TWI648328B - Polyethylene resin composition - Google Patents

Abstract

The present invention provides a resin composition containing a high-density polyethylene for producing a film having excellent tearing properties, sealing properties, and coating properties. The invention is a polyethylene resin composition with a density of 930 to 960 kg / m ³ , a melt flow rate of 1 to 20 g / 10 minutes at 190 ° C. and 2.16 kg, and a CFC device at the bottom When performing TREF (elevated temperature dissolution classification) measurement under the above conditions, one or more peaks of the dissolution temperature-dissolution amount curve appear below 80 ° C, and one or more peaks appear above 90 ° C, which becomes the peak of the maximum amount of dissolution ( Wmax) appears at 90 ° C or higher, and the maximum value is 10% by weight or more of the total dissolution amount. (1) Weigh 20 mg of the above polyethylene resin composition and inject 0.5 ml of o-dichlorobenzene; (2) Hold at 140 ° C for 120 minutes to completely dissolve the above polyethylene resin composition, and introduce the solution into a TREF column; (3) Reduce the temperature from 140 ° C to 40 ° C at 0.5 ° C / min, and precipitate at the column for 20 minutes at 40 ° C; (4) Increase the temperature from 40 ° C to 140 ° C at 1 ° C each time at each temperature After the temperature was maintained for 15 minutes or more, TREF measurement was performed to measure the amount of dissolution.

Description

Polyethylene resin composition

The present invention relates to a polyethylene resin composition.

Generally, polyethylene is used as a raw material for many films and sheets such as food packaging films, pharmaceutical packaging films, and agricultural sheets. Among them, the vast majority of polyethylene is used for individual packaging of canned food packaging materials, food packaging, and snacks. Polyethylene is roughly classified into two types according to the manufacturing method. The first type is polyethylene that is synthesized at a relatively low pressure through a catalyst, and can be divided into three types: high density polyethylene, medium density polyethylene, and linear low density polyethylene. The second type is a high-pressure low-density polyethylene synthesized at a relatively high pressure using a radical initiator. Examples of catalysts used in polyethylene synthesis include Ziegler catalysts and metallocene catalysts. Polyethylene synthesized by a metallocene catalyst exhibits a narrow molecular weight distribution and a narrow composition distribution, and is used in many fields. For example, Patent Document 1 below describes an invention using a high-density polyethylene having a metallocene catalyst as a main raw material, but it is not sufficient in terms of tearability, and it does not mention hand tearability. Further, in terms of improvement in tearability, a document in which a stretched film of a vinyl resin is found (for example, refer to Patent Document 2) has been found. However, it is necessary to extend the equipment, and it is not welcome in terms of equipment cost. Further, a technique for applying a material such as an antistatic agent in order to impart a function to a polyethylene film is known, but unevenness and shrinkage of the material are caused during the application, and the problem of how to apply uniformly remains (for example, refer to Patent Document 3). Further, for example, a multilayer laminate film often used in food packaging and the like described in Patent Document 4 requires sealing strength as the application is expanded, and improvement is urgently desired. [Prior Art Document] [Patent Document 1] Japanese Patent No. 5713438 [Patent Document 2] Japanese Patent Publication No. 61-41732 [Patent Document 3] Japanese Patent Laid-Open Publication No. 1-313532 [Patent Document 4] Japan Patent Publication No. 2015-128894

[Problems to be Solved by the Invention] In view of the above-mentioned situation, the present invention aims to provide a polyethylene resin composition for producing a film having no elongation and excellent tearing, hand tearing, sealing, and coating properties. . [Technical means to solve the problem] The present inventors made intensive studies in order to solve the above-mentioned problems, and as a result, found that a resin composition containing a high-density polyethylene that satisfies specific physical properties can solve the above-mentioned problems, and completed the present invention. That is, the present invention is as follows. [1] A polyethylene resin composition having a density of 930 to 960 kg / m ³ and a melt flow rate of 1 to 20 g / 10 minutes at 190 ° C and 2.16 kg, and using CFC (Cross fractionation When performing TREF (elevated temperature dissolution fractionation) measurement under the following conditions, one or more peaks of the dissolution temperature-dissolution curve appear at 80 ° C or more, and one or more at 90 ° C or more. The peak (Wmax) that becomes the maximum of the dissolution amount appears above 90 ° C, and the maximum value is more than 10% by weight of the total dissolution amount; (1) Weigh 20 mg of the above polyethylene resin composition and inject o-dichlorobenzene 0.5 ml; (2) Hold at 140 ° C for 120 minutes to completely dissolve the above polyethylene resin composition, and introduce the solution into a TREF column; (3) Reduce the temperature from 140 ° C to 40 ° C at 0.5 ° C / minute, and place in the column After the middle precipitation, the temperature was maintained at 40 ° C for 20 minutes. (4) The temperature was increased from 40 ° C to 140 ° C at 1 ° C each time, and the temperature was maintained at each temperature for 15 minutes or more. Then, TREF measurement was performed to measure the amount of dissolution. [2] The polyethylene resin composition according to claim 1, wherein the ratio Wmax / W1 of the maximum dissolution amount (Wmax) to the maximum dissolution amount (W1) at a dissolution temperature of 60 to 80 ° C measured by TREF is 2.0 or more . [3] The polyethylene resin composition according to [1] or [2], which contains 30 to 80% by mass of the high-density polyethylene resin (A) and 20 to 70% by mass of the high-density low-density polyethylene resin (B). . [4] The polyethylene resin composition according to any one of [1] to [3], wherein in a DSC (differential scanning calorimeter) measurement, it is melted at 180 ° C. for 5 minutes, and is cooled at a temperature of 80 The measurement is performed at a temperature of 1 ° C / min, and the temperature is 1 ° C higher than the extrapolated crystallization start temperature (Tic). At this time, the 1/2 isothermal crystallization time is 0.7 minutes or more. [5] The polyethylene resin composition according to any one of [1] to [4], wherein the high-density polyethylene resin (A) is an ethylene homopolymer, an ethylene-propylene copolymer, or an ethylene-butene copolymer. [6] The polyethylene resin composition according to any one of [1] to [5], wherein the high-density polyethylene resin (A) is obtained by using a supported metallocene catalyst (C) and a liquid auxiliary catalyst The component (D) is polymerized and produced. The supported metallocene catalyst (C) is composed of (a) a carrier substance, (b) an organoaluminum compound, and (c) a cyclic η-bondable anionic ligand. The transition metal compound (d) can be prepared by reacting with the transition metal compound having a cyclic η-bondable anionic ligand to form an activator that exhibits a complex of catalytic activity. [7] The polyethylene resin composition according to any one of claims 1 to 5, wherein the content of chlorine atoms is not more than 2.0 mass ppm relative to the polyethylene resin composition. [Effects of the Invention] According to the present invention, it is possible to provide a tearing and hand-tearing property which is good for a non-stretched film, and also has the coating property of an antistatic agent or the sealing property when forming a multilayer film. Polyethylene resin composition with excellent, clean and low pollution film.

Hereinafter, the form (it is also hereafter called "this embodiment") for implementing this invention is demonstrated in detail. The present invention is not limited to this embodiment, and can be implemented with various changes within the scope of the gist thereof. [Polyethylene resin composition] The density of the polyethylene resin composition in this embodiment is 930 to 960 kg / m³ When the melt flow rate at 190 ° C and 2.16 kg is 1 to 20 g / 10 minutes, and the TFC (temperature rising dissolution classification method) measurement is performed using a CFC device under the following conditions, the dissolution temperature-dissolution amount curve One or more peaks appear below 80 ° C and one or more above 90 ° C. The peak (Wmax) which becomes the maximum of the dissolution amount appears above 90 ° C, and the maximum value is more than 10% by weight of the total dissolution amount. (1) Weigh 20 mg of the above polyethylene resin composition and inject 0.5 ml of o-dichlorobenzene; (2) Hold at 140 ° C for 120 minutes to completely dissolve the above polyethylene resin composition, and introduce the solution into a TREF column; (3) Reduce the temperature from 140 ° C to 40 ° C at 0.5 ° C / min, and precipitate at the column for 20 minutes at 40 ° C; (4) Increase the temperature from 40 ° C to 140 ° C at 1 ° C each time at each temperature After the temperature was maintained for 15 minutes or more, a TREF measurement was performed to measure the eluted amount. The composition of the polyethylene resin composition of this embodiment is shown below, but the present invention is not limited to the following two types of polyethylene. As an example of this embodiment, a manufacturing method using an extruder for the high-density polyethylene resin (A) and the high-pressure method low-density polyethylene resin (B) will be described. The manufacturing method of the polyethylene resin composition according to this embodiment is preferably: high-density polyethylene resin (A) and high-pressure low-density polyethylene resin (B) with high-density polyethylene resin (A) and high-pressure low-density MFR (melt flow rate) ratio (A) / (B) of polyethylene resin (B) is 0.5 or more and 15 or less, and high-density polyethylene resin (A) and high-pressure low-density polyethylene resin (B) The density ratio (A) / (B) is 1.025 or more, and melt-kneading is performed. When the MFR ratio (A) / (B) is less than 0.5, the moldability is deteriorated, and when the MFR ratio (A) / (B) is more than 15, the dispersion becomes poor. When the MFR ratio and the density ratio are in the above ranges, the compatibility with (B) tends to be improved while maintaining the high crystalline component of (A). The polyethylene resin composition of this embodiment can be prepared by kneading the pellets of the high-density polyethylene resin (A) and the high-pressure method low-density polyethylene resin (B) by an extruder. The particles of the high-density polyethylene resin (A) and the high-pressure low-density polyethylene resin (B) are preferably based on the weight of each high-density polyethylene resin (A) and each high-pressure low-density polyethylene resin ( B) The way in which the difference in weight becomes a range of ± 1.0 mg is unified. There is a tendency that the particle diameters of different kinds of particles are uniform, that is, the weight of each is uniform, and it is not easy to classify in the funnel directly above the extruder, and the dispersibility tends to improve. In addition, the weight of each particle is an average value obtained by measuring the weight of 20 particles. The dispersibility of the resins (A) and (B) in the