JP2021070808A - ETHYLENE-α-OLEFIN COPOLYMER, METHOD OF PRODUCING ETHYLENE-α-OLEFIN COPOLYMER, ETHYLENE-BASED RESIN COMPOSITION, AND FILM - Google Patents

Abstract

To provide an ethylene-α-olefin copolymer capable of forming a film having excellent slipperiness and suppressed fish eyes, a method of producing the ethylene-α-olefin copolymer, an ethylene-based resin composition containing the ethylene-α-olefin copolymer, and a film containing the ethylene-α-olefin copolymer or the ethylene-based resin composition.SOLUTION: An ethylene-α-olefin copolymer according to the present invention has: a monomer unit (1) based on ethylene; and a monomer unit (2) based on an α-olefin having 3 to 20 carbon atoms, wherein a branching parameter is 0.70 to 0.90, and a light scattering area ratio is 1.60 to 3.60.SELECTED DRAWING: None

Description

The present invention relates to an ethylene-α-olefin copolymer, a method for producing the ethylene-α-olefin copolymer, an ethylene resin composition containing the ethylene-α-olefin copolymer, and the ethylene-α. -Regarding a film containing an olefin copolymer or the ethylene resin composition.

Conventionally, as a film for packaging foods, detergents, etc., a laminated film in which a base film and a sealant film are laminated is widely used. The sealant film is required to have excellent heat sealability, transparency and strength. As a sealant film having such performance, a film containing an ethylene-α-olefin copolymer has been proposed in recent years (for example, Patent Documents 1 and 2).

When producing a laminated film using a sealant film, the sealant film is further required to have excellent slipperiness. As a film having good slipperiness, for example, Patent Document 3 has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, and has a density of 915 kg / m ^3. The melt flow rate measured under the conditions of 950 kg / m ³ or less, a temperature of 190 ° C. and a load of 21.18 N is 0.0001 g / 10 minutes or more and 0.2 g / 10 minutes or less, and zero shear at a temperature of 190 ° C. A film containing an ethylene-α-olefin copolymer having a viscosity of 1 × 10 ⁵ Pa · sec or more and 1 × 10 ^{7 Pa · sec or less is disclosed.}

Japanese Unexamined Patent Publication No. 2004-256613 Japanese Unexamined Patent Publication No. 2000-44739 International Publication No. 2018/164169

However, although the film described in Patent Document 3 is excellent in slipperiness, there is a problem that the appearance is inferior because many fisheyes (film defects) occur.

The present invention has been made in view of such a problem, and is an ethylene-α-olefin copolymer capable of forming a film having excellent slipperiness and capable of suppressing the generation of fish eyes. , The method for producing the ethylene-α-olefin copolymer, the ethylene-based resin composition containing the ethylene-α-olefin copolymer, and the ethylene-α-olefin copolymer or the ethylene-based resin composition. It is an object of the present invention to provide a film containing the above.

The ethylene-α-olefin copolymer according to the present invention contains a monomer unit (1) based on ethylene and a monomer unit (2) based on an α-olefin having 3 to 20 carbon atoms, and is described below. The degree of cross-linking parameter represented by the formula (i) is 0.70 or more and 0.90 or less, and the light scattering area ratio represented by the following formula (ii) is 1.60 or more and 3.60 or less.

（式中、Ｍは、エチレン−α−オレフィン共重合体の絶対分子量を示す。Ｗ_Ｍは、絶対分子量Ｍにおけるエチレン−α−オレフィン共重合体の重量分率を示す。ｇ’_Ｍは、絶対分子量Ｍにおける固有粘度比を示す。）

(Wherein, M is .W _M is indicative of the absolute molecular weight of the ethylene -α- olefin copolymer, .g _'M indicating the weight fraction of ethylene -α- olefin copolymer in an absolute molecular weight M, the absolute The intrinsic viscosity ratio at the molecular weight M is shown.)

（式中、ＬＳは、エチレン−α−オレフィン共重合体をオルトジクロロベンゼンに２ｍｇ／ｍＬの濃度で溶解させた溶液の光散乱面積を示す。ＬＳ’は、標準ポリエチレンＮＩＳＴ１４７５ａをオルトジクロロベンゼンに２ｍｇ／ｍＬの濃度で溶解させた溶液の光散乱面積を示す。）

(In the formula, LS indicates the light scattering area of a solution in which an ethylene-α-olefin copolymer is dissolved in orthodichlorobenzene at a concentration of 2 mg / mL. LS'indicates standard polyethylene NIST1475a in 2 mg orthodichlorobenzene. Indicates the light scattering area of the solution dissolved at a concentration of / mL.)

In the method for producing an ethylene-α-olefin copolymer according to the present invention, an ethylene-based monomer unit (1) and an α-olefin-based monomer unit (2) having 3 to 20 carbon atoms are used. A method for producing an ethylene-α-olefin copolymer containing an ethylene-α-olefin copolymer, which comprises the following steps (a) to (c).
(A) Prepolymerization of ethylene and α-olefin having 3 to 20 carbon atoms in the presence of a catalyst component formed by contacting a metallocene complex, an organic aluminum compound, and a co-catalyst carrier. Step of obtaining a catalyst component (b) A step of contacting an organic aluminum compound with oxygen gas and then contacting with an electron donating compound to obtain a coordination compound (c) The prepolymerization catalyst component and the coordination compound A step of gas-phase polymerization of ethylene and α-olefin having 3 to 20 carbon atoms in the presence of a polymerization catalyst formed by contacting ethylene-α-olefin copolymer to obtain an ethylene-α-olefin copolymer.

The ethylene-based resin composition according to the present invention comprises the above-mentioned ethylene-α-olefin copolymer and an ethylene-based polymer containing an ethylene-based monomer unit (however, the ethylene-α-olefin copolymer is (Different) and contains.

The film according to the present invention contains the above-mentioned ethylene-α-olefin copolymer or the above-mentioned ethylene-based resin composition.

According to the present invention, an ethylene-α-olefin copolymer capable of forming a film having excellent slipperiness and capable of suppressing the generation of fisheye, and the ethylene-α-olefin copolymer. A production method, an ethylene-based resin composition containing the ethylene-α-olefin copolymer, and a film containing the ethylene-α-olefin copolymer or the ethylene-based resin composition can be provided.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

<Definition>
In the present specification, the following terms are defined or explained as follows.

The "ethylene-α-olefin copolymer" is a copolymer having a monomer unit based on ethylene and a monomer unit based on α-olefin, and the total mass of the copolymer is 100. In terms of mass%, it means a copolymer in which the total content of ethylene-based monomeric units and α-olefin-based monomeric units is 95% by mass or more.

The "ethylene-based polymer" is a polymer having a monomer unit based on ethylene, and the content of the monomer unit based on ethylene is 50 when the total mass of the polymer is 100% by mass. A polymer having a mass% or more.

The "α-olefin" refers to a linear or branched olefin having a carbon-carbon unsaturated double bond at the α-position.

The "ethylene-based resin composition" refers to a composition containing an ethylene-based polymer.

The melt flow rate (hereinafter, also referred to as MFR) in the present specification is a value (unit: g / 10 minutes) measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N in accordance with the method A specified in JIS K7210-1995. ).

The density in the present specification refers ^{to a value (unit: kg / m 3} ) measured according to the method A specified in JIS K7112-1980 after performing the annealing described in JIS K6760-1980.

<Ethylene-α-olefin copolymer>
The ethylene-α-olefin copolymer (hereinafter, also referred to as component (A)) according to the present embodiment is based on an ethylene-based monomer unit (1) and an α-olefin having 3 to 20 carbon atoms. Includes the monomeric unit (2). The monomer unit (2) is preferably a monomer unit based on an α-olefin having 4 to 8 carbon atoms.

Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4 -Methyl-1-pentene, 4-methyl-1-hexene and the like can be mentioned. Among these, the α-olefin having 3 to 20 carbon atoms is preferably 1-hexene, 4-methyl-1-pentene, or 1-octene, and is 1-hexene or 1-octene. Is more preferable. As the monomer unit (2) based on the α-olefin having 3 to 20 carbon atoms, one type may be used alone, or two or more types may be used in combination.

When the total mass of the component (A) is 100% by mass, the content of the monomer unit (1) is preferably 90% by mass or more, and preferably 97% by mass or less. Further, when the total mass of the component (A) is 100% by mass, the content of the monomer unit (2) is preferably 3% by mass or more, and preferably 10% by mass or less. In one embodiment, the component (A) has a monomer unit (1) content of 90% by mass or more and a monomer unit (2) content when the total mass is 100% by mass. It is 10% by mass or less.

Examples of the component (A) include ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, and ethylene-1-butene-1-hexene. Examples thereof include a polymer, an ethylene-1-butene-4-methyl-1-pentene copolymer, an ethylene-1-hexene-1-octene copolymer, and an ethylene-1-butene-1-octene copolymer. Among these, the component (A) is an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, an ethylene-1-butene-1-hexene copolymer, or an ethylene-1-butene-1. It is preferably an octene copolymer, more preferably an ethylene-1-hexene copolymer or an ethylene-1-butene-1-hexene copolymer.

The component (A) may have other monomer units based on a monomer other than ethylene and α-olefin having 3 to 20 carbon atoms. Other monomers include, for example, conjugated diene such as butadiene or isoprene; non-conjugated diene such as 1,4-pentadiene; acrylic acid; acrylic acid ester such as methyl acrylate or ethyl acrylate; methacrylic acid; methacrylic acid. Methacrylic acid esters such as methyl or ethyl methacrylate; vinyl acetate and the like can be mentioned.

The component (A) has a degree of cross-linking parameter represented by the following formula (i) of 0.70 or more and 0.90 or less, preferably 0.70 or more and 0.80 or less.

In the formula (i), M represents the absolute molecular weight of the ethylene-α-olefin copolymer. W _M denotes the weight fraction of ethylene -α- olefin copolymer in an absolute molecular weight M. g _'M denotes the intrinsic viscosity ratio of the absolute molecular weight M.

The weight fraction _{W M} and intrinsic viscosity ratio g _'M of the absolute molecular weight ethylene -α- olefin copolymer in M the absolute molecular weight M ethylene -α- olefin copolymer ¹⁰ 4.3 to 10 ^5. Measure in the range of ^5.

Intrinsic viscosity ratio g _'M can be calculated using (iii) below formula.
_{g 'M = [η] M} /(6.31×10 -4 × M 0.69) ··· (iii)

In the formula (iii), M indicates the absolute molecular weight of the ethylene-α-olefin copolymer. [Η] _M indicates the intrinsic viscosity of the ethylene-α-olefin copolymer at the absolute molecular weight M.

In the above equation (iii), ^{the value of (6.31 × 10 -4} × M ^0.69 ) is such that the absolute molecular weight M of the ethylene-α-olefin copolymer is the same as the absolute molecular weight of the standard polyethylene NIST1475a. It can be calculated as being. That is, the value of (6.31 × 10 ^-4 × M ^0.69 ) corresponds to the intrinsic viscosity of the standard polyethylene NIST1475a at the absolute molecular weight M.

In the above formula (i) and (iii) wherein the absolute molecular weight of the ethylene -α- olefin copolymer M, the weight fraction W _M ethylene -α- olefin copolymer in an absolute molecular weight _M, and, at the absolute molecular weight M The intrinsic viscosity [η] _M of the ethylene-α-olefin copolymer can be measured using a gel permeation chromatograph (GPC) equipped with a differential refractometer, a viscosity detector and a light scattering detector. ..

