethylene pellets. The evaluation results of the obtained polyethylene pellets are shown in Table 2.

[0086] [Table 1]

[0087] [Table 2] [Industrial Applicability]

[0088] The resin modifier of the present invention provides a resin composition that has high mechanical strength and excellent kneadability, and therefore is excellent in durability and moldability. This makes it possible to reduce the thickness of molded articles and extend the product life by improving the mechanical strength of the molded articles using conventional molding methods.

Claims

1. A resin modifier characterized by being a polyethylene polymer that satisfies the following properties (1) and (2): (1): The melt flow rate (HLMFR) conforming to JIS K 6922-2:1997 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 (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 (i), the following (2-1) to (2-3) are satisfied: y=a×(1 / (2π(σ ２ )) （１／２） ) exp(-((x-μ) ２ ) / (2(s ２ ))) formula (i) (Here, a is the peak intensity, σ is the standard deviation, x is the variable, and μ is x at the peak top.) (2-1): The weight average molecular weight, calculated as linear polyethylene, based on 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): A linear polyethylene-equivalent weight-average molecular weight of 10,000 to 500,000, based on a peak on the low molecular weight side, and a molecular weight distribution of more than 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 greater than 5 / 95 and smaller than 80 / 20.

2. The resin modifier according to claim 1, characterized in that the ethylene polymer has a weight average molecular weight of 10,000 to 500,000 in terms of linear polyethylene due to the low molecular weight peak, and a molecular weight distribution of more than 5.0 and 10.0 or less.

3. The resin modifier according to claim 1 or 2, which is a polyethylene polymer that also satisfies the following (3), (4-1) and / or (4-2): (3) The molecular weight distribution, calculated as linear polyethylene, measured by GPC is 4.0 or more and less than 50. (4-1): The crystal melting peak (Tm1) in the first scan measured using a differential scanning calorimeter (DSC) by raising the temperature from 0°C to 230°C at a heating rate of 10°C / min is single-peaked. (4-2): After the first scan, the sample is left for 5 minutes, cooled to −20° C. at a rate of 10° C. / min, left for 5 minutes, and then heated again from −20° C. to 230° C. at a rate of 10° C. / min (second scan). The melting point (Tm2) in the second scan is measured, and the difference between Tm1 and Tm2 (ΔTm=Tm1−Tm2) is −1° C. or more and less than 15° C., and the ratio (ΔH2 / ΔH1) of the heat of fusion in the first scan (ΔH1) to the heat of fusion in the second scan (ΔH2) is 0.94 or more.

4. 3. The resin modifier according to claim 1, wherein the polyethylene polymer is an ethylene homopolymer.

5. A resin composition comprising 1 to 100 parts by weight of the resin modifier according to claim 1 or 2 relative to 100 parts by weight of resin.

6. 6. The resin composition according to claim 5, wherein the resin is an ethylene-based resin.

7. 6. The resin composition according to claim 5, wherein the resin is high-density polyethylene.

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