polyethylene resin composition of this embodiment affects the tear strength. That is, if the above-mentioned dispersibility is low and unevenness occurs in the mixed state of the resins (A) and (B), the film obtained from the polyethylene resin composition becomes a film with poor tearability. In addition, in the film obtained from the polyethylene resin composition having low dispersibility, there are disadvantages in that it is impossible to tear directly in the hand tear test, but to tear in a zigzag shape or diagonally. Therefore, it is desirable that the resins (A) and (B) are completely mixed at a molecular level. The extruder used for kneading the particles of the high-density polyethylene resin (A) and the high-pressure low-density polyethylene resin (B) may be a uniaxial or biaxial extruder, and any extruder may be used. . Regarding the polyethylene resin composition of the present embodiment, when the TREF (temperature rising dissolution classification) measurement was performed using a CFC device under the following conditions, the maximum value (Wmax) of the dissolution amount was 10% by weight or more of the total dissolution amount. When the maximum value of the dissolution amount during TREF measurement is 10% by weight or more, the distribution of the melting point of the polyethylene resin composition is narrow. That is, it means that crystals of relatively uniform size are formed during cooling. The uniform crystal size in the film indicates that the tearing cracks tend to expand when tearing, and show good tearing properties. The maximum value of the dissolution amount is preferably 12% by weight or more, and more preferably 13 to 17.5%. Furthermore, as a temperature which shows the maximum value of the elution amount, it is preferable that it is 90 degreeC or more from a viewpoint of the tearability of a film. The temperature showing the maximum value is preferably 92 to 105 ° C, and more preferably 93 to 100 ° C. In the TREF measurement, the ratio Wmax / W1 of the maximum dissolution amount to the total dissolution amount (W1) at the temperature between 60 and 80 ° C in the Wmax and TREF measurement is the value showing the best value of tearability. index. That is, if Wmax / W1 is less than 2.0, the resin (A) will decrease, the crystals with relatively uniform size will decrease, and the resin (B) with more branches will increase. As a result, the tear strength is increased and the tearability is decreased. Therefore, Wmax / W1 is preferably 2.0 or more, and more preferably 2.3 or more. There is no limit to the upper limit of Wmax / W1. In view of the content of the resin (B) specified in this patent, it is estimated to not exceed 6. The polyethylene resin composition of this embodiment is preferably melted at 180 ° C for 5 minutes in a DSC measurement, and compared with the extrapolated crystallization start temperature (Tic ) The 1/2 isothermal crystallization time when measured at a higher temperature of 1 ° C is 0.7 minutes or more. Furthermore, it is more preferably 0.8 minutes or more. When a film is formed from the polyethylene resin composition, the resin melted in the extruder is extruded from the lip of the T-die, and is instantly cooled by a cooling roller, but the crystallization rate is slower at this time, so that The ratio of crystalline polyethylene in the film is reduced. In particular, the crystallization ratio of the crystalline polyethylene derived from the resin (A) is low. If the crystalline portion of the above-mentioned crystalline polyethylene is relatively hard and the ratio of the crystals is reduced, the amorphous portion having a relatively low strength increases on the contrary. Therefore, tearing is likely to be enlarged due to the amorphous portion, and thus tearability is improved. The chlorine content of the polyethylene resin composition is preferably 2.0 mass ppm or less and more preferably 1.0 mass ppm or less with respect to the polyethylene resin composition. By setting the chlorine content of the polyethylene resin composition to 2.0 mass ppm or less with respect to the polyethylene resin composition, corrosion of a molding machine and the like can be suppressed, and the amount of metal components contained in the polymer can be reduced. Furthermore, when it is used as a surface protective film for a protected material such as a metal which is easily affected by chlorine and hydrochloric acid, there is a tendency that the protected material can be prevented from rusting and the like. Furthermore, by reducing the chlorine content, it is possible to avoid adding a neutralizing agent represented by a fatty acid salt to the polyethylene composition. As a result, it is possible to prevent the neutralizing agent from oozing out of the molded body, and to prevent the build-up of fat and fine particles in the pores during molding, thereby obtaining a low-pollution and clean molded product. The chlorine content of the polyethylene resin composition can be controlled by using the following catalysts and appropriately adjusting the polymerization conditions and the like. The chlorine content of the polyethylene resin composition can be measured by the method described in the examples. [High-density polyethylene (A)] The high-density polyethylene (A) in this embodiment is specifically a polyethylene homopolymer or an ethylene-α-olefin copolymer, and when the polyethylene resin composition is formed into a film From the viewpoint of tearability, an ethylene homopolymer, an ethylene-propylene copolymer, or an ethylene-butene copolymer is preferred. The high-density polyethylene (A) in this embodiment can be produced by the following production method using a supported metallocene catalyst (C) (hereinafter also referred to as a supported geometrically restricted metallocene catalyst). The high-density polyethylene resin (A) in this embodiment is preferably produced by polymerizing a supported metallocene catalyst (C) and a liquid auxiliary catalyst component (D). The supported metallocene The catalyst (C) is composed of (a) an inorganic carrier material, (b) an organoaluminum compound, (c) a transition metal compound having a cyclic η-bonding anionic ligand, and (d) An activator prepared by reacting a transition metal compound of an η-bonding anionic ligand to form a complex that exhibits catalytic activity. The density (JIS K7112) of the high-density polyethylene resin (A) in this embodiment is preferably 940 kg / m from the viewpoint of tearability when the polyethylene resin composition is made into a film.³ Above, more preferably 942 kg / m³ Above, and further preferably 945 kg / m³ the above. The upper limit of the density of the high-density polyethylene resin (A) is not particularly limited, but it is preferably 970 kg / m³ the following. The density of the high-density polyethylene resin (A) can be controlled by the content of the α-olefin in the high-density polyethylene resin. It can be controlled by its manufacturing conditions. The density of the high-density polyethylene resin (A) can be measured by the method described in the examples. The melt flow rate (JIS K7210) of the high-density polyethylene resin (A) of this embodiment at 190 ° C and 2.16 kg is preferably 1 to 70 g / 10 minutes, more preferably 8 to 50 g / 10 minutes, and further It is preferably 12 to 40 g / 10 minutes. By setting the MFR of the high-density polyethylene resin (A) to 1 g / 10 minutes or more, it is possible to prevent the tear strength from being too high and to form a processable melt-viscosity film. In addition, high-density polyethylene having a viscosity of 70 g / 10 minutes or more is difficult to be formed into a film because the viscosity during melting is too low. Specifically, there are the following problems: In the T-die forming, the shrinkage between the T-die and the cooling roll is too large to obtain a wide film, and in the inflation forming, the parison is deformed and cannot stand. The melt flow rate of the high-density polyethylene resin (A) can be adjusted by changing the polymerization temperature or using hydrogen as a chain transfer agent. The melt flow rate of the high-density polyethylene resin (A) can be measured by the method described in the examples. From the viewpoint of processability, the molecular weight distribution Mw / Mn of the high-density polyethylene resin (A) according to this embodiment is preferably 2 to 6, more preferably 2.5 to 5.5, and even more preferably 3 to 5. The molecular weight distribution Mw / Mn of the high-density polyethylene resin (A) can be controlled by its production conditions. The supported geometrically limited metallocene catalyst (C) that can be used in the manufacturing steps of the high-density polyethylene (A) is not particularly limited, and at least (a) an inorganic carrier substance (hereinafter also referred to as "component (a) ) "," (A) "), (b) organoaluminum compounds (hereinafter also referred to as" component (b) "," (b) "), (c) those having a cyclic η-bonding anionic ligand Transition metal compounds (hereinafter also referred to as "components (c)", "(c)") and (d) can react with the transition metal compound having a cyclic η-bondable anionic ligand to form a catalytic activity An activator of the complex (hereinafter also referred to as "component (d)", "(d)") is prepared. (A) The inorganic carrier material is not particularly limited, and examples thereof include SiO₂ (Silicon dioxide), Al₂ O₃ , MgO, TiO₂ Isooxide; MgCl₂ And other halides. The preferred carrier material is SiO₂ . (a) The average particle diameter of the inorganic carrier substance is 1.0 μm or more and 50 μm or less, preferably 2.0 μm or more and 40 μm or less, and more preferably 3.0 μm or more and 30 μm or less. The average particle diameter of the inorganic carrier material is an average particle diameter in volume conversion measured by a measuring method based on a laser light scattering method. Specifically, measurement can be performed using "SALD-2100" manufactured by Shimadzu Corporation. (a) The compressive strength of the inorganic carrier material is 1 MPa or more and 30 MPa or less, preferably 2 MPa or more and 25 MPa or less, and more preferably 3 MPa or more and 20 MPa or less. (a) The compressive strength of the inorganic carrier material is an indicator of the degree of susceptibility to cracking. The lower the value, the more likely it is to crack. Specifically, the compressive strength of the inorganic carrier substance can be measured using a "micro compression tester MCT-510" manufactured by Shimadzu Corporation, etc., and the compressive strength of arbitrarily selected 10 or more particles can be measured, and the average value can be used as the compressive strength. By setting the average particle size and compressive strength of (a) the inorganic carrier material within the above-mentioned range, it is possible to partially break the surface by increasing the number of stirring revolutions during the preparation of the catalyst, thereby supporting the catalyst inside the carrier material. The active site tends to form a highly crystalline polyethylene in the catalyst by supplying the catalyst to polymerization. (a) The inorganic support material is preferably treated with (b) an organoaluminum compound as necessary. The "treatment" herein refers to (b) organoaluminum compound added dropwise while stirring to disperse the inorganic carrier material in an inert solvent, and the mixture is stirred at 0 ° C to 70 ° C for 30 minutes or more, whereby the presence of the inorganic support material is obtained. The active hydrogen on the surface of the substance reacts with the organoaluminum compound. Examples of preferred (b) organoaluminum compounds include alkyl aluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum; diethylaluminum hydride, Alkyl aluminum hydrides such as isobutylaluminum hydride; aluminum alkoxides such as aluminum diethylethanolate and dimethyl aluminum methoxide; aluminum such as methylalumoxane, isobutylalumoxane, and methyl isobutylalumoxane Oxane is not limited to these. Among these, trialkylaluminum and aluminum alkoxide are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are more preferred. The above-mentioned supported geometrically limited metallocene catalyst contains (c) a transition metal compound (hereinafter also simply referred to as a "transition metal compound") having a cyclic η-bondable anionic ligand. The "transition metal compound" is not particularly limited, and may be represented by the following formula (1), for example. L_l MX_p X '_q (1) In formula (1), M represents a transition metal belonging to Group 4 of the periodic table having an oxidation number of η5 bond with one or more ligands L of +2, +3, or +4. In the formula (1), each of L independently represents a cyclic η-bondable anionic ligand. The cyclic η-bonding anionic ligand is, for example, cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl, and these groups may have any one independently selected from Among hydrocarbyl, halogen, halogen-substituted hydrocarbyl, amine hydrocarbyl, hydrocarbyl, dihydrocarbylamino, hydrocarbylphosphino, silyl, aminosilyl, hydrocarbylsilyl, and halosilyl groups of up to 20 non-hydrogen atoms 1 to 8 substituents, and further 2 L may be substituted by hydrocarbon diyl, halohydrocarbadiyl, alkyleneoxy, alkyleneamino, siladiyl containing up to 20 non-hydrogen atoms ), Halosilane diyl, amino silane and other divalent substituents. In formula (1), X each independently represents a monovalent anionic sigma-bond-type ligand having up to 60 non-hydrogen atoms, and a divalent anionic sigma-type coordination with M being divalently bonded. A radical, or a divalent anionic sigma-bond-type ligand that is bonded to M and L with a valence of 1 each. In the formula (1), X 'each independently represents a neutral Lewis base coordination compound selected from the group consisting of a phosphine, an ether, an amine, an olefin, and a conjugated diene having a carbon number of 4 to 40. In Formula (1), l represents an integer of 1 or 2. In the formula (1), p represents an integer of 0, 1, or 2, and X represents a monovalent anionic sigma-bond-type ligand or a divalent bivalent bonded to M and L by a valence of each valence. In the case of an anionic σ-bonding ligand, p represents an integer less than 1 in the number of oxidations of the form of M, and X represents a divalent anionic σ-bonding ligand that is divalently bonded to M. In this case, p represents an integer that is less than +1 or more than the oxidation number of M. In Formula (1), q represents an integer of 0, 1, or 2. In the (c) transition metal compound represented by formula (1), l is preferably 1. (c) A preferable example of the transition metal compound is a compound represented by the following formula (2). [Chemical 1]In formula (2), M represents titanium, zirconium, or hafnium having a formal oxidation number of +2, +3, or +4. Moreover, in formula (2), R¹ Each independently represents hydrogen, a hydrocarbyl group, a silyl group, a germanium group, a cyano group, a halogen group, or a composite group of these, each of which may each have up to 20 non-hydrogen atoms, and adjacent R¹ They can be bonded to each other to form a divalent derivative such as a hydrocarbon diyl group, a silane diyl group, and a germane diyl group to form a ring. In formula (2), X '' each independently represents a halogen, a hydrocarbyl group, a hydrocarbyloxy group, a hydrocarbylamino group, or a silyl group, each of which has at most 20 non-hydrogen atoms, and 2 X '' can form a carbon number of 5 ~ 30 neutral conjugated diene or divalent derivative. In formula (2), Y represents -O-, -S-, -NR³ -Or-PR³ -, Z means -SiR³ ₂ -, -CR³ ₂ -, -SiR³ ₂ -SiR³ ₂ -, -CR³ ₂ -CR³ ₂ -, -CR³ = CR³ -, -CR³ ₂ -SiR³ ₂ -Or-GeR³ ₂ -Here R³ Each independently represents an alkyl group or an allyl group having 1 to 12 carbon atoms. In formula (2), n represents an integer of 1 to 3. (C) The transition metal compound is more preferably a compound represented by the following formula (3) and the following formula (4). [Chemical 2][Chemical 3]In formulas (3) and (4), R¹ Each independently represents hydrogen, a hydrocarbyl group, a silyl group, a germanium group, a cyano group, a halogen group, or a composite group thereof, and each may have up to 20 non-hydrogen atoms. In formulas (3) and (4), M represents titanium, zirconium, or hafnium. In the formulae (3) and (4), Z and Y represent the same groups as those shown in the formula (2). In formulas (3) and (4), X and X 'represent the same groups as those represented by X "in formula (2). In the formulae (3) and (4), p represents 0, 1, or 2, respectively, and q represents 0 or 1, respectively. When p represents 2 and q represents 0, the oxidation number of M is +4 and X represents halogen, hydrocarbyl, hydrocarbyloxy, dihydrocarbamido, dihydrocarbylphosphino, hydrocarbylthio, silane, or a combination thereof And has up to 20 non-hydrogen atoms. In formulas (3) and (4), when p represents 1 and q represents 0, respectively, the oxidation number of M is +3 and X represents a group selected from allyl, 2- (N, N-dimethylamino) Stabilized anionic ligands in methyl) phenyl and 2- (N, N-dimethyl) aminobenzyl; or derivatives of M with an oxidation number of +4 and X representing a divalent conjugated diene Or M together with X to form a metal cyclopentenyl. In formulas (3) and (4), when p represents 0 and q represents 1, respectively, the oxidation number of M is +2 and X 'is a neutral conjugated or non-conjugated diene and can be optionally passed through 1 More than one hydrocarbyl group is substituted, and X ′ may contain up to 40 carbon atoms and form a π-type complex with M. Further preferred examples of the (c) transition metal compound are compounds represented by the following formula (5) and the following formula (6). [Chemical 4][Chemical 5]In formula (5) and formula (6), R¹ Each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms. In addition, M represents titanium, and Y represents -O-, -S-, -NR.³ -, -PR³ -. In formulae (5) and (6), Z represents -SiR³ ₂ -, -CR³ ₂ -, -SiR³ ₂ -SiR³ ₂ -, -CR³ ₂ -CR³ ₂ -, -CR³ = CR³ -, -CR³ ₂ -SiR³ ₂ -Or-GeR³ ₂ -, R³ Each independently represents hydrogen or a hydrocarbyl group, a hydrocarbyl group, a silyl group, a halogenated alkyl group, a halogenated allyl group, or a composite group of these, and these may have up to 20 non-hydrogen atoms, and, if necessary, two of Z R³ R or Z in each other³ With R in Y³ Can be bonded to each other to form a ring. In the formula (5) and the formula (6), X and X 'represent the same groups as those shown in the formula (3) or the formula (4). In formulae (5) and (6), p represents 0, 1, or 2, respectively, and q represents 0 or 1, respectively. Wherein, when p represents 2 and q represents 0, the oxidation number of M is +4, and X each independently represents a methyl group or a benzyl group. In addition, when p represents 1, q represents 0, the oxidation number of M is +3, and X represents 2- (N, N-dimethyl) aminobenzyl, or the oxidation number of M is +4, and X Represents 2-butene-1,4-diyl. When p represents 0 and q represents 1, the oxidation number of M is +2, and X 'represents 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene. The diene can be exemplified as an asymmetric diene forming a metal complex, which is actually a mixture of geometric isomers. The (c) transition metal compound is preferably, for example, [(N-third butylamidinoamino) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] dimethyl titanium., [(N-Third-butylphosphoniumamino) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium dichloride, [(N-Third-butylphosphoniumamino) (tetramethyl -Η5-cyclopentadienyl) dimethylsilane] 1,3-pentadiene titanium, and [(N-third butylamidinoamino) (tetramethyl-η5-cyclopentadienyl) Dimethylsilane] diphenyl titanium and the like are more preferably [(N-third butylamidinoamino) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] dimethyl titanium. The aforementioned supported geometrically limited metallocene catalyst contains (d) an activator that can react with a transition metal compound to form a complex that exhibits catalytic activity (hereinafter also referred to as "(d) activator", "activator" "). Generally, in metallocene catalysts, the complex formed by the (c) transition metal compound and the (d) activator as a catalyst active species exhibits a higher olefin polymerization activity. In the method for producing high-density polyethylene (A) in this embodiment, the (d) activator is not particularly limited, and examples thereof include a compound represented by the following formula (7). [L-H]_d ⁺ [M_m Q_p ]_d ^- ・ ・ ・ (7) In formula (7), [L-H]_d ⁺ Bronister acid for proton-donating property, and L for neutral Lewis base. Moreover, in formula (7), [M_m Q_p ]_d ^- Compatible non-coordinating anions, M represents a metal or metalloid selected from Groups 5 to 15 of the periodic table, and Q each independently represents a hydride, dialkylamido, halide, alkoxy Group, allyloxy group, hydrocarbyl group or substituted hydrocarbon group having up to 20 carbon atoms, and Q as a halide is 1 or less. In the formula (7), m represents an integer of 1 to 7, p represents an integer of 2 to 14, d represents an integer of 1 to 7, and p-m = d. (d) A more preferable example of the activator is a compound represented by the following formula (8). [L-H]_d ⁺ [M_m Q_n (G_q (T-H)_r )_z ]_d ^- ・ ・ ・ (8) In formula (8), [L-H]_d ⁺ Bronister acid for proton-donating property, and L for neutral Lewis base. Moreover, in formula (8), [M_m Q_n (G_q (T-H)_r )_z ]_d ^- Compatible non-coordinating anions, M represents a metal or metalloid selected from Groups 5 to 15 of the periodic table, and Q each independently represents a hydride, dialkylamido, halide, alkoxy Group, allyloxy group, hydrocarbyl group or substituted hydrocarbon group having up to 20 carbon atoms, and Q as a halide is 1 or less. In formula (8), G represents a polyvalent hydrocarbon group having a valence of r + 1 bonded to M and T, and T represents O, S, NR, or PR. Here, R represents a hydrocarbon group, a trialkylsilyl group, a trialkyl germanium group, or hydrogen. In formula (8), m represents an integer of 1 to 7, n represents an integer of 0 to 7, q represents an integer of 0 or 1, r represents an integer of 1 to 3, z represents an integer of 1 to 8, and d represents An integer from 1 to 7, n + z-m = d. (d) A further preferred example of the activator is a compound represented by the following formula (9). [L-H]^＋ [BQ₃ Q₁ ]^- ・ ・ ・ (9) In formula (9), [L-H]⁺ Bronister acid for proton-donating property, and L for neutral Lewis base. Moreover, in formula (9), [BQ₃ Q₁ ]^- Compatible non-coordinating anions, B represents boron, Q³ For pentafluorophenyl, Q¹ A substituted allyl group having 6 to 20 carbon atoms having one OH group as a substituent. Examples of the proton-improving Bronsted acid in formulae (7), (8), and (9) include, for example, triethylammonium, tripropylammonium, tri (n-butyl) ammonium, and trimethylammonium. Ammonium, tributylammonium, tri (n-octyl) ammonium, diethylmethylammonium, dibutylmethylammonium, dibutylethylammonium, dihexylmethylammonium, dioctylmethylammonium, didecyl Methylammonium, di (dodecyl) methylammonium, di (tetradecyl) methylammonium, bis (hexadecyl) methylammonium, bis (octadecyl) methylammonium, di (Eicosyl) methylammonium and bis (hydrogenated tallow alkyl) methylammonium trialkyl-substituted ammonium cations; such as