The conditions for GPC measurement are shown below.
-GPC device: HLC-8121 GPC / HT (manufactured by Tosoh Corporation)
-Light scattering detector: PD2040 (manufactured by Precision Detectors)
-Laser light source: Wavelength 685 nm
-Viscosity detector: H502 (manufactured by Viscotek)
-GPC column: GMHHR-H (S) HT (manufactured by Tosoh Corporation) x 3-Sample solution concentration: 2 mg / mL
・ Injection amount: 300 μL
-Measurement temperature: 140 ° C
-Dissolution conditions: Stir at 145 ° C for 2 hours-Solvent and mobile phase: Ortodichlorobenzene containing 0.05% by mass of dibutylhydroxytoluene (Wako special grade)
-Mobile phase flow velocity: 1.0 mL / min-Measurement time: Approximately 1 hour-Molecular weight standard substance: Standard polystyrene-Data acquisition interval: 1.74 seconds

As for the degree of cross-linking parameter, in the method for producing an ethylene-α-olefin copolymer described later, for example, ethylene bis (indenyl) zirconium diphenoxide is used as a catalyst component, and a zinc compound is supported on a fine particle carrier as a co-catalyst carrier. The amount of oxygen gas used in contact with the organoaluminum compound is 1 to 100 mol% with respect to the number of moles of aluminum atoms of the organoaluminum compound, and triisobutylaluminum is used as the organoaluminum compound. The amount of the donor compound used is set to 1 to 50 mol% with respect to the number of moles of aluminum atoms of the organoaluminum compound, and the polymerization pressure is set to 1 to 3 MPa, so that the amount is in the range of 0.70 or more and 0.90 or less. Can be adjusted.

The light scattering area ratio of the component (A) represented by the following formula (ii) is 1.60 or more and 3.60 or less, preferably 2.70 or more and 3.00 or less.

In formula (ii), LS indicates the light scattering area of a solution of an ethylene-α-olefin copolymer dissolved in orthodichlorobenzene at a concentration of 2 mg / mL. LS'indicates the light scattering area of a solution of standard polyethylene NIST1475a dissolved in orthodichlorobenzene at a concentration of 2 mg / mL.

In the above equation (ii), the light scattering areas LS and LS'can be measured by using liquid chromatography (LC) equipped with a light scattering detector.

The conditions for LC measurement are shown below.
-LC device: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
・ Separation column: None ・ Measurement temperature: 140 ℃
-Solvent and mobile phase: Ortodichlorobenzene containing 0.05% by mass of dibutylhydroxytoluene (Wako special grade)
-Mobile phase flow velocity: 1.0 mL / min-Sample solution concentration: 2 mg / mL
・ Injection amount: 300 μL
-Molecular weight standard substance: Standard polystyrene-Data acquisition interval: 1.74 seconds

The light scattering area ratio is such that in the method for producing an ethylene-α-olefin copolymer described later, the amount of oxygen gas used in contact with the organoaluminum compound is 1 to 100 mol% with respect to the number of moles of aluminum atoms of the organoaluminum compound. Triisobutylaluminum is used as the organoaluminum compound, the electron-donating compound is brought into contact with the mixed contact material of organoaluminum and oxygen, and the amount of the electron-donating compound used is adjusted to the number of moles of aluminum atoms of the organoaluminum compound. On the other hand, the ratio of hydrogen to ethylene during gas phase polymerization should be adjusted to the range of 1.60 or more and 3.60 or less by a method such as 1 to 50 mol% or 0.15% to 0.40%. Can be done.

The component (A) has a melt flow rate (MFR) of 0.010 g / 10 minutes or more measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N from the viewpoint of reducing the extrusion load during film formation. It is more preferable, 0.020 g / 10 minutes or more, and even more preferably 0.030 g / 10 minutes or more. Further, from the viewpoint of further improving the slipperiness of the film, the component (A) preferably has an MFR of 0.2 g / 10 minutes or less, more preferably 0.015 g / 10 minutes or less, and 0. It is more preferably 1.013 g / 10 minutes or less. In one embodiment, the component (A) has an MFR of 0.010 g / 10 minutes or more and 0.2 g / 10 minutes or less. In the measurement of the MFR of the component (A), a sample containing about 1000 ppm of an antioxidant in the component (A) is usually used. The MFR is in the range of 0.010 g / 10 minutes or more and 0.2 g / 10 minutes or less by adjusting the chain transfer agent concentration during gas phase polymerization in the method for producing an ethylene-α-olefin copolymer described later. Can be adjusted to.

It components (A), from the viewpoint of improving the slipperiness of the film, it is preferable that density of 910 kg / ^{m 3} or more, more preferably 918 kg / ^{m 3} or more and 922 kg / ^{m 3} or more Is even more preferable. Further, component (A), from the viewpoint of suppressing the occurrence of fish eyes of the film, it is preferable that density of 940 kg / ^{m 3} or less, more preferably 935 kg / ^{m 3} or less, 930 kg / ^{m 3} or less Is more preferable. In one embodiment, the component (A) has a density of 910 kg / m ³ or more and 940 kg / m ³ or less. ^{The density can be adjusted to a range of 910 kg / m 3} or more and 940 kg / m ³ or less by adjusting the α-olefin concentration during vapor phase polymerization in the method for producing an ethylene-α-olefin copolymer described later. it can.

The component (A) is the ratio of the z-average molecular weight (hereinafter, also referred to as Mz) to the weight average molecular weight (hereinafter, also referred to as Mw) (hereinafter, referred to as Mz / Mw) from the viewpoint of further improving the slipperiness of the film. ) Is preferably 2.0 or more, more preferably 2.1 or more, and even more preferably 2.2 or more. Further, the component (A) preferably has Mz / Mw of 5.0 or less, more preferably 4.0 or less, and 3.0 or less, from the viewpoint of suppressing the generation of fish eyes in the film. It is more preferable to have. The component (A) has Mz / Mw of 2.0 or more and 5.0 or less in one embodiment, Mz / Mw of 2.1 or more and 4.0 or less in another embodiment, and still another aspect. Mz / Mw is 2.2 or more and 3.0 or less. Mz / Mw can be controlled by adjusting the amount of the electron donating compound used with respect to the amount of the organoaluminum compound used during the gas phase polymerization. Specifically, by adjusting the amount of the electron-donating compound used to the amount of the organoaluminum compound used as a molar ratio of 6% to 12% with respect to the organoaluminum, Mz / Mw is adjusted to 2.0 or more and 5.0 or less. Can be controlled.

The weight average molecular weight (Mw) and z average molecular weight (Mz) can be measured using a gel permeation chromatograph (GPC) apparatus equipped with a differential refractive index detector. The conditions for GPC measurement are shown below.
-GPC device: HLC-8121 GPC / HT (manufactured by Tosoh Corporation)
-GPC column: TSKgelGMH _6- HT (manufactured by Tosoh Corporation)
-Measurement temperature: 140 ° C
-Solvent and mobile phase: Ortodichlorobenzene containing 0.05% by mass of dibutylhydroxytoluene (Wako special grade)
-Mobile phase flow velocity: 1.0 mL / min-Sample solution concentration: 1 mg / mL
・ Injection amount: 300 μL
-Molecular weight standard substance: Standard polystyrene-Data acquisition interval: 2.5 seconds

The component (A) preferably has an intrinsic viscosity (hereinafter referred to as [η]; the unit is dl / g) of 1.0 dl / g or more from the viewpoint of further improving the slipperiness of the film. , 1.2 dl / g or more, and even more preferably 1.3 dl / g or more. Further, the component (A) preferably has a [η] of 2.0 dl / g or less, more preferably 1.9 dl / g or less, from the viewpoint of suppressing the generation of fish eyes in the film. It is more preferably .7 dl / g or less. In one embodiment, the component (A) has [η] of 1.0 dl / g or more and 2.0 dl / g or less, and in another embodiment, 1.2 dl / g or more and 1.9 dl / g or less. In still other embodiments, it is 1.3 dl / g or more and 1.7 dl / g or less. [Η] of the component (A) is measured using a Ubbelohde viscometer at a temperature of 135 ° C. using tetralin as a solvent.

The ethylene-α-olefin copolymer according to the present embodiment contains an ethylene-based monomer unit (1) and an α-olefin-based monomer unit (2) having 3 to 20 carbon atoms. The degree of cross-linking parameter represented by the above formula (i) is 0.70 or more and 0.90 or less, and the light scattering area ratio represented by the above formula (ii) is 1.60 or more and 3.60 or less. The ethylene-α-olefin copolymer can maintain the degree of branching of the polymer in a desired range by setting the degree of cross-linking parameter within the above range, and as a result, a film having excellent slipperiness. Can be formed. Further, the ethylene-α-olefin copolymer maintains the content of the gel component (component having a large molecular weight) contained in the polymer within a desired range by setting the light scattering area ratio within the above range. As a result, it is possible to form a film having excellent slipperiness and capable of suppressing the occurrence of fish eyes.

The ethylene-α-olefin copolymer according to the present embodiment preferably has a crosslinkability parameter of 0.70 or more and 0.80 or less. With such a structure, a film having better slipperiness can be formed.

The ethylene-α-olefin copolymer according to the present embodiment preferably has a light scattering area ratio of 2.70 or more and 3.00 or less. With such a configuration, it is possible to form a film having better slipperiness and capable of further suppressing the occurrence of fish eyes.

The ethylene-α-olefin copolymer according to the present embodiment has a monomer unit (1) content of 90% by mass or more and a monomer unit (2) when the total mass is 100% by mass. The content of is preferably 10% by mass or less. With such a configuration, it is possible to form a film having better slipperiness and capable of further suppressing the occurrence of fish eyes.

The ethylene-α-olefin copolymer according to the present embodiment has a melt flow rate (MFR) of 0.010 g / 10 minutes or more and 0.2 g / 10 minutes or less measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N. Is preferable. When the MFR of the ethylene-α-olefin copolymer is 0.010 g / 10 minutes or more, the extrusion load during film formation can be reduced. Further, when the MFR of the ethylene-α-olefin copolymer is 0.2 g / 10 minutes or less, a film having more excellent slipperiness can be formed.

The ethylene-α-olefin copolymer according to the present embodiment preferably has a density of 910 kg / m ³ or more and 940 kg / m ³ or less. When the density of the ethylene-α-olefin copolymer is 910 kg / m ³ or more, a film having more excellent slipperiness can be formed. Further, when the density of the ethylene-α-olefin copolymer is 940 kg / m ³ or less, it is possible to form a film capable of further suppressing the generation of fish eyes.

<Method for producing ethylene-α-olefin copolymer>
The method for producing an ethylene-α-olefin copolymer (component (A)) according to the present embodiment comprises the above-mentioned ethylene-based monomer unit (1) and the above-mentioned α-olefin having 3 to 20 carbon atoms. A method for producing an ethylene-α-olefin copolymer containing the monomer unit (2) based on the above, which comprises the following steps (a) to (c).
(A) Prepolymerization of ethylene and α-olefin having 3 to 20 carbon atoms in the presence of a catalyst component formed by contacting a metallocene complex, an organic aluminum compound, and a co-catalyst carrier. Step of obtaining a catalyst component (b) A step of contacting an organic aluminum compound with oxygen gas and then contacting with an electron donating compound to obtain a coordination compound (c) The prepolymerization catalyst component and the coordination compound A step of gas-phase polymerization of ethylene and α-olefin having 3 to 20 carbon atoms in the presence of a polymerization catalyst formed by contacting ethylene-α-olefin copolymer to obtain an ethylene-α-olefin copolymer.

In step (a), the metallocene complex is a transition metal compound having a ligand containing a cyclopentadiene-type anionic skeleton. As the metallocene complex, a transition metal compound represented by the following general formula [1] or a dimer of a μ-oxo type transition metal compound thereof is preferable.
L ² _a M ² X ¹ _b ... [1]
(In the equation, M ² is a transition metal atom of the Group 3-11 of the Periodic Table or the lanthanoid series. L ² is a group having a cyclopentadiene-type anion skeleton, and are a plurality of L ² directly linked to each other? Alternatively, they may be linked via residues containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. X ¹ is a halogen atom or a hydrocarbon group (provided that it is a cyclopentadiene type). (Excluding groups having an anionic skeleton) or hydrocarbon oxy groups. A represents 2 and b represents 2.)

In the general formula [1], M ² is a transition metal atom of the Group 3-11 or Lantanoid series of the Periodic Table (IUPAC 1989), for example, a scandium atom, an yttrium atom, a titanium atom, a zirconium atom, a hafnium atom, and a vanadium. Examples thereof include an atom, a niobium atom, a tantalum atom, a chromium atom, an iron atom, a ruthenium atom, a cobalt atom, a rhodium atom, a nickel atom, a palladium atom, a samarium atom, and an itterbium atom. ^{M 2} in the general formula [1] is preferably a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a chromium atom, an iron atom, a cobalt atom or a nickel atom, and is a titanium atom, a zirconium atom or a hafnium atom. Is more preferable, and a zirconium atom is further preferable.

In the general formula [1], L ² is eta ⁵ - a (substituted) indenyl group, the two L ² may be different even in the same. Two L ² each other, a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, are linked via a bridging group containing a sulfur atom or a phosphorus atom. eta ⁵ - (substituted) indenyl group may eta ⁵ may have a substituent - represents an indenyl group.

The (substituted) indenyl group, at least, 5, eta ⁵ 6-position is a hydrogen atom - - eta ⁵ in L ² (substituted) indenyl group, specifically, eta ⁵ - indenyl group, eta ⁵ -2-methylindenyl group, eta ^{5-3-methylindenyl} group, eta ^{5-4-methylindenyl} group, eta ^{5-7-methylindenyl} group, η ⁵ -2-tert- butyl indenyl group, eta ⁵ -3-tert-butyl indenyl group, η ⁵ -4-tert- butylindenyl group, η ⁵ -7-tert- butyl indenyl group, eta ^{5-2,3-dimethyl-indenyl} group, eta ⁵ 4,7-dimethyl-indenyl group, eta ^{5-2,4,7-trimethyl} indenyl group, eta ^{5-2-methyl-4-isopropylindenyl} group, eta ^5-4-phenyl indenyl group, eta ⁵ -2-methyl-4-phenyl indenyl group, eta ^{5-2-methyl-4-naphthyl} indenyl group, substituted versions thereof, and the like. ^{In this specification, "η 5-} " may be omitted from the name of the transition metal compound. L ² is preferably an indenyl group.

The two (substituted) indenyl groups are linked via a cross-linking group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples of the cross-linking group include an alkylene group such as an ethylene group and a propylene group; a substituted alkylene group such as a dimethylmethylene group and a diphenylmethylene group; a substituted silylene such as a silylene group, a dimethylsilylene group, a diphenylsilylene group and a tetramethyldisylylene group. Group: Examples include heteroatoms such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom. The cross-linking group is preferably an ethylene group, a dimethylmethylene group, or a dimethylsilylene group, and more preferably an ethylene group.

^{Examples of X 1} in the general formula [1] include a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene anion skeleton), a hydrocarbon oxy group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group, an alkenyl group and the like. Examples of the hydrocarbon oxy group include an alkoxy group, an aralkyloxy group, an aryloxy group and the like.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, a neopentyl group and an amyl group. Examples thereof include an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-pentadecyl group and an n-eicosyl group. The alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group substituted with the halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a per. Fluorohexyl group, perfluorooctyl group, perchloropropyl group, perchlorobutyl group, perbromopropyl group and the like can be mentioned. All of these alkyl groups are alkoxy groups such as methoxy group and ethoxy group; aryloxy group such as phenoxy group; aralkyloxy group such as benzyloxy group, even if some hydrogen atoms are substituted. Good.

Examples of the aralkyl group include a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, a (4-methylphenyl) methyl group, a (2,3-dimethylphenyl) methyl group, and (2). , 4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) Methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethyl) (Phenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n- Butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, Examples thereof include (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group and the like. The aralkyl group is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group is substituted. It may have as a group.

Examples of the aryl group include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-kisilyl group, a 2,4-kisilyl group, a 2,5-kisilyl group, and 2,6-. Kisilyl group, 3,4-kisilyl group, 3,5-kisilyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4 , 5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethyl Phenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butyl Phenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group And so on. The aryl group may be, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group. It may have as a substituent.

Examples of the alkenyl group include an allyl group, a metharyl group, a crotyl group, a 1,3-diphenyl-2-propenyl group and the like.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, a neopentoxy group and an n-hexoxy group. Examples thereof include an n-octoxy group, an n-dodesoxy group, an n-pentadesoxy group, an n-icosoxy group and the like. Examples of the alkoxy group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy group such as methoxy group and ethoxy group; aryloxy group such as phenoxy group; aralkyloxy group such as benzyloxy group and the like. It may have as a substituent.

Examples of the aralkyloxy group include a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, a (4-methylphenyl) methoxy group, and a (2,3-dimethylphenyl) methoxy group. (2,4-Dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethyl) (Phenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5 -Trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, ( 2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propyl) (Phenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n) -Octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like can be mentioned. The aralkyloxy group includes, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group and the like. May be used as a substituent.

Examples of the aryloxy group include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, a 2,4-dimethylphenoxy group, and a 2,5-dimethyl group. Phenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group , 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6 -Trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethyl Phenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6 -Di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy Group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2 , 3,5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group , Ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group , N-Tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like. The aryloxy group includes, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group and the like. May be used as a substituent. X ¹ is preferably a chlorine atom, a methoxy group, or a phenoxy group, more preferably a chlorine atom or a phenoxy group, and even more preferably a phenoxy group.

Specific examples of the metallocene-based complex include dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, and dimethylsilylenebis (". 2,3-Dimethylindenyl) titanium dichloride, dimethylsilylenebis (2,4,7-trimethylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylenebis (2) −Phenylindenyl) Titanium Dichloride, Dimethylsilylenebis (4-phenylindenyl) Titanium Dichloride, Dimethylsilylenebis (2-Methyl-4-phenylindenyl) Titanium Dichloride, Dimethylsilylenebis (2-Methyl-4-naphthylinde) Nyl) Titanium dichloride, a compound in which titanium of these compounds is changed to zirconium or hafnium, a compound in which dimethylsilylene is changed to methylene, ethylene, dimethylmethylene (isopropyridene), diphenylmethylene, diethylsilylene, diphenylsilylene or dimethoxycilylene, dichloride Difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxyd, diethoxydo, di (n-propoxide), di (isopropoxide), diphenoxide or di (pentafluorophenoxide) And so on.

Metallocene-based complexes include ethylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylmethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium diphenoxide, dimethylsilylenebis (indenyl) zirconium diphenoxide, Alternatively, it is preferably dimethylmethylenebis (indenyl) zirconium diphenoxide, more preferably ethylenebis (indenyl) zirconium diphenoxide.

In the step (a), examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, and trinormaloctylaluminum, and triisobutylaluminum and trinormalaloctylaluminum are preferable. More preferably, it is triisobutylaluminum.

In the step (a), the co-catalyst carrier (hereinafter, also referred to as the component (H)) is a carrier in which the component (I) is supported on the fine particle carrier.

The component (I) is preferably a zinc compound. That is, the component (H) is preferably a carrier in which a zinc compound is supported on a fine particle carrier. Examples of the zinc compound include compounds obtained by contacting diethylzinc (I1), fluorinated phenol (I2), and water (I3).

Examples of the fluorinated phenol (I2) include 3,4,5-trifluorophenol, 3,4,5-tris (trifluoromethyl) phenol, and 3,4,5-tris (pentafluorophenyl) phenol, 3 , 5-Difluoro-4-pentafluorophenylphenol, 4,5,6,7,8-pentafluoro-2-naphthol and the like. The fluorinated phenol is preferably 3,4,5-trifluorophenol.

The fine particle carrier is a porous substance having a 50% volume average particle diameter of 10 to 500 μm. The 50% volume average particle size is measured by, for example, a light scattering laser diffraction method. Examples of the fine particle carrier include inorganic substances and organic polymers. Examples of the inorganic substance include inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ ; smectite, montmorillonite, hectorite, and laponite. , Clay such as saponite and clay minerals. Examples of the organic polymer include polyethylene, polypropylene, styrene-divinylbenzene copolymer and the like. The fine particle carrier is preferably a fine particle carrier made of an inorganic substance (hereinafter, referred to as an inorganic fine particle carrier).

The pore volume of the fine particle carrier is usually 0.3 to 10 mL / g. The specific surface area of the fine particle carrier is usually 10 to 1000 m ² / g. The pore volume and the specific surface area are measured by the gas adsorption method, and the pore volume is determined by analyzing the amount of gas desorption by the BJH method and the specific surface area by analyzing the amount of gas adsorption by the BET method.

The components (H) are the component (I), diethylzinc (I1), fluorinated phenol (I2) and water (I3), an inorganic fine particle carrier (H1), and trimethyldisilazane (((CH _{3 ) 3} ). It can be obtained by contacting Si) _{2 NH) (H2).}

The inorganic fine particle carrier (H1) is preferably silica gel.

In the method for producing the component (I), the amount of each component (I1), component (I2), and component (I3) used is the molar ratio of the amount of each component used. When the component (I3) = 1: y: z, y and z can be used so as to satisfy the following formula.
| 2-y-2z | ≤1 ... [2]
z ≧ −2.5y + 2.48 ・ ・ ・ [3]
y <1 ... [4]
(In the above equations [2] to [4], y and z represent numbers larger than 0.)

The molar ratio y of the amount of the component (I2) used to the amount of the component (I1) used and the molar ratio z of the amount of the component (I3) used to the amount of the component (I1) are the above formulas [2], [ 3] and [4] are not particularly limited as long as they are satisfied. y is usually 0.55 to 0.99, preferably 0.55 to 0.95, more preferably 0.6 to 0.9, and 0.7 to 0.8. Is even more preferable. In order to obtain the ethylene-α-olefin copolymer according to the present embodiment, y is preferably 0.55 or more. When y is 1 or more, the obtained film containing the ethylene-α-olefin copolymer may cause an appearance defect such as fish eye.

The number of moles of zinc atoms derived from diethylzinc (I1) contained in 1 g of particles obtained by contact between diethylzinc (I1) and the inorganic fine particle carrier (H1) is preferably 0.1 mmol or more, more preferably 0. The amount of the component (I1) and the component (H1) used is adjusted so as to be 5 to 20 mmol. The amount of trimethyldisilazane (H2) used with respect to the component (H1) is preferably 0.1 mmol or more, more preferably 0.5 to 20 mmol of the component (H2) with respect to 1 g of the component (H1).

The amount of the metallocene complex used is preferably ^{5 × 10 -6 to} 5 × 10 ^-4 mol with respect to 1 g of the component (H). The amount of the organoaluminum compound used is preferably 1 to 2000 in terms of the ratio (Al / M) of the number of moles of aluminum atoms of the organoaluminum compound to the number of moles of metal atoms of the metallocene complex.

More specifically, the step (a) preferably includes the following steps (a1) to (a5).
Step (a1): A step of heat-treating a saturated aliphatic hydrocarbon compound solution containing a metallocene complex at 40 ° C. or higher to obtain a heat-treated product. Step (a2): The heat-treated product and co-catalyst carrier obtained in step (a1). Step (a3): Step of contacting the contact-treated product obtained in step (a2) with an organic aluminum compound to obtain a catalyst component (a4): Step (a3) Step (a5): Step of classifying the prepolymerized catalyst component obtained in step (a4) by prepolymerizing ethylene in the presence of the catalyst component obtained in

The saturated aliphatic hydrocarbon compound solution containing the metallocene complex in the step (a1) is prepared by, for example, a method of adding the metallocene complex to the saturated aliphatic hydrocarbon compound solvent. The metallocene complex is usually added as a powder or a slurry of a saturated aliphatic hydrocarbon compound solution.