N, N-dimethylaniline, N, N-diethylbenzene N, N-dialkylaniline cations such as ammonium, N, N-2,4,6-pentamethylaniline and N, N-dimethylbenzylaniline; triphenylcarbocations, but Not limited to these. Among these proton-imparting Bronsted acids, trialkyl-substituted ammonium cations are preferred, and bis (hydrogenated tallow alkyl) methylammonium is more preferred. Examples of the above-mentioned compatible non-coordinating anions in formulae (7), (8), and (9) include triphenyl (hydroxyphenyl) borate and diphenyl-bis (hydroxyphenyl) ) Borate, triphenyl (2,4-dihydroxyphenyl) borate, tris (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-di-trifluoromethyl) Phenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) borate, tris (pentafluorophenyl) Phenyl) (4-hydroxycyclohexyl) borate, tris (pentafluorophenyl) (4- (4'-hydroxyphenyl) phenyl) borate and tris (pentafluorophenyl) (6-hydroxy-2 -Naphthyl) borate, but is not limited thereto. Such compatible non-coordinating anions are also referred to as "borate compounds". From the viewpoint of catalyst activity and the viewpoint of reducing the total content of Al, Mg, Ti, Zr, and Hf, it is preferable that the activator of the supported geometrically-limited metallocene catalyst contains a borate compound as a compatible one. Non-coordinating anions. Preferred examples of the borate compound include tris (pentafluorophenyl) (4-hydroxyphenyl) borate. As the (d) activator, an organometallic oxygen compound having a unit represented by the following formula (10) can also be used. [Chemical 6]In formula (10), M² Represents metals or metalloids of Groups 13 to 15 of the periodic table, R each independently represents a hydrocarbon group or substituted hydrocarbon group having 1 to 12 carbon atoms, n represents the valence of metal M2, and m represents an integer of 2 or more. (d) Another preferred example of the activator is an organoaluminum oxy compound containing a unit represented by the following formula (11). [Chemical 7]In the formula (11), R represents an alkyl group having 1 to 8 carbon atoms, and m represents an integer of 2 to 60. (d) A more preferable example of the activator is methylalumoxane containing a unit represented by the following formula (12). [Chemical 8]In the formula (12), m represents an integer of 2 to 60. In addition, in the manufacturing method of the high-density polyethylene (A) in this embodiment, in addition to using the supported geometrically limited type metallocene catalyst of the above-mentioned components (a) to (d), an organic material may be used as necessary. Aluminum compounds act as catalysts. The organoaluminum compound is not particularly limited, and examples thereof include compounds represented by the following formula (13). AlR_n X_3-n (13) In formula (13), R represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or allyl group having 6 to 20 carbon atoms, and X represents halogen, hydrogen, or Alkoxy, n represents an integer of 1 to 3. The organoaluminum compound may be a mixture of compounds represented by formula (13). The above-mentioned supported geometrically-limited metallocene catalyst can be obtained by supporting the component (b), the component (c), and the component (d) on the component (a). As a method for supporting the component (b), the component (c), and the component (d), it is preferable to add the component (b) to a suspension obtained by dispersing the component (a) in an inert solvent, and the temperature is from 0 ° C to 70 ° C. By stirring at 30 ° C for 30 minutes or more, the active hydrogen existing on the surface of the carrier material is allowed to react with the organoaluminum compound. Next, the component (c) and the component (d) are added to the suspension of the component (a) after reacting with the component (b) simultaneously at 40 to 50 ° C at 20 to 50% by mass of the total input amount, and the remainder is left. 50 to 80% by mass are simultaneously added dropwise at 10 to 15 ° C. Thereby, there is a tendency that a catalyst active site can be formed inside the component (a), and by supplying the catalyst to polymerization, a highly crystalline polyethylene can be generated inside the catalyst. The component (c) and the component (d) are preferably liquid or solid. In addition, the component (b), the component (c), and the component (d) can be used by being diluted with an inert solvent at the time of supporting. Examples of the inert solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; benzene, toluene, Aromatic hydrocarbons such as xylene; mixtures of these, but not limited to them. The inert solvent is preferably used after removing impurities such as water, oxygen, and sulfur components using a desiccant, an adsorbent, or the like. The component (b) is preferably 1.0 × 10 in terms of Al atom conversion with respect to 1.0 g of the component (a).^-5 ～ 1.0 × 10^-1 Mohr, more preferably 1.0 × 10^-4 ～ 5.0 × 10^-2 Moore range, the component (c) is preferably 1.0 × 10^-7 ～ 1.0 × 10^-3 Mohr, more preferably 5.0 × 10^-7 ～ 5.0 × 10^-4 Moore range, preferably component (d) is 1.0 × 10^-7 ～ 1.0 × 10^-3 Mohr, more preferably 5.0 × 10^-7 ～ 5.0 × 10^-4 Mor's Range. The amount of each component and the method of supporting it are determined based on the activity, economy, powder characteristics, and rust in the reactor. Regarding the obtained supported geometrically limited metallocene catalysts, in order to remove organoaluminum compounds, borate compounds, and titanium compounds that are not supported on the carrier, an inert solvent may be used and decantation or filtration may be used. Cleaning. The above-mentioned series of dissolution, contact, and cleaning operations are preferably performed at a temperature of -30 ° C or higher and 80 ° C or lower selected for each unit operation. A more preferable range of such a temperature is 0 ° C to 50 ° C. In addition, a series of operations to obtain one of the supported geometrically limited metallocene catalysts is preferably performed in a dry inert environment. The supported geometrically limited metallocene catalyst can be used alone in the copolymerization step of ethylene and α-olefin in the manufacturing step of the high-density polyethylene (A) in this embodiment, but in order to prevent solvent or reaction poisoning, An organoaluminum compound as a liquid auxiliary catalyst component (D) can be used in coexistence. As the organic aluminum compound as the liquid auxiliary catalyst component (D), for example, alkyl groups such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum can be preferably cited. Aluminium; Alkyl hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; aluminum alkoxides such as diethylaluminum ethoxide; methylalumoxane, isobutylalumoxane and methyl isobutylaluminum oxyhydroxide Alumoxane such as alkane is not limited thereto. Among these, trialkylaluminum and aluminum alkoxide are preferred. More preferred is triisobutylaluminum. The polymerization method in the manufacturing step of the high-density polyethylene (A) in this embodiment is preferably a slurry polymerization method. When polymerization is performed, the polymerization pressure is usually preferably 0.1 MPaG or more and 10 MPaG or less, and more preferably 0.3 MPaG or more and 3.0 MPaG or less. The polymerization temperature is preferably 20 ° C or higher and 115 ° C or lower, and more preferably 50 ° C or higher and 85 ° C or lower. The solvent used in the slurry polymerization method is preferably an inert solvent for diluting the component (b), the component (c), and the component (d) during the above-mentioned loading, and more preferably an inert hydrocarbon solvent. Examples of the inert hydrocarbon solvent include hydrocarbon solvents having 6 to 8 carbon atoms, and specific examples thereof include aliphatic hydrocarbons such as hexane, heptane, and octane; and alicyclic hydrocarbons such as cyclohexane and methylcyclopentane. ; A mixture of these. The polymerization method in the manufacturing step of the high-density polyethylene (A) in this embodiment is preferably continuous polymerization. Ethylene gas, solvent, catalyst, etc. are continuously supplied into the polymerization system and continuously discharged together with the produced high-density polyethylene (A), thereby suppressing a part of the high-temperature state caused by the rapid ethylene reaction, and making the polymerization system More stable tendency. When ethylene reacts in a uniform state, there is a tendency to suppress the widening of the molecular weight distribution. In the case of copolymerizing ethylene with an α-olefin, it is preferable to remove a certain amount of ethylene, hydrogen, and α-olefin by using an instantaneous evaporation tank after the polymerizer, and then keep it at a specific state without supplying raw materials. Conditions in the buffer tank. The lower limit of the temperature of the buffer tank is preferably 65 ° C or higher, more preferably 68 ° C or higher, and even more preferably 70 ° C or higher. The upper limit of the temperature of the buffer tank is preferably 80 ° C or lower, and more preferably 75 ° C or lower. The instant evaporation tank is a device that removes a certain amount of ethylene, hydrogen, and α-olefins by reducing the pressure below the polymerizer. The ease of removal changes in the following order, that is, the hydrogen with a smaller molecular weight is most easily removed, and then In this order, ethylene and α-olefin. Therefore, the composition of the raw materials in the instantaneous evaporation tank is greatly changed compared to the inside of the polymerizer, and the concentrations of ethylene and α-olefin are relatively high. By keeping the composition in the buffer tank, unlike the polymerizer, the concentration of the raw material is low and the concentration of the chain transfer agent is low. Under this condition, the polymerization is slowly performed without the catalyst being inactivated, thereby improving the performance. The density polyethylene powder tends to form crystals of the same size inside. Generally, the ethylene-α-olefin copolymer tends to decrease crystallinity depending on the amount of α-olefin, but by using the above-mentioned production method, high crystallinity can be maintained. The solvent separation method in the manufacturing method of the high-density polyethylene (A) in this embodiment may include a decantation method, a centrifugal separation method, a filter filtration method, and the like, and more preferably, the high-density polyethylene (A) and the solvent Centrifugation with higher separation efficiency. The amount of the solvent contained in the high-density polyethylene (A) after the solvent separation is not particularly limited, and it is preferably 50% by mass or more and 90% by mass or less relative to the mass of the high-density polyethylene (A), and more It is preferably 55% by mass or more and 85% by mass or less, and still more preferably 60% by mass or more and 80% by mass or less. As a method for deactivating a catalyst for synthesizing the high-density polyethylene (A), it is preferred to perform the separation after separating the high-density polyethylene (A) from a solvent. The agent for inactivating the catalyst is not particularly limited, and examples thereof include oxygen, water, and alcohols. When drying in the manufacturing method of the high-density polyethylene (A) in this embodiment, it is preferable to implement it in the state which circulates inert gas, such as nitrogen and argon. The drying temperature is preferably 50 ° C or higher and 150 ° C or lower, more preferably 50 ° C or higher and 140 ° C or lower, and even more preferably 50 ° C or higher and 130 ° C or lower. If the drying temperature is 50 ° C or higher, it tends to be dried efficiently. On the other hand, if the drying temperature is 150 ° C. or lower, there is a tendency that it can be dried in a state in which decomposition or crosslinking of the high-density polyethylene (A) is suppressed. In addition to the above-mentioned components, other known components useful in the production of the high-density polyethylene (A) may be contained. [High-pressure method low-density polyethylene resin (B)] The density (JIS K7112) of the high-pressure method low-density polyethylene resin (B) in this embodiment is preferably 910 to 930 kg / m³ , More preferably 912 ～ 927 kg / m³ , And more preferably 915 to 925 kg / m³ . The density of the high-pressure low-density polyethylene resin (B) was 910 kg / m³ The above results in a film that can maintain a moderate hardness and has tearability. The density of the high-pressure low-density polyethylene resin (B) was 930 kg / m.³ Hereinafter, the melting point can be maintained moderately, and the sealability can be maintained. The density of the high-pressure method low-density polyethylene (B) tends to decrease if the peak temperature of the polymerization reaction is increased, and also tends to increase if the polymerization pressure is increased. The density of the high-pressure method low-density polyethylene resin (B) can be measured by the method described in the examples. The melt flow rate (JIS K7210) of the high-pressure low-density polyethylene resin (B) of this embodiment at 190 ° C and 2.16 kg is preferably 1 to 20 g / 10 minutes, and more preferably 1.5 to 15 g / 10 minutes. , And more preferably 2 to 10 g / 10 minutes. By setting the MFR of the high-pressure low-density polyethylene resin (B) to 1 g / 10 minutes or more, it is possible to maintain the drapeability at the time of T-die molding and further suppress FE (fisheye, fisheye). In addition, by setting the MFR of the high-pressure method low-density polyethylene resin (B) to 20 g / 10 minutes or less, there is a tendency that the shrinkage at the time of T-die molding can be further suppressed. The MFR of the high-pressure low-density polyethylene (B) tends to increase if the peak temperature of the polymerization reaction is increased, and it tends to decrease if the polymerization pressure is increased. The melt flow rate of the high-pressure method low-density polyethylene resin (B) can be measured by the method described in the examples. From the viewpoint of processability, the molecular weight distribution Mw / Mn of the high-pressure method low-density polyethylene resin (B) of this embodiment is preferably 2 to 30, more preferably 3 to 25, and even more preferably 5 to 20. The molecular weight distribution Mw / Mn of the high-pressure method low-density polyethylene resin (B) can be controlled by its production conditions. The high-pressure low-density polyethylene (B) in the present embodiment can be obtained by subjecting ethylene to radical polymerization in an autoclave or tubular reactor. When using an autoclave-type reactor, the polymerization conditions may be set to a polymerization temperature of 200 to 300 ° C. and a polymerization pressure of 100 to 250 MPa, for example, in the presence of a peroxide functioning as an initiator. On the other hand, in the case of using a tubular reactor, the polymerization conditions are set to a polymerization temperature of 180 to 400 ° C. and a polymerization pressure of 100 to 400 MPa in the presence of a peroxide and a chain transfer agent, for example. The temperature may be 200 to 350 ° C, and the polymerization pressure may be 150 to 350 MPa. The peroxide is not particularly limited, and examples thereof include methyl ethyl ketone peroxide and peroxyketals (specifically 1,1-bis (third butyl peroxide) 3,3,5 -Trimethylcyclohexane, 1,1-bis (third butyl peroxide) cyclohexane, 2,2-bis (third butyl peroxide) octane, 4,4-bis (peroxide Tributyl) n-butyl valerate, 2,2-bis (third butyl peroxide) butane, etc.), hydroperoxides (specifically third butyl hydroperoxide, cumene hydroperoxide) , Dicumyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, etc., dialkyl peroxides (specifically di-peroxide Butyl, dicumyl peroxide, bis (third butyl isopropyl) benzene, third butyl cumene peroxide, 2,5-dimethyl-2,5-di (peroxide Tertiary butyl) hexane, 2,5-dimethylbis (third butyl peroxide) hexane-3, etc.), difluorenyl peroxide (specifically ethyl ethoxylate, isobutyl fluorenyl peroxide, Octyl peroxide, 3,5,5-trimethylhexyl peroxide, benzoyl peroxide, etc.), dicarbonate peroxides (specifically dicarbon peroxide) Diisopropyl ester, bis (2-ethylhexyl) peroxycarbonate, di-n-propyl peroxydicarbonate, bis (2-ethoxyethyl) peroxycarbonate, dimethoxy peroxydicarbonate Isopropyl ester, dimethoxyisopropylperoxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxydicarbonate, diallylperoxydicarbonate, etc.), peroxy Esters (specifically third butyl peracetate, third butyl peroxyisobutyrate, third butyl pervalerate, third butyl percaprylate, third butyl peroxydecanoate , Tertiary butyl peroxydecanoate, Cumyl peroxy neodecanoate, Tertiary butyl peroxy-2-ethylhexanoate, Tertiary butyl peroxy 3,5,6-trimethylhexanoate Ester, third butyl peroxy laurate, third butyl peroxy benzoate, third butyl peroxy isopropyl carbonate, cumyl peroxy octanoate, third hexyl peroxydecanoate, Tertiary hexyl pivalate, tertiary butyl peroxyhexanoate, tertiary hexaperoxyperhexanoate, cumyl peroxy neohexanoate, etc.) Allyl peroxide Acid tert-butyl ester and the like. The peroxide is preferably fed to the polymerization reactor in a state diluted with an isoalkane-based solvent, and the concentration of the peroxide is preferably 5% by mass or more and 35% by mass or less. The isoalkane-based solvent is not particularly limited. For example, a solvent having a carbon number of 10 or more and 15 or less is preferable. Specifically, isodecane, isoundecane, and isododecane are preferable. It is thought that the isoalkane that can be used as a chain transfer agent is added to the polymerization system in a state in which it is in contact with the peroxide of the initiator at a high concentration by being fed by dilution in an isoalkane-based solvent, so it is easy to produce The beginning of a long chain branch. Furthermore, by using two or more kinds of peroxides having different starting temperatures in combination, a starting point of a long-chain branch is easily generated. When the number of long-chain branches increases, the forming process is stabilized, and the dispersion state with the high-density polyethylene is improved, which contributes to the improvement of tearability. The chain transfer agent for adjusting molecular weight is not particularly limited, and examples thereof include alkanes, olefins, and ketones having 3 to 6 carbon atoms. Specific examples include propane, butane, isobutane, pentane, and isopentane. Alkane, hexane, isohexane, propylene, butene, pentene, hexene, methyl ethyl ketone, diethyl ketone, methylpropyl ketone, dipropyl ketone, and the like. [Examples] Hereinafter, this embodiment will be described in more detail based on examples. However, this embodiment is not limited to the following examples. First, the measurement methods and evaluation criteria for each physical property and evaluation will be described below. (Physical property 1) The MFR of the polyethylene obtained in the MFR production example was measured at 190 ° C and a load of 2.16 kg in accordance with ASTM-D-1238. (Physical property 2) Density The density of polyethylene obtained in the production example was measured by a density gradient tube method in accordance with JIS K6760. (Physical property 3) TREF (temperature rising dissolution classification method) measurement For the polyethylene compositions produced in the examples and comparative examples, the dissolution temperature-dissolution amount curve measured by TREF (temperature rising dissolution classification method) was performed as follows. The weight fraction Wmax of the dissolution amount, the dissolution integration amount, and the maximum dissolution amount at each temperature was determined, and the weight fraction W1 of the local maximum dissolution amount between 60 ° C and 80 ° C was determined. First, a sample solution in which 20 mg of a polyethylene composition was dissolved in 0.5 ml of o-dichlorobenzene was prepared and introduced into a sample chamber. Thereafter, the sample chamber was heated from room temperature to 140 ° C. at 40 ° C./minute and held for 120 minutes. Next, the temperature of the sample chamber was reduced to 40 ° C at a rate of 0.5 ° C / min, and then maintained for 20 minutes to precipitate the sample on the surface of the filler in the sample chamber. Thereafter, the temperature of the sample chamber and the column was sequentially increased from 40 ° C to 120 ° C at a temperature increase rate of 20 ° C / min. When the temperature was raised, the temperature was maintained at each temperature for 21 minutes, and then the temperature was raised to the next temperature. The concentration of the sample (polyethylene composition) dissolved at each temperature was detected. In addition, the dissolution temperature-dissolution amount curve was measured based on the weight fraction (mass%) of the dissolution amount of the sample (polyethylene composition) and the temperature in the column at this time, and the temperature at each temperature was calculated. Dissolution amount. The measurement conditions are as follows.・ Equipment: Automated 3D analyzer CFC-2 manufactured by Polymer ChAR company. ・ Column: Stainless steel microsphere column (3/8 inch outer diameter, 150 mm length). Benzene (for high performance liquid chromatography) • Sample solution concentration: 20 mg of sample (ethylene polymer) / o-dichlorobenzene 0.5 mL • Injection volume: 0.5 mL • Pump flow rate: 1.0 mL / min • Detector: Infrared spectrophotometer IR4 manufactured by Polymer ChAR Company • Detection wave number: 3.42 μm • Sample dissolution conditions: 140 ° C × 120 minutes (physical properties 4) 1/2 isothermal crystallization time (DSC measurement) 1/2 isothermal crystallization The crystallization time (DSC measurement) is a measurement sample of 8 to 9 mg. After measuring the extrapolated crystallization starting temperature using DSC8000 manufactured by PERKIN ELMER, the isothermal crystallization is performed at a temperature 1 ° C higher than the temperature, and the measured value is measured. . 1. Measurement of extrapolated crystallization initiation temperature The extrapolated crystallization initiation point was measured in the following procedure.・ Temperature distribution (1) Hold at 50 ° C for 1 minute (2) Warm up from 50 ° C to 180 ° C at 200 ° C / minute (3) Hold at 180 ° C for 5 minutes (4) Reduce temperature from 180 ° C at 10 ° C / minute To 50 ° C • The extrapolated crystallization initiation temperature is calculated based on the above results by a method in accordance with JIS K7121. 2. 1/2 isothermal crystallization The measurement of 1/2 isothermal crystallization time is performed in the following procedure.