Examples of the saturated aliphatic hydrocarbon compound used for preparing a saturated aliphatic hydrocarbon compound solution containing a metallocene-based complex include propane, normal butane, isopentane, normal pentane, isopentane, normal hexane, cyclohexane, and heptane. Be done. As the saturated aliphatic hydrocarbon compound solution, one kind of these saturated aliphatic hydrocarbon compounds may be used alone, or two or more kinds may be used in combination. The saturated aliphatic hydrocarbon compound preferably has a boiling point of 100 ° C. or lower at normal pressure, more preferably 90 ° C. or lower at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, normal. It is more preferably hexane or cyclohexane.

In the heat treatment of the saturated aliphatic hydrocarbon compound solution containing the metallocene complex, the temperature of the saturated aliphatic hydrocarbon compound solvent containing the metallocene complex may be adjusted to a temperature of 40 ° C. or higher. During the heat treatment, the solvent may be allowed to stand or the solvent may be agitated. The temperature is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of improving the moldability of the film. Further, the temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, from the viewpoint of enhancing the catalytic activity. The heat treatment time is usually 0.5 to 12 hours. The time is preferably 1 hour or more, and more preferably 2 hours or more, from the viewpoint of improving the moldability of the film. Further, the time is preferably 6 hours or less, and more preferably 4 hours or less, from the viewpoint of stability of the catalyst performance.

In the step (a2), the heat-treated product and the component (H) may come into contact with each other. Examples of the method of contacting include a method of adding the component (H) to the heat-treated product, and a method of adding the heat-treated product and the component (H) to the saturated aliphatic hydrocarbon compound. The component (H) is usually added as a powder or a slurry of a saturated aliphatic hydrocarbon compound solvent.

The temperature of the contact treatment in the step (a2) is preferably 70 ° C. or lower, more preferably 60 ° C. or lower. The temperature is preferably 10 ° C. or higher, more preferably 20 ° C. or higher. The contact treatment time is usually 0.1 hour or more and 2 hours or less.

In the step (a3), the contact-treated product obtained in the step (a2) may be brought into contact with the organoaluminum compound. As a method of contacting, for example, a method of adding an organoaluminum compound to the contact-treated product obtained in the step (a2), or a contact-treated product obtained in the step (a2) in a saturated aliphatic hydrocarbon compound. And an organoaluminum compound are added.

The temperature of the contact treatment in the step (a3) is preferably 70 ° C. or lower, more preferably 60 ° C. or lower. Further, the temperature is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, from the viewpoint of efficiently expressing the activity of the prepolymerization. The contact treatment time is usually 0.01 to 0.5 hours.

The contact treatment in the step (a3) is preferably carried out in the presence of ethylene, and if necessary, an α-olefin having 3 to 20 carbon atoms may coexist. Examples of the ethylene and α-olefin include olefins which are raw materials for prepolymerization. The amount of ethylene and α-olefin is preferably 0.05 g or more and 1 g or less per 1 g of the component (H).

In the above steps (a1) to (a3), the saturated aliphatic hydrocarbon compound, the component (H), the metallocene complex, and the organoaluminum compound are separately added to the prepolymerization reactor, thereby causing the step (a1). ) To (a3) may be performed in a prepolymerization reactor, steps (a2) and (a3) may be performed in a prepolymerization reactor, or step (a3) may be prepolymerized. It may be carried out in a reactor.

In the step (a4), ethylene and an α-olefin having 3 to 20 carbon atoms are prepolymerized (a small amount of ethylene and an α-olefin are polymerized) in the presence of the catalyst component obtained in the step (a3). This is a step of obtaining a polymerization catalyst component. The prepolymerization is usually carried out by a slurry polymerization method, and the prepolymerization may be carried out by any of a batch type, a semi-batch type and a continuous type. Further, the prepolymerization may be carried out by adding a chain transfer agent such as hydrogen.

When the prepolymerization is carried out by the slurry polymerization method, a saturated aliphatic hydrocarbon compound is usually used as the solvent. Examples of the saturated aliphatic hydrocarbon compound include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, and heptane. As the saturated aliphatic hydrocarbon compound solution, one kind of these saturated aliphatic hydrocarbon compounds may be used alone, or two or more kinds may be used in combination. As the saturated aliphatic hydrocarbon compound, the boiling point at normal pressure is preferably 100 ° C. or lower, more preferably the boiling point at normal pressure is 90 ° C. or lower, and propane, normal butane, isobutane, normal pentane, isopentane, It is more preferably normal hexane or cyclohexane.

When the prepolymerization is carried out by the slurry polymerization method, the amount of the component (H) per liter of the solvent is usually 0.1 to 600 g, preferably 0.5 to 300 g, as the slurry concentration. The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be changed as appropriate, but the temperature at which the prepolymerization is started is preferably 45 ° C. or lower, and more preferably 40 ° C. or lower. The partial pressure of the olefins in the gas phase portion during the prepolymerization is usually 0.001 to 2 MPa, more preferably 0.01 to 1 MPa. The prepolymerization time is usually 2 minutes to 15 hours.

Examples of the α-olefin having 3 to 20 carbon atoms used in the prepolymerization include propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene and 1-decene. Examples thereof include 1-dodecene, 4-methyl-1-pentene and 4-methyl-1-hexene. Among these, the α-olefin having 3 to 20 carbon atoms is preferably 1-hexene, 4-methyl-1-pentene, or 1-octene, and is 1-hexene or 1-octene. Is more preferable. As the α-olefin having 3 to 20 carbon atoms, one type may be used alone, or two or more types may be used in combination.

The content of the prepolymerized polymer in the prepolymerization catalyst component is usually 0.01 to 1000 g, preferably 0.05 to 500 g, preferably 0.1 to 200 g, per 1 g of the component (H). More preferably.

In the step (a5), the prepolymerization catalyst component obtained in the step (a4) is dried by nitrogen flow, and then passed through a sieve through which the fine prepolymerization catalyst particles for olefin polymerization pass, so that the fine particles under the sieve are passed. This is a step of removing various prepolymerization catalyst components. The sieve mesh opening is usually 100 μm to 200 μm, preferably 140 μm to 160 μm. The step (a5) is usually carried out in an atmosphere of an inert gas such as nitrogen or argon.

More specifically, the step (b) preferably includes the following steps (b1) and (b2).
Step (b1): Contacting the organoaluminum compound with oxygen gas to obtain a contact-treated product Step (b2): Contacting the contact-treated product obtained in step (b1) with an electron-donating compound to coordinate Step to obtain compound

In the step (b1), the amount of oxygen gas used in contact with the organoaluminum compound is preferably 1 to 100 mol%, preferably 5 to 80 mol%, based on the number of moles of aluminum atoms of the organoaluminum compound. More preferably, it is more preferably 10 to 40 mol%.

The temperature of the contact treatment in the step (b1) is preferably 70 ° C. or lower, more preferably 50 ° C. or lower. The temperature is preferably 30 ° C. or higher, more preferably 40 ° C. or higher.

In the step (b2), examples of the electron donating compound include triethylamine, triisobutylamine, trinormal octylamine and the like, and triethylamine is preferable.

The amount of the electron donating compound used is preferably 1 to 50 mol%, more preferably 3 to 20 mol%, based on the number of moles of aluminum atoms of the organoaluminum compound.

In the step (b2), the contact-treated product obtained in the step (b1) may be brought into contact with the electron-donating compound. As a method of contacting, for example, a method of adding an electron donating compound to the contact-treated product obtained in the step (b1) is used.

The temperature of the contact treatment in the step (b2) is preferably 70 ° C. or lower, more preferably 50 ° C. or lower. The temperature is preferably 30 ° C. or higher, more preferably 40 ° C. or higher.

In step (c), an ethylene-α-olefin copolymer is obtained by using a vapor phase polymerization method. Preferably, a continuous vapor phase polymerization method is used to obtain an ethylene-α-olefin copolymer. The gas phase polymerization reaction apparatus used in the continuous vapor phase polymerization method is usually an apparatus having a fluidized bed type reaction vessel, and an apparatus having a fluidized bed type reaction vessel having an enlarged portion is preferable. A stirring blade may be installed in the reaction vessel.

In the step (c), the polymerization catalyst is a polymerization catalyst containing a prepolymerization catalyst component, and as a method of supplying the prepolymerization catalyst component to the continuous polymerization reaction tank for forming the particles of the component (A), argon is usually used. A method of supplying in a water-free state using an inert gas such as Nitrogen, hydrogen, ethylene, or the like, or a method of dissolving or diluting each component in a solvent and supplying in a solution or slurry state is used.

The polymerization temperature is usually lower than the temperature at which the component (A) melts, preferably 0 to 150 ° C, more preferably 30 to 100 ° C, and further preferably 70 ° C to 87 ° C. preferable. Hydrogen may be added in order to adjust the melt fluidity of the component (A). Hydrogen is preferably controlled to be 0.01 to 1.1 mol% with respect to 100 mol% of ethylene. The ratio of hydrogen to ethylene during the vapor phase polymerization can be controlled by the amount of hydrogen generated during the polymerization and the amount of hydrogen added during the polymerization. An inert gas may coexist in the mixed gas of the polymerization reaction tank.

After the step of producing the component (A) in the continuous gas phase polymerization reaction tank, the step of transferring the component (A) to a container different from the gas phase polymerization reaction tank and bringing it into contact with water may be included. In this step, it is preferable that water is mixed with nitrogen and heated to 50 ° C. or higher to come into contact with the component (A). Further, it is preferable that the water mixed with nitrogen has a vapor pressure lower than the saturated vapor pressure and comes into contact with the component (A) as a gas. Further, the contact time between water and the component (A) is usually 0.5 to 3 hours, preferably 1 to 2 hours.

The method for producing an ethylene-α-olefin copolymer according to the present embodiment includes an ethylene-based monomer unit (1) and an α-olefin-based monomer unit (2) having 3 to 20 carbon atoms. A method for producing an ethylene-α-olefin copolymer comprising the above steps (a) to (c). The ethylene-α-olefin copolymer obtained by the above-mentioned production method can form a film having excellent slipperiness and capable of suppressing the generation of fish eyes.

In the method for producing an ethylene-α-olefin copolymer according to the present embodiment, it is preferable that the co-catalyst carrier is a carrier in which a zinc compound is supported on a fine particle carrier. With such a structure, a film having excellent slipperiness can be formed.

<Ethylene resin composition>
The ethylene-based resin composition according to the present embodiment is an ethylene-based polymer containing the above-mentioned ethylene-α-olefin copolymer (component (A)) and an ethylene-based monomer unit (however, the above-mentioned ethylene-α). -Contains (different from the olefin copolymer) (hereinafter, also referred to as component (B)).

The component (B) has a melt flow rate (MFR) measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N from the viewpoint of film molding processability, particularly from the viewpoint of reducing the extrusion load during film formation. It is preferably 0.010 g / 10 minutes or more, more preferably 0.1 g / 10 minutes or more, and further preferably 1 g / 10 minutes or more. Further, the component (B) is preferably 5 g / 10 minutes or less, more preferably 4 g / 10 minutes or less, and further preferably 3 g / 10 minutes or less from the viewpoint of film strength. In one embodiment, the component (B) has an MFR of 0.010 g / 10 minutes or more and 5 g / 10 minutes or less. In the measurement of the MFR of the component (B), a sample containing about 1000 ppm of an antioxidant in the component (B) is usually used. The MFR can be adjusted in the range of 0.010 g / 10 minutes or more and 5 g / 10 minutes or less by adjusting the chain transfer agent concentration at the time of polymerization.

It component (B), from the viewpoint of further improving the slipperiness of the film, it is preferable that density of 910 kg / ^{m 3} or more, more preferably 911kg / ^{m 3} or more and 912 kg / ^{m 3} or more Is even more preferable. Further, it is the component (B), from the viewpoint of improving the strength of the film, it is preferable that density of 940 kg / ^{m 3} or less, more preferably 930 kg / ^{m 3} or less, 920 kg / ^{m 3} or less Is even more preferable. In one embodiment, the component (B) has a density of 910 kg / m ³ or more and 940 kg / m ³ or less.

In one embodiment, the component (B) has a melt flow rate of 0.01 g / 10 min or more and 5 g / 10 min or less and a density of 910 kg / m ^{3 measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N.} More than 940 kg / m ³ or less.

The component (B) is the ratio of the z-average molecular weight (hereinafter, also referred to as Mz) to the weight average molecular weight (hereinafter, also referred to as Mw) (hereinafter, also referred to as Mz) from the viewpoint of improving the heat sealability, transparency, strength, etc. of the film. , Mz / Mw) is preferably 1.3 or more, more preferably 1.4 or more, and even more preferably 1.5 or more. Further, from the viewpoint of reducing the extrusion load during film formation, the component (B) preferably has Mz / Mw of 2.2 or less, more preferably 2.1 or less, and 2.0 or less. Is more preferable. The component (B) has Mz / Mw of 1.3 or more and 2.2 or less in one embodiment, Mz / Mw of 1.4 or more and 2.1 or less in another embodiment, and still another aspect. Mz / Mw is 1.5 or more and 2.0 or less. The weight average molecular weight (Mw) and the z average molecular weight (Mz) are determined by the same method as for the component (A).

The component (B) can be produced by polymerizing ethylene in the presence of a metallocene-based polymerization catalyst or a Ziegler-Natta-based polymerization catalyst.

Examples of the metallocene-based polymerization catalyst include the following catalysts (C1) to (C4).
(C1) A catalyst composed of a component containing a transition metal compound having a group having a cyclopentadiene-type skeleton and a component containing an armoxane compound (C2) A component containing the transition metal compound and ions such as tritylborate and aniliniumborate. Catalyst (C3) composed of a component containing a sex compound A catalyst (C4) (C1) to (C3) composed of a component containing the transition metal compound, a component containing the ionic compound, and an organoaluminum compound. A catalyst obtained by supporting or impregnating each component described in any one of the above with _{an inorganic particulate carrier such as SiO 2} , Al ₂ O _3, or a particulate polymer carrier such as an olefin polymer such as ethylene or styrene.

The Ziegler-Natta-based polymerization catalyst is a so-called Mg-Ti-based Ziegler catalyst (for example, "Catalyst Utilization Dictionary; published by the 2004 Industrial Research Council"), which is a combination of a solid catalyst component in which a titanium compound is supported on a magnesium compound and organoaluminum. , "Application system diagram-Transition of olefin polymerization catalyst-; published by the Institute of Invention and Innovation in 1995", etc.) is preferably used.

The catalyst used for producing the component (B) is preferably a metallocene-based polymerization catalyst from the viewpoint of film strength.

Examples of the polymerization method of the component (B) include bulk polymerization, solution polymerization, slurry polymerization, gas phase polymerization, and high-pressure ion polymerization. Here, bulk polymerization refers to a method of polymerizing using a liquid olefin as a medium at a polymerization temperature, and solution polymerization and slurry polymerization are inert hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, and octane. A method of polymerizing in a solvent. Further, the gas phase polymerization refers to a method of polymerizing a gaseous monomer in the medium using a gaseous monomer as a medium. These polymerization methods may be either a batch type or a continuous type, and may be a single-stage type performed in a single polymerization tank or a multi-stage type performed in a polymerization apparatus in which a plurality of polymerization reaction tanks are connected in series. But it may be. Various conditions (polymerization temperature, polymerization pressure, monomer concentration, catalyst addition amount, polymerization time, etc.) in the polymerization step may be appropriately determined.

The ethylene resin composition preferably has a content of the component (A) of 1% by mass or more, preferably 5% by mass, based on a total content of the component (A) and the component (B) of 100% by mass. More preferably, it is more preferably 10% by mass or more. Further, the ethylene resin composition preferably contains 30% by mass or less of the component (A) with respect to 100% by mass of the total content of the component (A) and the component (B). It is more preferably mass% or less, and further preferably 25 mass% or less. In one embodiment, the ethylene resin composition has a content of the component (A) of 1% by mass or more and 30% by mass or less with respect to a total content of the component (A) and the component (B) of 100% by mass. Is.

The method for producing the ethylene-based resin composition is not particularly limited, and examples thereof include known blending methods. Known blending methods include, for example, a method of dry blending each polymer, a method of melt blending, and the like. Examples of the dry blending method include a method using various blenders such as a Henschel mixer and a tumbler mixer. Examples of the melt blending method include a method using various mixers such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, and a thermal roll.

The ethylene-based resin composition according to the present embodiment contains an ethylene-α-olefin copolymer (component (A)) and an ethylene-based polymer containing an ethylene-based monomer unit (component (B)). To do. With such a configuration, it is possible to form a film having excellent slipperiness and capable of suppressing the occurrence of fish eyes.

The ethylene resin composition according to the present embodiment has a melt flow rate of 0.01 g / 10 minutes or more and 5 g / 10 minutes or less and a density of 910 kg / m measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N. it is preferably ³ or more 940 kg / ^{m 3} or less. With such a configuration, it is possible to form a film having better slipperiness and capable of further suppressing the occurrence of fish eyes.

The ethylene resin composition according to the present embodiment contains the ethylene-α-olefin copolymer based on 100% by mass of the total content of the ethylene-α-olefin copolymer and the ethylene polymer. The amount is preferably 1% by mass or more and 30% by mass or less. With such a configuration, it is possible to form a film having better slipperiness and capable of further suppressing the occurrence of fish eyes.

<Film>
The film according to this embodiment contains the above-mentioned ethylene-α-olefin copolymer or the above-mentioned ethylene-based resin composition.

The film may contain a lubricant and / or an anti-blocking agent. Further, as the additive, for example, an antioxidant, a neutralizing agent, a weather resistant agent, an antistatic agent, an antifogging agent, a drip-free agent, a pigment, a filler and the like may be contained.

The film preferably has a lubricant and / or antiblocking agent content of 200 ppm by weight or less. The content of the lubricant and / or antiblocking agent in the film is more preferably 100 ppm by weight or less, further preferably 50 ppm by weight or less, and particularly preferably 30 ppm by weight or less. The film preferably contains substantially no lubricant and / or antiblocking agent.

The film may be a single-layer film composed of only the above-mentioned ethylene-α-olefin copolymer or the above-mentioned ethylene-based resin composition-containing layer α, or a multilayer film containing the above-mentioned layer α. There may be. When the film is a multilayer film, at least one of the two surface layers of the multilayer film may be a multilayer film having layer α.

The film is a multilayer film having a layer α and a layer β containing an ethylene-based polymer (however, the layer β is different from the layer α), and at least of the two surface layers of the multilayer film. One surface layer may be a multilayer film which is a layer α.

The film is a multilayer film having a layer α and a layer γ containing no ethylene polymer (however, the layer γ is different from the layer α), and among the two surface layers of the multilayer film, At least one surface layer may be a multilayer film having layer α.

Examples of the ethylene-based polymer contained in the layer β in the multilayer film include high-pressure low-density polyethylene and an ethylene-α-olefin copolymer containing no component (A).

In the multilayer film, examples of the material constituting the layer γ include cellophane, paper, paperboard, woven fabric, aluminum foil, polyamide resin such as nylon 6 and nylon 66, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, and polypropylene resin. And so on.

A multilayer film having a layer α and a layer γ, wherein at least one of the two surface layers of the multilayer film is a layer α, for example, a layer α and a layer γ A bilayer film having the above, wherein one surface layer is layer α and the other surface layer is layer γ.

A multilayer film having a layer α and a layer γ, wherein at least one of the two surface layers of the multilayer film is a layer α, for example, a layer α and a layer β. Examples of the multilayer film having the layer γ include a multilayer film in which one surface layer is the layer α and the other surface layer is the layer γ.

Examples of the method for producing a single-layer film and a multilayer film include an extrusion molding method such as an inflation film molding method and a T-die film molding method, an injection molding method, and a compression molding method. The method for producing the single-layer film and the multilayer film is preferably an inflation film molding method.

When the multilayer film is a multilayer film having a layer α and a layer γ, as a method for producing the multilayer film, for example, a single layer film composed of only the layer α or a multilayer film having the layer α and the layer β. Can be mentioned by a lamination method in which the film is laminated on the layer γ. Examples of the lamination method include a dry laminating method, a wet laminating method, and a sand laminating method. The lamination method is preferably a dry laminating method.

The film according to this embodiment can be used as a packaging container and is used for packaging various contents. Examples of the contents include foods, beverages, seasonings, milk and the like, dairy products, pharmaceuticals, electronic parts such as semiconductor products, pet foods, pet care products, detergents, toiletry products and the like.

The film according to this embodiment contains the above-mentioned ethylene-α-olefin copolymer or the above-mentioned ethylene-based resin composition. With such a configuration, the film has excellent slipperiness and can suppress the occurrence of fish eyes.

The ethylene-α-olefin copolymer, the method for producing the ethylene-α-olefin copolymer, the ethylene resin composition, and the film according to the present embodiment are not limited to the above embodiments. Various modifications can be made without departing from the gist of the present invention. Further, the configurations and methods of embodiments other than the above may be arbitrarily adopted and combined, and the configurations and methods according to the above one embodiment are applied to the configurations and methods according to the above other embodiments. You may.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Measuring method]
The measured values of each item in Examples and Comparative Examples were measured according to the following method.

<Elemental analysis>
Zn: A sulfuric acid aqueous solution (concentration 1M) was added to the sample, and then ultrasonic waves were irradiated to extract the metal component. The obtained solution was quantified by ICP emission spectrometry.
F: The sample was burned in a flask filled with oxygen, the generated combustion gas was absorbed by a sodium hydroxide aqueous solution (10%), and the obtained aqueous solution was quantified by an ion electrode method.

<Melt flow rate (MFR, unit: g / 10 minutes)>
The measurement was carried out under the conditions of a temperature of 190 ° C. and a load of 21.18 N according to the method A specified in JIS K7210-1995.

<Density (unit: kg / m ³ )>
After performing the annealing described in JIS K6760-1980, the measurement was performed according to the method A specified in JIS K7112-1980.

<Mw>
The polystyrene-equivalent weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) measurement.
-GPC device: HLC-8121 GPC / HT (manufactured by Tosoh Corporation)
・ GPC column: TSKgelGMH _6- HT (manufactured by Tosoh Corporation) x 3 ・ Measurement temperature: 140 ° C
-Solvent and mobile phase: Ortodichlorobenzene containing 0.05% by mass of dibutylhydroxytoluene (Wako special grade)
-Mobile phase flow velocity: 1.0 mL / min-Injection volume: 300 μL
・ Detector: Differential refractometer ・ Molecular weight standard substance: Standard polystyrene ・ Data acquisition interval: 2.5 seconds

<Extreme viscosity ([η], unit: dl / g)>
The polymer was dissolved in a tetralin solvent and measured at 135 ° C. using an Ubbelohde viscometer. A film containing an ethylene-α-olefin copolymer having an intrinsic viscosity in the range of 1.4 to 1.6 is more excellent in slipperiness and more suppresses the occurrence of fish eyes.

<Melting point (Tm, unit: ° C), crystallization temperature (Tc, unit: ° C)>
Thermal analyzer Measured by the method of the following steps 1) to 3) using a differential scanning calorimeter (manufactured by Diamond DSC Perkin Elmer). The melting point was determined as the endothermic peak of the heat flow curve observed during step 3), and the crystallization temperature was determined as the exothermic peak of the heat flow curve observed during step 2).
1) Hold about 10 mg of sample in a nitrogen atmosphere at 150 ° C for 5 minutes 2) Cool 150 ° C to 20 ° C (5 ° C / min) Hold for 2 minutes 3) Raise 20 ° C to 150 ° C (5 ° C / min)
A film containing an ethylene-α-olefin copolymer having a small difference Tm-Tc between Tm and Tc is excellent in slipperiness.