・ Measurement sequence: (1) Hold at 50 ° C for 1 minute; (2) Increase temperature from 50 ° C to 180 ° C at 200 ° C / minute; (3) Hold at 180 ° C for 5 minutes; (4) Reduce temperature from 180 ° C at 80 ° C / minute. To extrapolated crystallization temperature + 1 ° C (5) Hold at extrapolated crystallization temperature + 1 ° C for 5 minutes (6) Define the time for the heating curve to become a peak as 1/2 isothermal crystallization time (physical property 5) Elmendorf tear strength is made using Hokushin40 mm extruder (screw diameter 40 mm, die width 300 mm, die lip opening 0.6 mm), cylinder temperature 230 ° C, die temperature 230 ° C, extrusion capacity 10 kg / hour, winding speed 18m The polyethylene resin composition was molded per minute to produce a film including a polyethylene resin having a width of 25 cm and a thickness of 35 μm. The thickness of the obtained film was measured, and the tear strength was measured according to JIS K7128-2. The obtained tear strength was converted into 1 cm in thickness. (Physical property 6) Hand tear property With respect to the hand tear property, the film was torn by hand in the MD direction (Machine direction), and evaluated according to the following criteria. ○: A film that was torn straight was good. Δ: The film torn in a zigzag shape was slightly better. ×: The film which could not be torn straight and was torn diagonally was made defective. (Physical property 7) Coating property The above-mentioned (physical property 5) film-forming film was cut into a square of 20 cm × 20 cm, subjected to corona treatment, and then placed on a flat plate. On this film, a 5% solution of Rezem P-677 (non-silicon release agent) manufactured by Zhongjing Oil and Fat was applied by a wire rod applicator (No. 50). On the surface of the coated film, when the area where the solution was repelled from the surface of the film was less than 1%, it was evaluated as ◎, when it was 1 to 5%, it was evaluated as Δ, and when it was more than 5%, it was evaluated as ×. (Physical property 8) Sealability The evaluation of the sealability was performed by extruding and laminating the polyethylene resin composition on a 20 μm aluminum film, and measuring the sealability of the obtained film by a tensile tester. Extrusion lamination method: Use a uniaxial extruder with a straight manifold as the die nozzle, set the die lip width to 400 mm, and the die lip gap to 0.7 mm. The resin was extruded at a resin temperature of 310 ° C, passed through an air hole of 140 mm, and laminated onto an aluminum foil rolled out by a winder. Thereafter, the laminated film was cooled by a cooling roller of a half mirror specification, and the laminated film was wound on a winder. Heat seal strength: using a heat sealer (manufactured by Inspection Machine Industry Co., Ltd.) at a seal temperature of 100 ° C and a seal pressure of 2 kg / cm² The sealing time is 1 second. The laminated film obtained by the above-mentioned extrusion lamination method is heat-sealed. Using a tensile tester (manufactured by Orientec), the peel strength of the sealed portion was measured at a tensile speed of 300 mm / min. When the heat seal strength is greater than 4 N / 15 mm, it is evaluated as good, when it is 3 to 4 N / 15 mm, it is evaluated as good, and when it is less than 3 N, it is evaluated as bad. (Physical property 9) Chlorine content measurement method Approximately 0.05 g of each polyethylene resin composition obtained in the examples and comparative examples was placed in a quartz boat, and was made by an automatic combustion device AQF-100 manufactured by Mitsubishi ANALYTECH combustion. The combustion gas generated by the absorption solution with tartaric acid added in advance was quantified by the internal standard method with tartaric acid as an internal standard substance by an ion chromatography analysis device ICS-1500 manufactured by Dionex Corporation. The unit is mass ppm. In Examples and Comparative Examples, a resin material produced by the following method was used. [Preparation of catalyst] (1) Preparation of supported geometrically limited metallocene catalyst [A] In an autoclave with a capacity of 1.8 L, the catalyst carrier for dehydration at 600 ° C was used for silica (average particle size). Diameter 15 μm, compressive strength 3 MPa) 40 g was dispersed in 800 mL of hexane under a nitrogen environment to obtain a slurry. While maintaining the obtained slurry at 25 ° C, 84 mL of a hexane solution (concentration 1 mol / L) of triethylaluminum was added while stirring. Thereafter, the mixture was stirred for 2 hours to react triethylaluminum with the surface hydroxyl group of silicon dioxide to obtain a hexane slurry of component [a1] whose surface hydroxyl group of silicon dioxide was terminated with triethylaluminum. On the other hand, [(N-Third-butylamidoamino) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] dimethyl titanium (hereinafter, referred to as "titanium complex" ) 200 mmol was dissolved in 1000 mL of Isopar E (registered trademark) (trade name of a hydrocarbon mixture manufactured by Exxon Chemical Company (USA)), 20 mL of a 1 mol / L hexane solution of n-butyl ethyl magnesium was added, and The concentration of the titanium complex was adjusted to 0.1 mol / L to obtain a component [b1]. Further, 5.7 g of tris (pentafluorophenyl) (4-hydroxyphenyl) borate bis (hydrogenated tallow alkyl) methylammonium (hereinafter, referred to as "borate compound") was added to 50 mL of toluene to make it Dissolve to obtain a 100 mmol / L toluene solution of a borate compound. To the toluene solution of the borate compound at room temperature was added 5 mL of a 1 mol / L hexane solution of diethylaluminum ethoxide, and then hexane was added so that the concentration of the borate compound in the solution became 70 mmol / L. Then, it stirred at room temperature for 1 hour, and obtained the reaction mixture [c] containing a borate compound. After heating the above [a1] slurry to 45-50 ° C, set the stirring speed to 600 rpm, and simultaneously add [c] 9.2 mL and [b1] 6.4 mL to the above [a1] slurry over 20 minutes. Then, it stirred at 50 degreeC for 1 hour, and the catalyst active seed was penetrated into the inside of a silica. Thereafter, the supernatant containing the unreacted borate compound and the titanium complex in the obtained reaction mixture was removed by decantation, whereby the catalyst active species was carried inside the silicon dioxide. After further lowering the temperature to 10 to 15 ° C, [c] 36.8 mL and [b1] 25.6 mL were simultaneously added dropwise over 80 minutes, and then stirred at 15 to 20 ° C for 3 hours to thereby make the titanium complex and borate The reaction and precipitation cause the catalyst active species to be physically adsorbed on the surface of silicon dioxide. Thereafter, the supernatant liquid containing the unreacted borate compound and titanium complex in the obtained reaction mixture is removed by decantation, thereby obtaining a catalyst active species formed on the surface and inside of the silicon dioxide. Supported geometrically limited metallocene catalyst [A] (In the following [preparation of polyethylene], it is represented only as [A]). (2) Preparation of load-carrying geometrically limited metallocene catalyst [B] Prepared in an autoclave with a capacity of 1.8 L, and used as a catalyst carrier for dehydration at 500 ° C for silica (average particle size 15 μm, compressive strength) (35 MPa) 40 g were dispersed in 800 mL of hexane under a nitrogen atmosphere to obtain a slurry. While maintaining the obtained slurry at 25 ° C with stirring, 84 mL of a triethylaluminum hexane solution (concentration of 1 mol / L) was added, followed by stirring for 2 hours to bring the surface of triethylaluminum and silicon dioxide The hydroxyl group reacts to obtain a hexane slurry of the component [a2] whose surface hydroxyl group of silicon dioxide is capped with triethylaluminum. On the other hand, [(N-Third-butylamidoamino) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] dimethyl titanium (hereinafter, referred to as "titanium complex" ) 200 mmol was dissolved in 1000 mL of Isopar E (registered trademark) (trade name of a hydrocarbon mixture manufactured by Exxon Chemical Company (USA)), and AlMg previously synthesized from triethylaluminum and dibutylmagnesium was added.₆ (C₂ H₅ )₃ (n-C₄ H₉ )₁₂ 20 mL of a 1 mol / L hexane solution was further added to adjust the titanium complex concentration to 0.1 mol / L to obtain a slurry of component [b2]. After the slurry of the above component [a2] was heated to 20 to 25 ° C, the stirring speed was set to 300 rpm, and the reaction containing the borate compound in the above (1) was added dropwise to the slurry of [a2] simultaneously over 60 minutes The mixture of [c] 46 mL and [b2] 32 mL was further stirred for 3 hours to react and precipitate the titanium complex with borate to physically adsorb the catalytically active species on the surface of silicon dioxide. Thereafter, the supernatant liquid containing the unreacted borate compound and titanium complex in the obtained reaction mixture is removed by decantation, thereby obtaining a load of catalyst active species formed on the surface of the silicon dioxide. Type geometrically limited type metallocene catalyst [B] (in the following [preparation of polyethylene], it is represented only as [B]). (3) Preparation of Ziegler-Natta catalyst [C] 1) Synthesis of carrier. An 8 L stainless steel autoclave fully substituted with nitrogen was charged with 2 mol / L trichlorosilane hexane solution 1,000 mL. , AlMg was added dropwise over 4 hours while stirring at 65 ° C₅ (C₄ H₉ )₁₁ (OC₄ H₉ )₂ The hexane solution of the represented organic magnesium compound was 2,550 mL (equivalent to 2.68 mol of magnesium), and the reaction was continued while stirring at 65 ° C for 1 hour. After the reaction was completed, the supernatant was removed and washed 4 times with 1,800 mL of hexane. The solid was analyzed, and as a result, the magnesium contained in the solid per 1 g was 8.31 mmol. 2) Preparation of Ziegler-Natta catalyst [C] In 1,970 mL of hexane slurry containing 110 g of the above carrier, and stirred at 10 ° C for 1 hour while adding 1 mol / L of tetrachloride 110 mL of titanium hexane solution and 1.0 mol / L of AlMg₅ (C₄ H₉ )₁₁ (OSiH)₂ 110 mL of the hexane solution of the indicated organomagnesium compound. After the addition, the reaction was continued at 10 ° C for 1 hour. After the reaction was completed, the supernatant was removed by decantation and washed twice with hexane, thereby preparing a Ziegler-Natta catalyst [C] as a solid catalyst component (the following [preparation of polyethylene] (Only expressed as [C]). [Preparation of polyethylene] (1) High-density polyethylene (A) [Production of high-density polyethylene (A-1)] A high-density polyethylene was obtained by a continuous slurry polymerization method shown below. Specifically, continuous polymerization was performed using a 340 L dish-type polymerization reactor equipped with a stirring device under conditions of a polymerization temperature of 80 ° C., a polymerization pressure of 0.98 MPa, and an average residence time of 3.2 hours. The polymerization rate was 10 kg / hour. Dehydrated n-hexane was supplied as a solvent at 40 L / hour, 1.4 mmol / hour in terms of Ti atom was supplied as the catalyst [A], and 20 mmol / hour was used as a liquid auxiliary catalyst. Triisobutyl aluminum as a medium component. In addition, hydrogen for molecular weight adjustment was supplied so that the gas phase concentration relative to ethylene and 1-butene became 0.25 mol%, and 1-butene was used such that the gas phase concentration relative to ethylene was 0.37 mol%. Supply, thereby copolymerizing ethylene with 1-butene. The slurry concentration was 27% by weight. The catalyst is supplied from the vicinity of the liquid level of the polymerizer, and ethylene and 1-butene are supplied from the bottom of the polymerizer. The polymerization slurry in the polymerization reactor was introduced into the instant evaporation tank at a pressure of 0.05 MPa and a temperature of 70 ° C in such a manner that the level of the polymerization reactor was kept constant to separate a certain amount of unreacted ethylene, 1-butene, and hydrogen. Thereafter, it was introduced into a buffer tank having a pressure of 0.30 MPa and a temperature of 65 ° C. under the condition of an average residence time of 1.0 hour. Next, the slurry is continuously fed into a centrifugal separator with the level of the buffer tank kept constant, and the powder is separated from other solvents and the like. The separated high-density polyethylene powder was dried at 85 ° C while blowing nitrogen gas. In this drying step, steam is sprayed on the powder mist to inactivate the catalyst and the auxiliary catalyst. For the obtained high-density polyethylene powder, without using additives such as neutralizers or antioxidants, TEX-44 (screw diameter 44 mm, L / D = 35; L: raw material supply port to discharge port) manufactured by Japan Steel Manufacturing Co., Ltd. was used. Distance (m), D: inner diameter (m)) of a biaxial extrusion molding machine, melt-kneading at an extrusion capacity of 30 kg / hour and a temperature of 200 ° C, using a wire cutting machine manufactured by Toshiba Machinery, to A high-density polyethylene (A-1) was obtained by cutting and granulating with 12 cutters at 550 rpm. The average weight of one granule was 18.5 mg. Table 1 shows the evaluation results of the MFR and density of the high-density polyethylene (A-1). [Production of high-density polyethylene (A-2)] Hydrogen was supplied so that the gas phase concentration of ethylene and 1-butene became 0.32 mol%, and 1-butene was formed at a gas phase concentration of ethylene to The high-density polyethylene (A-2) was obtained in the same manner as in the production of the high-density polyethylene (A-1), except that it was supplied at 0.21 mol%. The average weight of one granule was 17.5 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-density polyethylene (A-3)] Hydrogen was supplied so that the gas phase concentration relative to ethylene and 1-butene became 0.56 mol%, and 1-butene was obtained at a gas phase concentration relative to ethylene. The high-density polyethylene (A-3) was obtained in the same manner as in the production of the high-density polyethylene (A-1), except that it was supplied at 0.06 mol%. The average weight of one granule was 18.0 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-density polyethylene (A-4)] Hydrogen was supplied so that the gas phase concentration relative to ethylene was 0.47 mol%, 1-butene was not supplied, and a buffer tank was not used. The high-density polyethylene (A-4) is obtained by the same operation as the production of the high-density polyethylene (A-1). The average weight of one pellet was 17.7 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-density polyethylene (A-5)] Hydrogen was supplied so that the gas phase concentration relative to ethylene became 0.17 mol%. 1-butene was not supplied, and a buffer tank was not used. The high-density polyethylene (A-4) is obtained by the same operation as the production of the high-density polyethylene (A-1). The average weight of one granule was 18.3 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-density polyethylene (A-6)] The polymerization temperature was set to 83 ° C, the polymerization pressure was set to 0.80 MPa, and [C] was used as a catalyst to make hydrogen gas phase concentration relative to ethylene and 1-butene. It was changed to 44.33 mol%, and the gas phase concentration of 1-butene relative to ethylene was 0.64 mol%, and a buffer tank was not used. Except for this, the same operation as in the production of high-density polyethylene (A-1) was performed. Polymerize to obtain high density polyethylene powder. 300 mass ppm of tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester as an antioxidant was added to the obtained high-density polyethylene powder. Granulation was carried out in the same manner as in the production of high-density polyethylene (A-1) to obtain high-density polyethylene (A-6). The average weight of one granule was 16.0 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-density polyethylene (A-7)] The polymerization temperature was set to 85 ° C, the polymerization pressure was set to 1.0 MPa, the gas phase concentration of hydrogen relative to ethylene was 64 mol%, and 1-butene was not supplied. Other than this, a high-density polyethylene (A-7) is obtained by the same operation as the production of the high-density polyethylene (A-6). The average weight of one granule was 17.2 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-density polyethylene (A-8)] The polymerization temperature was set to 85 ° C, the polymerization pressure was set to 0.95 MPa, the gas phase concentration of hydrogen relative to ethylene and propylene was 27.5 mol%, and 1-butene was A high-density polyethylene (A-8) was obtained by the same operation as in the production of high-density polyethylene (A-6) except that the gas phase concentration of ethylene was 3.3 mol%. The average weight of one granule was 16.5 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-density polyethylene (A-9)] The polymerization temperature was set to 85 ° C, the polymerization pressure was set to 0.95 MPa, the gas phase concentration of hydrogen relative to ethylene and propylene was 58 mol%, and 1-butene was relative A high-density polyethylene (A-9) was obtained by the same operation as in the production of high-density polyethylene (A-6), except that the gas phase concentration of ethylene was 1.6 mol%. The average weight of one granule was 19.0 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-density polyethylene (A-10)] Set the polymerization temperature to 75 ° C, the polymerization pressure to 0.8 MPa, the average residence time to 1.6 hours, and use [B] as a catalyst to adjust the molecular weight. Hydrogen was supplied so that the gas phase concentration relative to ethylene and 1-butene became 0.21 mol%, and 1-butene was supplied such that the gas phase concentration relative to ethylene became 0.27 mol%, whereby ethylene and 1 -Butene polymerization. In addition, dehydrated n-hexane is supplied from the bottom of the polymerizer. In order to contact the catalyst in advance, hydrogen is supplied from the catalyst introduction line together with the catalyst from the liquid level and the bottom of the polymerizer, and ethylene is supplied from the polymerizer. Bottom supply. The polymerization slurry in the polymerization reactor was introduced into the instant evaporation tank at a pressure of 0.08 MPa and a temperature of 75 ° C. with a certain level of the polymerization reactor to separate unreacted ethylene, 1-butene, and hydrogen. Next, the polymerization slurry is continuously fed to a centrifugal separator with the level of the polymerization reactor kept constant, and the polymer is separated from other solvents and the like. The separated high-density polyethylene powder was dried at 85 ° C while blowing nitrogen gas. Furthermore, in this drying step, steam is sprayed out of the polymerized powder in a mist form, and the catalyst and the auxiliary catalyst are deactivated. The obtained high-density polyethylene powder was granulated by the same operation as the high-density polyethylene (A-1) to obtain a high-density polyethylene (A-10). The average weight of one particle was 17.9 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-density polyethylene (A-11)] Hydrogen was supplied so that the gas phase concentration relative to ethylene and 1-butene became 0.12 mol%, and 1-butene was obtained at a gas phase concentration relative to ethylene. The high-density polyethylene (A-11) was obtained in the same manner as in the production of the high-density polyethylene (A-10), except that it was supplied in the form of 0.011 mol%. The average weight of one granule was 17.5 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-density polyethylene (A-12)] The polymerization temperature was set to 86 ° C, and the polymerization pressure was set to 1.0 MPa so that the gas phase concentration of hydrogen relative to ethylene became 46 mol%. In addition, a high-density polyethylene (A-12) was obtained by the same operation as in the production of the high-density polyethylene (A-6). The average weight of one pellet was 19.3 mg. The evaluation results of MFR and density are shown in Table 1. (2) High-pressure low-density polyethylene (B) [Manufacture of high-pressure low-density polyethylene (B-1)] In an autoclave reactor at a polymerization temperature of 256 ° C and a polymerization pressure of 168 MPa, use peracetic acid The third butyl ester and the third butyl peroctoate are diluted in isododecane in a molar ratio of 2: 8 and become 11% by mass as an initiator, and isobutane as a chain transfer agent It was fed at a rate of 1.85 mol% relative to ethylene to polymerize ethylene, and then melt-kneaded using a twin-screw extruder at a temperature of 50 kg / hour and 180 ° C, using a line manufactured by Toshiba Machinery The material was cut and granulated under the conditions of 16 blades and 700 rpm to obtain a high-pressure low-density polyethylene resin. The average weight of one granule was 17.5 mg. The evaluation results of MFR and density of the obtained high-pressure low-density polyethylene resin (B-1) are shown in Table 1. [Production of high-pressure low-density polyethylene (B-2)] In a tubular reactor, the average polymerization temperature was set to 305 ° C, the polymerization pressure was set to 191 MPa, and undiluted di-tert-butyl peroxide was used as the starting point. A high-pressure process low-density polyethylene (a high-pressure process low-density polyethylene (B-1) was obtained by the same operation as that of the high-pressure process low-density polyethylene (B-1) except that the propylene as a chain transfer agent was 0.3 mol% relative to ethylene. B-2). The average weight of one granule was 17.5 mg. The evaluation results of MFR and density are shown in Table 1. [Manufacture of high-pressure low-density polyethylene (B-3)] In an autoclave reactor, the polymerization temperature was set to 256 ° C, the polymerization pressure was set to 168 MPa, and undiluted third butyl peracetate was used as a starting point. Except for this, a high-pressure method low-density polyethylene (B-3) was obtained by the same operation as in the production of the high-pressure method low-density polyethylene (B-1). The average weight of one granule was 21.3 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-pressure low-density polyethylene (B-4)] In an autoclave reactor, the polymerization temperature was set to 258 ° C, the polymerization pressure was set to 120 MPa, and third butyl peracetate and third octanoic acid were used. Butyl ester was prepared by diluting it in isododecane so that it has a molar ratio of 1: 9 and 25% by mass. In addition, the low-density polyethylene (B-1) The same operation was performed to obtain a high-pressure process low-density polyethylene (B-4). The average weight of one granule was 18.6 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-pressure low-density polyethylene (B-5)] In an autoclave reactor, the polymerization temperature was set to 190 ° C and the polymerization pressure was set to 126 MPa. The third butyl acetate was obtained by diluting it in isododecane in a molar ratio of 7: 3 and 25% by mass as an initiator. In addition, a low-pressure polyethylene (B -1) The same operation was performed to obtain a high-pressure method low-density polyethylene (B-5). The average weight of one granule was 16.5 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-pressure low-density polyethylene (B-6)] In an autoclave reactor, the polymerization temperature was set to 183 ° C and the polymerization pressure was set to 191 MPa. The third butyl octanoate was diluted in isododecane at a molar ratio of 5: 5 to 13% by mass as an initiator, and methyl ethyl ketone as a chain transfer agent became ethylene relative to