<Calculation of cross-linking degree parameter>
The degree of cross-linking parameter is the ethylene-α-olefin copolymer weight in each Example and each Comparative Example using a gel permeation chromatograph (GPC) apparatus equipped with a differential refractometer, a viscosity detector and a light scattering detector. absolute molecular weight of polymer M, the weight fraction W _M ethylene -α- olefin copolymer in an absolute molecular weight _M, and, measuring the intrinsic viscosity [eta] _M of the absolute molecular weight ethylene -α- olefin copolymer in M Calculated by

The measurement conditions are shown below.
-GPC device: HLC-8121 GPC / HT (manufactured by Tosoh Corporation)
-Light scattering detector: PD2040 (manufactured by Precision Detectors)
-Laser light source: Wavelength 685 nm
-Viscosity detector: H502 (manufactured by Viscotek)
-GPC column: GMHHR-H (S) HT (manufactured by Tosoh Corporation) x 3-Sample solution concentration: 2 mg / mL
・ Injection amount: 300 μL
-Measurement temperature: 140 ° C
-Dissolution conditions: Stir at 145 ° C for 2 hours-Solvent and mobile phase: Ortodichlorobenzene containing 0.05% by mass of dibutylhydroxytoluene (Wako special grade)
-Mobile phase flow velocity: 1.0 mL / min-Measurement time: Approximately 1 hour-Molecular weight standard substance: Standard polystyrene-Data acquisition interval: 1.74 seconds

Specifically, a light scattering detector (LS) was connected to a GPC apparatus equipped with a differential refractive index detector (RI). The scattering angle used for light scattering detection was 90 °. A viscosity detector (VISC) was further connected to this GPC device. The LS and VISC were installed in the column oven of the GPC apparatus, and the LS, RI, and VISC were connected in this order.

For calibration of LS and VISC and correction of delay capacitance between detectors, 1 mg of Polycal TDS-PS-N (weight average molecular weight Mw 104,349, polydispersity 1.04), which is a polystyrene standard substance manufactured by Malvern. Used at a solution concentration of / mL.

Further, as the GPC column, three GMHHR-H (S) HTs (manufactured by Tosoh Corporation) were connected and used. Then, the temperature of the GPC column, the sample injection part, and each detector was set to 140 ° C.

The refractive index increment (dn / dc) of the sample and standard polyethylene NIST1475a in orthodichlorobenzene was −0.078 mL / g. The polystyrene standard substance dn / dc was 0.079 mL / g. The refractive index increment is the rate of change of the refractive index with respect to the change in density.

In determining the absolute molecular weight M and the intrinsic viscosity [η] _M (unit: dl / g) of the sample from the data of each detector, the data processing software OmniSEC (version 4.7) manufactured by Malvern is used, and the document "Size Exhibition" is used. The calculation was performed with reference to "Chromatography, Springer (1999)".

<Calculation of light scattering area ratio>
The light scattering area ratio was determined by adding the ethylene-α-olefin copolymers of each Example and each Comparative Example to orthodichlorobenzene at a concentration of 2 mg / mL using a liquid chromatography (LC) device equipped with a light scattering detector. It was calculated by measuring the light scattering area LS of the solution dissolved in (1) and the light scattering area LS'of the solution prepared by dissolving the standard polyethylene NIST1475a in orthodichlorobenzene at a concentration of 2 mg / mL.

The measurement conditions are shown below.
-LC device: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
-Light scattering detector: PD2040 (manufactured by Precision Detectors)
-Laser light source: Wavelength 685 nm
・ GPC column: None ・ Sample solution concentration: 2 mg / mL
・ Injection amount: 300 μL
-Measurement temperature: 140 ° C
-Dissolution conditions: Stir at 145 ° C for 2 hours-Automatic shaker for dissolution: DF-8020 (manufactured by Tosoh Corporation)
-Solvent and mobile phase: Ortodichlorobenzene containing 0.05% by mass of dibutylhydroxytoluene (Wako special grade)
・ Mobile phase flow velocity: 1.0 mL / min ・ Measurement time: Approximately 10 minutes ・ Data acquisition interval: 2.5 seconds

Specifically, a light scattering detector (LS) was connected to the LC device. The scattering angle used for light scattering detection was 90 °. The LS was installed in the column oven of the LC device.

The sample was dissolved by the following procedure in detail. First, a 30 mL screw vial is filled with a 40.0 mg sample and a 20.0 mL solvent and sealed tightly. The screw vial is set in DF-8020 (manufactured by Tosoh Corporation), and the sample is stirred at 140 ° C. for 2 hours to prepare the sample. Dissolved. The sample solution obtained by the above method was filtered using a cylindrical filter paper having a pore diameter of 8 μm (Whatman cylindrical filter paper diameter 18 mm × length 55 mm, model number: 280-185) before analysis. Filtration is performed at 140 ° C. or higher to avoid precipitation of the sample, soak the cylindrical filter paper in the sample solution, allow it to stand for 10 minutes in the soaked state for equilibrium, and then use the sample solution leached inside the cylindrical filter paper for analysis. did. Filtration was performed within 20 minutes to avoid changes in the concentration of the sample solution due to evaporation of the solvent.

The GPC column and guard column were not used in order to prevent the ultra-high molecular weight component from being trapped in the column. Further, in order to obtain a chromatogram, one SUS pipe having an inner diameter of 0.75 mm and a length of 5 m was attached between the sample injection part and the LS detector, and the temperature of the sample injection part and each detector was set to 140 ° C. ..

The obtained LS chromatogram was subjected to baseline treatment to calculate the light scattering area. In determining the light scattering area, the data processing software OmniSEC (version 4.7) manufactured by Malvern was used.

[Method for evaluating physical properties of film]
The physical characteristics of the films of Examples and Comparative Examples were evaluated according to the following method.

<Number of fish eyes (unit: pieces / m ² )>
The number of fish eyes of the produced film was analyzed using SCANTEC Elements 2 (manufactured by Nagase Sangyo Co., Ltd.) under the conditions of an inspection length of 100 m and an inspection width of 100 mm, and a film defect having a size of 0.2 mm or more per ^{1 m 2.} The number of (fish eyes) was measured. A film having a fisheye number of 30 / m ² or less was judged to be acceptable.

<Tanθ (slipperiness)>
Two 160 mm (length) × 80 mm (width) films were cut out from the produced film. One of the two films (hereinafter referred to as sample film (1)) was placed on an inclined plate of a friction angle measuring instrument (manufactured by Toyo Seiki Seisakusho Co., Ltd.). At this time, the upper surface of the sample film (1) was defined as the inner surface of the tube when the inflation film was formed. The other film (hereinafter, sample film (2)) was attached to the lower surface of a thread (weight 1 kg) of 100 mm (length) × 65 mm (width). At this time, the sample film (2) was attached so that the thread surface and the surface of the sample film (2), which was the outer surface of the tube at the time of forming the inflation film, were in contact with each other. The sample film (2) attached to the thread was placed so as to be in contact with the sample film (1) placed on the inclined plate. The tilt plate was tilted at a tilt rise speed of 2.7 ° / sec, the angle θ at which the thread started to move was measured, and the angle θ was displayed as tan θ (plane-plane). A film having a tan θ (plane-plane) of 1.6 or less was judged to be acceptable. Since the friction angle measuring device cannot make θ larger than 70 °, if the thread does not start moving when θ is 70 °, it is described as “not measurable”.

<Tensile breaking strength (unit: MPa)>
From the film-formed film, the longitudinal directions are the directions (MD) and the directions orthogonal to the MD direction (TD), respectively, according to the sampling method for tensile cutting load measurement described in JIS K 6781 6.4. A test piece was prepared. Using the obtained test piece, a tensile test was performed under the conditions of a chuck distance of 80 mm, a marked line distance of 40 mm, and a tensile speed of 500 mm / min to determine the tensile breaking strength. A film having a high tensile breaking strength is excellent in mechanical strength.

<Tension breaking elongation (unit:%)>
From the film-formed film, the longitudinal directions are the directions (MD) and the directions orthogonal to the MD direction (TD), respectively, according to the sampling method for tensile cutting load measurement described in JIS K 6781 6.4. A test piece was prepared. Using the obtained test piece, a tensile test was conducted under the conditions of a chuck distance of 80 mm, a marked line distance of 40 mm, and a tensile speed of 500 mm / min to determine tensile elongation at break. A film having a high tensile elongation at break is excellent in mechanical strength.

[Manufacturing of component (A)]
The component (A) was produced according to the following production example.

<Manufacturing example 1>
-Production of component (H) Component (H) was produced in the same manner as in the preparation of component (A) of Examples 1 (1) and (2) described in JP-A-2009-79180. As a result of elemental analysis, Zn = 11% by mass and F = 6.4% by mass.

· The prepolymerized catalyst component inner volume 9000 liters equipped with a stirrer autoclave produced previously purged with nitrogen, after the addition of butane 4.15M ^3, racemic - added ethylenebis (1-indenyl) zirconium phenoxide 6.0mol The temperature of the autoclave was raised to 50 ° C., and stirring was performed for 2 hours. Next, 60.4 kg of the produced component (H) was added to the autoclave. Then, the temperature of the autoclave was lowered to 30 ° C., and after the inside of the system was stabilized, 5 kg of ethylene and 5 liters of hydrogen (normal temperature and pressure) were added to the autoclave, and then triisobutylaluminum was diluted to 20 wt% with n-hexane. Prepolymerization was initiated by adding 35.1 L of solution. Ethylene and hydrogen (normal temperature and pressure) are supplied to the autoclave at 60 kg / hr and 30 liters / hr for 30 minutes, respectively, and then the temperature is raised to 50 ° C., and ethylene and hydrogen (normal temperature and pressure) are 159 kg / hr, respectively. And 0.54 m ³ / hr supplied to the autoclave. Prepolymerization was carried out for a total of 15.4 hours. After completion of the prepolymerization, ethylene, butane, hydrogen and the like were purged, and the remaining solid was vacuum dried at room temperature to obtain a prepolymerization catalyst component containing 41.1 g of polyethylene per 1 g of the component (H). The [η] of the polyethylene was 1.21 dl / g. Then, the obtained prepolymerization catalyst component was put into a high boulder manufactured by Toyo Hitech Co., Ltd. equipped with a mesh having a mesh size of 162 μm in a nitrogen atmosphere, and fine powder was removed to remove the fine prepolymerization catalyst. A prepolymerization catalyst component from which the component was removed was obtained.

-Production of polymer In the presence of the obtained prepolymerization catalyst component, copolymerization of ethylene, 1-butene and 1-hexene was carried out in a continuous flow bed gas phase polymerizer, and ethylene-1-butene-1- A powder of a hexene copolymer (hereinafter referred to as LLDPE-1) was obtained. As the polymerization conditions, the polymerization temperature was 89 ° C., the polymerization pressure was 2 MPa; the average ratio of the amount of hydrogen to 100 mol% of ethylene was 0.35%; the molar amount of 1-butene with respect to the total of ethylene, 1-butene and 1-hexene. The ratio was 1.45%, and the molar ratio of 1-hexene was 0.53%. Ethylene, 1-butene, 1-hexene and hydrogen were continuously supplied to keep the gas composition constant during the polymerization. In addition, the prepolymerization catalyst component, triisobutylaluminum (molar ratio of triisobutylaluminum to the powder weight of LLDPE-1 0.44 mol / t), triethylamine (molar ratio to triisobutylaluminum 10.7%), and oxygen (tri). A molar ratio of 24% to isobutylaluminum) was continuously supplied. The order of contact of the prepolymerization catalyst component, triisobutylaluminum, triethylamine, and oxygen is as follows: first, triisobutylaluminum and oxygen are brought into contact with each other to obtain a contact-treated product, and then the contact-treated product and triethylamine are brought into contact with each other. The order was to obtain a coordination compound, put the coordination compound into a gas phase polymerization tank, and finally bring it into contact with the prepolymerization catalyst component. The total powder weight of the fluidized bed was kept constant at 50.7 tons. The average polymerization time was 7.4 hr. The LLDPE-1 powder was transferred to the hopper via a transfer pipe connecting the continuous fluidized bed vapor phase polymerization apparatus and the hopper. Water was brought into contact with the powder of LLDPE-1 by charging the hopper with a mixed gas in which nitrogen having a flow rate of 250 m ³ / hr and water having a flow rate of 6 L / hr were mixed and heated to 65 ° C. The contact time with water in the hopper was 1.3 hours. The LLDPE-1 powder after contact with water was transferred to another hopper through a transfer pipe, and nitrogen was passed through the hopper to dry the LLDPE-1 powder. Using an extruder (LCM50 manufactured by Kobe Steel, Ltd.), the dried LLDPE-1 powder has a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature. Granulation was performed under the conditions of 200 to 230 ° C. to obtain pellets of LLDPE-1. The physical characteristics of the obtained LLDPE-1 pellets were evaluated, and the results are shown in Table 1.

<Manufacturing example 2>
-Production of polymer In the presence of the prepolymerization catalyst component of Production Example 1, copolymerization of ethylene, 1-butene and 1-hexene was carried out in a continuous flow bed gas phase polymerization apparatus, and ethylene-1-butene-1 was carried out. -A powder of a hexene copolymer (hereinafter referred to as LLDPE-2) was obtained. As the polymerization conditions, the polymerization temperature was 89 ° C., the polymerization pressure was 2 MPa; the average ratio of the amount of hydrogen to 100 mol% of ethylene was 0.35%; the molar amount of 1-butene with respect to the total of ethylene, 1-butene and 1-hexene. The ratio was 1.34%, and the molar ratio of 1-hexene was 0.52%. Ethylene, 1-butene, 1-hexene and hydrogen were continuously supplied to keep the gas composition constant during the polymerization. Further, the prepolymerization catalyst component, triisobutylaluminum (molar ratio of triisobutylaluminum to the powder weight of LLDPE-2: 0.40 mol / t), triethylamine (molar ratio to triisobutylaluminum: 9.7%), and oxygen (tri). A molar ratio of 24% to isobutylaluminum) was continuously supplied. The order of contact of the prepolymerization catalyst component, triisobutylaluminum, triethylamine, and oxygen was the same as in Production Example 1. The total powder weight of the fluidized bed was kept constant at 52.2 tons. The average polymerization time was 7.1 hr. The LLDPE-2 powder was transferred to the hopper via a transfer pipe connecting the continuous fluidized bed vapor phase polymerization apparatus and the hopper. Water was brought into contact with the LLDPE-2 powder by pouring water heated to 100 ° C. or higher into the hopper. The contact time with water in the hopper was 1.3 hours. The LLDPE-2 powder after contact with water was transferred to another hopper through a transfer pipe, and nitrogen was passed through the hopper to dry the LLDPE-2 powder. Using an extruder (LCM50 manufactured by Kobe Steel, Ltd.), the dried LLDPE-2 powder has a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature. Granulation was performed under the conditions of 200 to 230 ° C. to obtain pellets of LLDPE-2. The physical characteristics of the obtained LLDPE-2 pellets were evaluated, and the results are shown in Table 1.

<Manufacturing example 3>
-Production of polymer In the presence of the prepolymerization catalyst component of Production Example 1, copolymerization of ethylene, 1-butene and 1-hexene was carried out in a continuous flow bed gas phase polymerization apparatus, and ethylene-1-butene-1 was carried out. -A powder of a hexene copolymer (hereinafter referred to as LLDPE-3) was obtained. As the polymerization conditions, the polymerization temperature was 89 ° C., the polymerization pressure was 2 MPa; the average ratio of the amount of hydrogen to 100 mol% of ethylene was 0.33%; the molar amount of 1-butene with respect to the total of ethylene, 1-butene and 1-hexene. The ratio was 1.33%, and the molar ratio of 1-hexene was 0.53%. Ethylene, 1-butene, 1-hexene and hydrogen were continuously supplied to keep the gas composition constant during the polymerization. In addition, the prepolymerization catalyst component, triisobutylaluminum (molar ratio of triisobutylaluminum to the powder weight of LLDPE-3 0.44 mol / t), triethylamine (molar ratio to triisobutylaluminum 10.2%), and oxygen (tri). A molar ratio of 24% to isobutylaluminum) was continuously supplied. The order of contact of the prepolymerization catalyst component, triisobutylaluminum, triethylamine, and oxygen was the same as in Production Example 1. The total powder weight of the fluidized bed was kept constant at 52.9 tons. The average polymerization time was 6.6 hr. The LLDPE-3 powder was transferred to the hopper via a transfer pipe connecting the continuous fluidized bed vapor phase polymerization apparatus and the hopper. Water was brought into contact with the powder of LLDPE-3 by charging the hopper with a mixed gas in which nitrogen having a flow rate of 250 m ³ / hr and water having a flow rate of 6 L / hr were mixed and heated to 65 ° C. The contact time with water in the hopper was 1.3 hours. The LLDPE-3 powder after contact with water was transferred to another hopper through a transfer pipe, and nitrogen was passed through the hopper to dry the LLDPE-3 powder. Using an extruder (LCM50 manufactured by Kobe Steel, Ltd.), the dried LLDPE-3 powder has a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature. Granulation was performed under the conditions of 200 to 230 ° C. to obtain pellets of LLDPE-3. The physical characteristics of the obtained LLDPE-3 pellets were evaluated, and the results are shown in Table 1.

<Manufacturing example 4>
-Production of polymer In the presence of the prepolymerization catalyst component of Production Example 1, copolymerization of ethylene, 1-butene and 1-hexene was carried out in a continuous flow bed gas phase polymerization apparatus, and ethylene-1-butene-1 was carried out. -A powder of a hexene copolymer (hereinafter referred to as LLDPE-4) was obtained. As the polymerization conditions, the polymerization temperature was 89 ° C., the polymerization pressure was 2 MPa; the average ratio of the amount of hydrogen to 100 mol% of ethylene was 0.28%; the molar amount of 1-butene with respect to the total of ethylene, 1-butene and 1-hexene. The ratio was 1.37%, and the molar ratio of 1-hexene was 0.55%. Ethylene, 1-butene, 1-hexene and hydrogen were continuously supplied to keep the gas composition constant during the polymerization. Further, the prepolymerization catalyst component, triisobutylaluminum (molar ratio of triisobutylaluminum to the powder weight of LLDPE-4 0.47 mol / t), triethylamine (molar ratio to triisobutylaluminum 9.0%), and oxygen (tri). A molar ratio of 24% to isobutylaluminum) was continuously supplied. The order of contact of the prepolymerization catalyst component, triisobutylaluminum (molar ratio of triisobutylaluminum to the powder weight of LLDPE-4: 0.47 mol / t), triethylamine, and oxygen was the same as in Production Example 1. The total powder weight of the fluidized bed was kept constant at 52.7 tons. The average polymerization time was 6.8 hr. The LLDPE-4 powder was transferred to the hopper via a transfer pipe connecting the continuous fluidized bed vapor phase polymerization apparatus and the hopper. Water was brought into contact with the powder of LLDPE-4 by charging the hopper with a mixed gas in which nitrogen having a flow rate of 250 m ³ / hr and water having a flow rate of 6 L / hr were mixed and heated to 65 ° C. The contact time with water in the hopper was 1.3 hours. The LLDPE-4 powder after contact with water was transferred to another hopper through a transfer pipe, and nitrogen was passed through the hopper to dry the LLDPE-4 powder. Using an extruder (LCM50 manufactured by Kobe Steel, Ltd.), the dried LLDPE-4 powder has a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature. Granulation was performed under the conditions of 200 to 230 ° C. to obtain pellets of LLDPE-4. The physical characteristics of the obtained LLDPE-4 pellets were evaluated, and the results are shown in Table 1.

<Manufacturing example 5>
-Production of polymer In the presence of the prepolymerization catalyst component of Production Example 1, copolymerization of ethylene, 1-butene and 1-hexene was carried out in a continuous flow bed gas phase polymerization apparatus, and ethylene-1-butene-1 was carried out. -A powder of a hexene copolymer (hereinafter referred to as LLDPE-5) was obtained. As the polymerization conditions, the polymerization temperature was 89 ° C., the polymerization pressure was 2 MPa; the average ratio of the amount of hydrogen to 100 mol% of ethylene was 0.22%; the molar amount of 1-butene with respect to the total of ethylene, 1-butene and 1-hexene. The ratio was 1.35%, and the molar ratio of 1-hexene was 0.51%. Ethylene, 1-butene, 1-hexene and hydrogen were continuously supplied to keep the gas composition constant during the polymerization. In addition, the prepolymerization catalyst component, triisobutylaluminum (molar ratio of triisobutylaluminum to the powder weight of LLDPE-5: 0.42 mol / t), triethylamine (molar ratio to triisobutylaluminum: 10.2%), and oxygen (tri). A molar ratio of 24% to isobutylaluminum) was continuously supplied. The order of contact of the prepolymerization catalyst component, triisobutylaluminum, triethylamine, and oxygen was the same as in Production Example 1. The total powder weight of the fluidized bed was kept constant at 52.0 tons. The average polymerization time was 7.1 hr. The LLDPE-5 powder was transferred to the hopper via a transfer pipe connecting the continuous fluidized bed vapor phase polymerization apparatus and the hopper. Water was brought into contact with the powder of LLDPE-5 by adding a mixed gas in which nitrogen having a flow rate of 250 m ^{3 / hr and water having a flow rate of 6 L / hr were mixed and heated to 65 ° C. into the hopper.} The contact time with water in the hopper was 1.3 hours. The LLDPE-5 powder after contact with water was transferred to another hopper through a transfer pipe, and nitrogen was passed through the hopper to dry the LLDPE-5 powder. Using an extruder (LCM50 manufactured by Kobe Steel, Ltd.), the dried LLDPE-5 powder is fed at a feed rate of 50 kg / hr, screw rotation speed of 450 rpm, gate opening of 50%, suction pressure of 0.1 MPa, and resin temperature. Granulation was performed under the conditions of 200 to 230 ° C. to obtain pellets of LLDPE-5. The physical characteristics of the obtained LLDPE-5 pellets were evaluated, and the results are shown in Table 1.

<Manufacturing example 6>
-Production of prepolymerization catalyst component After adding 41 liters of butane to an autoclave with an internal volume of 210 liters that had been replaced with nitrogen in advance, 60.9 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added to the autoclave. Was heated to 50 ° C. and stirred for 2 hours. Next, 0.60 kg of the component (H) obtained in Production Example 1 was added to the autoclave. Then, the temperature of the autoclave was lowered to 31 ° C., and after the inside of the system was stabilized, 0.1 kg of ethylene and 0.1 liter of hydrogen (normal temperature and pressure) were added to the autoclave, and then 240 mmol of triisobutylaluminum was added for prepolymerization. It started. Ethylene and hydrogen (normal temperature and normal pressure) were supplied to the autoclave at 0.5 kg / hr and 1.1 liter / hr, respectively, for 30 minutes, and then the temperature was raised to 50 ° C., and ethylene and hydrogen (normal temperature and normal pressure) were added. They were supplied to the autoclave at 2.7 kg / hr and 8.2 liters / hr, respectively. Prepolymerization was carried out for a total of 10.0 hours. After completion of the prepolymerization, ethylene, butane, hydrogen and the like were purged, and the remaining solid was vacuum dried at room temperature to obtain a prepolymerization catalyst component containing 39.6 g of polyethylene per 1 g of the component (H). The [η] of the polyethylene was 1.17 dl / g.