ethylene. Except for 0.71 mol%, the high-pressure method low-density polyethylene (B-6) was obtained by the same operation as that of the high-pressure method low-density polyethylene (B-1). The average weight of one granule was 18.7 mg. The evaluation results of MFR and density are shown in Table 1. [Manufacture of high-pressure low-density polyethylene (B-7)] In an autoclave reactor, the polymerization temperature was set to 230 ° C, the polymerization pressure was set to 201 MPa, and the third butyl peroctoate and the third peracetic acid were used. Butyl ester was obtained by diluting it in isododecane at a molar ratio of 6: 4 and becoming 10% by mass as an initiator, so that isobutane as a chain transfer agent was 3.85 mol% relative to ethylene, except that Otherwise, a high-pressure method low-density polyethylene (B-7) was obtained by the same operation as in the production of the high-pressure method low-density polyethylene (B-1). The average weight of one granule was 18.0 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-pressure low-density polyethylene (B-8)] In a tubular reactor, the polymerization temperature was set to 300 ° C, the polymerization pressure was set to 255 MPa, and undiluted di-tert-butyl peroxide was used as a starting point. A high-pressure process low-density polyethylene (B -8). The average weight of one granule was 18.0 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-pressure low-density polyethylene (B-9)] In a tubular reactor, the average polymerization temperature was set to 285 ° C, and the polymerization pressure was set to 265 MPa. Tributyl ester is obtained by diluting the molar ratio of 4: 6 in isododecane as the starting agent, so that the propylene as a chain transfer agent becomes 1.0 mol% relative to ethylene. The same operation was performed for the production of the density polyethylene (B-1) to obtain a high-pressure method low-density polyethylene (B-9). The average weight of one granule was 16.9 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-pressure low-density polyethylene (B-10)] In an autoclave reactor, the polymerization temperature was set to 256 ° C, the polymerization pressure was set to 122 MPa, and third butyl peracetate and third octanoic acid were used. Butyl ester was prepared by diluting it in isododecane so that it has a molar ratio of 1: 9 and 30% by mass. In addition, the low-density polyethylene (B-1) The same operation was performed to obtain a high-pressure low-density polyethylene (B-10). The average weight of one granule was 17.3 mg. The evaluation results of MFR and density are shown in Table 1. [Production of high-pressure low-density polyethylene (B-11)] In an autoclave reactor, the polymerization temperature was set to 208 ° C and the polymerization pressure was set to 112 MPa. The third butyl octanoate was diluted with isododecane at a molar ratio of 5: 5 and 30% by mass as an initiator. In addition, the low-density polyethylene (B -1) The same operation was performed to obtain a high-pressure low-density polyethylene (B-11). The average weight of one granule was 18.6 mg. The evaluation results of MFR and density are shown in Table 1. [Manufacture of high-pressure low-density polyethylene (B-12)] In an autoclave reactor, the polymerization temperature was set to 245 ° C, the polymerization pressure was set to 170 MPa, and undiluted third butyl peroxide acetate was used as a starting point. Except for the initiator, a high-pressure low-density polyethylene (B-12) was obtained by the same operation as in the production of the high-pressure low-density polyethylene (B-1). The average weight of one granule was 15.3 mg. The evaluation results of MFR and density are shown in Table 1. (3) Polyethylene resin composition [Example 1] A-1 as a high-density polyethylene resin and B-7 as a high-density low-density polyethylene resin were used, and uniaxial extrusion manufactured by Nippon Steel Co., Ltd. was used. Out of the machine (screw diameter 65 mm, L / D = 28), A-1 and B-7 were made into 40% by mass and 60% by mass, respectively, and melt-kneaded at an extrusion rate of 30 kg / hour and 200 ° C The polyethylene resin composition PE-1 was obtained by cutting and granulating under the conditions of 12 blades and 600 rpm. The evaluation results are shown in Table 1. [Example 2] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1 except that A-2 and B-9 were made 45% by mass and 55% by mass, respectively. Composition PE-2. The evaluation results are shown in Table 1. [Example 3] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-3 and B-1 were 50% by mass and 50% by mass, respectively. Composition PE-3. The evaluation results are shown in Table 1. [Example 4] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-4 and B-1 were 60% by mass and 40% by mass, respectively. Composition PE-4. The evaluation results are shown in Table 1. [Example 5] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-5 and B-4 were 80% by mass and 20% by mass, respectively. Composition PE-5. The evaluation results are shown in Table 1. [Example 6] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-2 and B-5 were 70% by mass and 30% by mass, respectively. Composition PE-6. The evaluation results are shown in Table 1. [Example 7] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-3 and B-6 were 80% by mass and 20% by mass, respectively. Composition PE-7. The evaluation results are shown in Table 1. [Example 8] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-4 and B-10 were 80% by mass and 20% by mass, respectively. Composition PE-8. The evaluation results are shown in Table 1. [Example 9] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-5 and B-11 were 30% by mass and 70% by mass, respectively. Composition PE-9. The evaluation results are shown in Table 1. [Comparative Example 1] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-6 and B-1 were 54 mass% and 46 mass%, respectively. Composition PE-10. The evaluation results are shown in Table 1. [Comparative Example 2] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-7 and B-2 were made 45% by mass and 55% by mass, respectively. Composition PE-11. The evaluation results are shown in Table 1. [Comparative Example 3] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-8 and B-8 were 80% by mass and 20% by mass, respectively. Composition PE-12. The evaluation results are shown in Table 1. [Comparative Example 4] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-9 and B-3 were 20% by mass and 80% by mass, respectively. Composition PE-13. The evaluation results are shown in Table 1. [Comparative Example 5] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-10 and B-12 were 50% by mass and 50% by mass, respectively. Composition PE-14. The evaluation results are shown in Table 1. [Comparative Example 6] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-11 and B-12 were 60% by mass and 40% by mass, respectively. Composition PE-15. The evaluation results are shown in Table 1. [Comparative Example 7] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1 except that A-12 and B-1 were 20% by mass and 80% by mass, respectively. Composition PE-16. The evaluation results are shown in Table 1. [Comparative Example 8] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-6 and B-1 were 80% by mass and 20% by mass, respectively. Composition PE-17. The evaluation results are shown in Table 1. [Comparative Example 9] A polyethylene resin was obtained by the same operation as in the production of the polyethylene resin composition PE-1 of Example 1, except that A-3 and B-12 were 50% by mass and 50% by mass, respectively. Composition PE-17. The evaluation results are shown in Table 1. The difference in weight between high-density polyethylene and high-pressure low-density polyethylene is large, and the particle size is not uniform. It is classified on the funnel directly above the extruder, so the dispersion is poor, and Wmax and the maximum dissolution peak temperature are lower. . [Table 1] [Industrial Applicability] The polyethylene resin composition of the present invention is excellent in tearability and hand tearability, and has high cleanliness. Therefore, it can be used as an easily tearable packaging material for food and medicine, The base material of the tape that can be torn in the horizontal direction can be used especially for easy tearing and cleanliness (non-polluting), and can be used as a packing material for rice balls. Furthermore, since the amount of chlorine is extremely small, it can also be used as a packaging material for electronic parts such as semiconductors and parts trays for avoiding malfunction due to the adhesion of chlorine atoms.

Claims (7)

A polyethylene resin composition having a density of 930 to 960 kg / m ³ , a melt flow rate of 1 to 20 g / 10 minutes at 190 ° C. and 2.16 kg, and a TFC using a CFC device under the following conditions (Determination of elevated temperature dissolution classification) During the measurement, one or more peaks of the dissolution temperature-dissolution amount curve appeared below 80 ° C, and one or more peaks appeared above 90 ° C. The peak (Wmax) that became the maximum of the dissolution amount was at 90 ° C. The above appears, and the maximum value is more than 10% by weight of the total dissolution amount; (1) Weigh 20 mg of the above polyethylene resin composition and inject 0.5 ml of o-dichlorobenzene; (2) Hold at 140 ° C for 120 minutes to make The polyethylene resin composition was completely dissolved, and the solution was introduced into a TREF column; (3) The temperature was lowered from 140 ° C to 0.5 ° C / min to 40 ° C, and it was precipitated in the column and kept at 40 ° C for 20 minutes; The temperature was raised from 40 ° C to 140 ° C at 1 ° C, and the temperature was maintained at each temperature for 15 minutes or more, and then TREF measurement was performed to measure the amount of dissolution. For example, the polyethylene resin composition of claim 1, wherein the ratio Wmax / W1 of the maximum dissolution amount (Wmax) to the maximum dissolution amount (W1) at a dissolution temperature of 60 to 80 ° C measured by TREF is 2.0 or more. The polyethylene resin composition according to claim 1 or 2, comprising 30 to 80% by mass of the high-density polyethylene resin (A) and 20 to 70% by mass of the low-density polyethylene resin (B) by the high-pressure method. For example, the polyethylene resin composition of claim 1 or 2, wherein in the DSC measurement, it is melted at 180 ° C for 5 minutes, and the temperature is lowered at a cooling rate of 80 ° C / minute under the extrapolated crystallization starting temperature (Tic ) The measurement was performed at a higher temperature of 1 ° C. At this time, the 1/2 isothermal crystallization time was 0.7 minutes or more. The polyethylene resin composition according to claim 3, wherein the high-density polyethylene resin (A) is an ethylene homopolymer, an ethylene-propylene copolymer, or an ethylene-butene copolymer. The polyethylene resin composition according to claim 3, wherein the high-density polyethylene resin (A) is produced by polymerizing a supported metallocene catalyst (C) and a liquid auxiliary catalyst component (D), The supported metallocene catalyst (C) consists of (a) a carrier substance, (b) an organoaluminum compound, (c) a transition metal compound having a cyclic η-bondable anionic ligand, and (d) An activator prepared by reacting a transition metal compound having a cyclic η-bondable anionic ligand to form a complex that exhibits catalytic activity. The polyethylene resin composition according to claim 1 or 2, wherein the content of the chlorine atom is not more than 2.0 mass ppm relative to the polyethylene resin composition.