-Production of polymer In the presence of the obtained prepolymerization catalyst component, copolymerization of ethylene and 1-hexene was carried out in a continuous flow bed gas phase polymerization apparatus, and an ethylene-1-hexene copolymer (hereinafter, LLDPE) was carried out. A powder (referred to as -6) was obtained. As the polymerization conditions, the polymerization temperature was 96 ° C., the polymerization pressure was 2 MPa; the average amount of hydrogen was 0.30% with respect to 100 mol% of ethylene; and the molar ratio of 1-hexene to the total of ethylene and 1-hexene was 0.86. %. Ethylene, 1-hexene and hydrogen were continuously supplied to keep the gas composition constant during the polymerization. Further, the prepolymerization catalyst component, triisobutylaluminum (molar ratio of triisobutylaluminum to the powder weight of LLDPE-6 0.47 mmol / kg), triethylamine (molar ratio to triisobutylaluminum 29%), oxygen (to triisobutylaluminum). (Mole ratio 21%) was continuously supplied. The order of contact of the prepolymerization catalyst component, triisobutylaluminum, triethylamine, and oxygen is such that triisobutylaluminum and triethylamine first contact, then the contact material in which oxygen contacts the contact material is charged into the gas phase polymerization tank, and finally. The order of contact was to contact the prepolymerization catalyst component. The total powder weight of the fluidized bed was kept constant at 80 kg. The average polymerization time was 3.7 hr. The obtained LLDPE-6 powder was transferred to the hopper via a transfer pipe connecting the continuous fluidized bed vapor phase polymerization apparatus and the hopper. Methanol was brought into contact with the powder of LLDPE-6 by adding methanol at room temperature to the hopper. The contact time with methanol in the hopper was 1 hour. The LLDPE-6 powder after contact with methanol was transferred to another hopper through a transfer pipe, and nitrogen was passed through the hopper to dry the LLDPE-6 powder. Using an extruder (LCM50 manufactured by Kobe Steel, Ltd.), the dried LLDPE-6 powder is fed at a feed rate of 50 kg / hr, screw rotation speed of 450 rpm, gate opening of 50%, suction pressure of 0.1 MPa, and resin temperature of 200 to 200. Granulation was performed under the condition of 230 ° C. to obtain pellets of LLDPE-6. The physical characteristics of the obtained LLDPE-6 pellets were evaluated, and the results are shown in Table 2.

<Manufacturing example 7>
-Production of polymer Copolymerization of ethylene and 1-hexene was carried out in a continuous flow bed vapor phase polymerization apparatus in the presence of the prepolymerization catalyst component from which the minute prepolymerization catalyst component obtained in Production Example 1 was removed. , Ethylene-1-hexene copolymer (hereinafter referred to as LLDPE-7) powder was obtained. As the polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa; the average ratio of the amount of hydrogen to 100 mol% of ethylene was 1.89%; and the molar ratio of 1-hexene to the total of ethylene and 1-hexene was 1. It was set to 29%. Ethylene, 1-hexene and hydrogen were continuously supplied to keep the gas composition constant during the polymerization. In addition, the prepolymerization catalyst component, triisobutylaluminum (molar ratio of triisobutylaluminum to the powder weight of LLDPE-7: 0.39 mol / t), and triethylamine (molar ratio to triisobutylaluminum: 4%) were continuously supplied. The total powder weight of the fluidized bed was kept constant at 43.5 tons. The average polymerization time was 4.2 hr. The LLDPE-7 powder was transferred to the hopper via a transfer pipe connecting the continuous fluidized bed vapor phase polymerization apparatus and the hopper. Water was brought into contact with the powder of LLDPE-7 by adding a mixed gas in which nitrogen having a flow rate of 250 m ^{3 / hr and water having a flow rate of 6 L / hr were mixed and heated to 65 ° C. into the hopper.} The contact time with water in the hopper was 0.97 hours. The LLDPE-7 powder after contact with water was transferred to another hopper through a transfer pipe, and nitrogen was passed through the hopper to dry the LLDPE-7 powder. Using an extruder (LCM50 manufactured by Kobe Steel, Ltd.), the dried LLDPE-7 powder is fed at a feed rate of 50 kg / hr, screw rotation speed of 450 rpm, gate opening of 50%, suction pressure of 0.1 MPa, and resin temperature. Granulation was performed under the conditions of 200 to 230 ° C. to obtain pellets of LLDPE-7. The physical characteristics of the obtained LLDPE-7 pellets were evaluated, and the results are shown in Table 2.

<Manufacturing example 8>
-Production of polymer High-pressure radical polymerization of ethylene was carried out using a tubular reactor under the conditions of an average reaction temperature of 256 ° C. and a reaction pressure of 229 MPa. The polymerization initiator was supplied from four locations in the tubular reactor. The polymerization initiator was supplied to the tubular reactor as a solution containing a mixed isoparaffinic hydrocarbon as a solvent. As the polymerization initiator, t-butylperoxy-2-ethylhexanoate and t-butylperoxybenzoate were used. Propylene was used as the chain transfer agent. The molten LDPE-1 was constructed using an extruder to obtain pellets of LDPE-1. The physical characteristics of the obtained LDPE-1 pellets are shown in Table 2.

<Manufacturing example 9>
-Production of polymer LLDPE-8 was produced by the same method as in Production Example 4 described in JP-A-2000-44739 (that is, the order of contact in which the prepolymerization catalyst component and triisobutylaluminum come into contact with each other). .. The powder of LLDPE-8 was granulated using an extruder to obtain pellets of LLDPE-8. The physical characteristics of the obtained LLDPE-8 were evaluated, and the results are shown in Table 2.

<Manufacturing example 10>
-Production of polymer In the presence of the prepolymerization catalyst component obtained in Production Example 6, copolymerization of ethylene, 1-butene and 1-hexene was carried out in a continuous flow bed vapor phase polymerization apparatus, and ethylene-1- A powder of a butene-1-hexene copolymer (hereinafter referred to as LLDPE-9) was obtained. As the polymerization conditions, the polymerization temperature was 88.6 ° C., the polymerization pressure was 2 MPa; the average ratio of the amount of hydrogen to 100 mol% of ethylene was 0.07%; and 1-butene with respect to the total of ethylene, 1-butene and 1-hexene. The molar ratio of 1-hexene was 1.23%, and the molar ratio of 1-hexene was 0.56%. Ethylene, 1-butene, 1-hexene and hydrogen were continuously supplied to keep the gas composition constant during the polymerization. In addition, the prepolymerization catalyst component, triisobutylaluminum (molar ratio of triisobutylaluminum to the powder weight of LLDPE-9: 0.56 mmol / kg), and triethylamine (molar ratio to triisobutylaluminum: 3.0%) are continuously supplied. did. The order of contact of the prepolymerization catalyst component, triisobutylaluminum, and triethylamine is that triisobutylaluminum and triethylamine first contact, and then the contact material is charged into the gas phase polymerization tank and contacts the prepolymerization catalyst component. It was a turn. The total powder weight of the fluidized bed was kept constant at 99 kg. The average polymerization time was 5.5 hr. The obtained LLDPE-9 powder was transferred to the hopper via a transfer pipe connecting the continuous fluidized bed vapor phase polymerization apparatus and the hopper. Methanol was brought into contact with the powder of LLDPE-9 by adding methanol at room temperature to the hopper. The contact time with methanol in the hopper was 1 hour. The LLDPE-9 powder after contact with methanol was transferred to another hopper through a transfer pipe, and nitrogen was passed through the hopper to dry the LLDPE-9 powder. Using an extruder (LCM50 manufactured by Kobe Steel, Ltd.), the dried LLDPE-9 powder is fed at a feed rate of 50 kg / hr, screw rotation speed of 450 rpm, gate opening of 50%, suction pressure of 0.1 MPa, and resin temperature of 200 to 200. Granulation was performed under the condition of 230 ° C. to obtain pellets of LLDPE-9. The physical characteristics of the obtained LLDPE-9 pellets were evaluated, and the results are shown in Table 2.

[Inflation film molding]
The following components (B) were used as the components (B) described in each Example and Comparative Example.
Ethylene-1-hexene copolymer 2-1 (LLDPE2-1): Metallocene-catalyzed linear low-density polyethylene Sumikasen E FV203N (manufactured by Sumitomo Chemical Co., Ltd., ethylene-1-hexene copolymer (without additives), MFR 2.0 g / 10 minutes, density 913 kg / m ³ , MFRR = 16.7)

<Example 1>
LLDPE-1 and LLDPE2-1 were mixed in a tumble mixer with a composition of 20:80. Next, the obtained mixture was subjected to an inflation film forming machine manufactured by Placo (full flight type screw single-screw extruder (diameter 30 mmφ, L / D = 28), die (die diameter 50 mmφ, lip gap 2.0 mm), two. An inflation film having a thickness of 50 μm was formed using a heavy slit air ring under processing conditions of a processing temperature of 170 ° C., an extrusion rate of 5.5 kg / hr, a frost line distance (FLD) of 200 mm, and a blow ratio of 1.8. Table 3 shows the physical properties of the inflation film.

<Example 2>
An inflation film was obtained in the same manner as in Example 1 except that LLDPE-2 and LLDPE2-1 were mixed with a tumble mixer in a blending composition of 20:80. Table 3 shows the physical characteristics of the obtained inflation film.

<Example 3>
An inflation film was obtained in the same manner as in Example 1 except that LLDPE-3 and LLDPE2-1 were mixed with a tumble mixer in a blending composition of 20:80. Table 3 shows the physical characteristics of the obtained inflation film.

<Example 4>
An inflation film was obtained in the same manner as in Example 1 except that LLDPE-4 and LLDPE2-1 were mixed with a tumble mixer in a blending composition of 20:80. Table 3 shows the physical characteristics of the obtained inflation film.

<Example 5>
An inflation film was obtained in the same manner as in Example 1 except that LLDPE-5 and LLDPE2-1 were mixed with a tumble mixer in a blending composition of 20:80. Table 3 shows the physical characteristics of the obtained inflation film.

<Comparative example 1>
An inflation film was obtained in the same manner as in Example 1 except that LLDPE-6 and LLDPE2-1 were mixed with a tumble mixer in a blending composition of 20:80. Table 4 shows the physical characteristics of the obtained inflation film.

<Comparative example 2>
An inflation film was obtained in the same manner as in Example 1 except that LLDPE-7 and LLDPE2-1 were mixed with a tumble mixer in a blending composition of 20:80. Table 4 shows the physical characteristics of the obtained inflation film.

<Comparative example 3>
An inflation film was obtained in the same manner as in Example 1 except that LDPE-1 and LLDPE2-1 were mixed with a tumble mixer in a blending composition of 20:80. Table 4 shows the physical characteristics of the obtained inflation film.

<Comparative example 4>
An inflation film was obtained in the same manner as in Example 1 except that LLDPE-8 and LLDPE2-1 were mixed with a tumble mixer in a blending composition of 20:80. Table 4 shows the physical characteristics of the obtained inflation film.

<Comparative example 5>
An inflation film was obtained in the same manner as in Example 1 except that LLDPE-9 and LLDPE2-1 were mixed with a tumble mixer in a blending composition of 20:80. Table 4 shows the physical characteristics of the obtained inflation film.

As can be seen from the results in Table 3, the ethylene-α-olefin copolymer of each example satisfying all the constituent requirements of the present invention is a film having excellent slipperiness and capable of suppressing the generation of fish eyes. Was able to form.

On the other hand, as can be seen from the results in Table 4, the polymer of Comparative Example 1 in which the organoaluminum compound and the electron-donating compound were brought into contact with each other, then with oxygen gas, and finally with the prepolymerization catalyst component was contained. Since the light scattering area ratio of the film exceeds the range specified in the present invention, a large amount of fish eyes are generated. Further, the film containing the polymer of Comparative Example 5 in which the organoaluminum compound and the electron-donating compound are brought into contact with each other and then brought into contact with the prepolymerization catalyst component has a light scattering area ratio exceeding the range specified in the present invention. Therefore, a large amount of fish eyes were generated.

Further, the films containing the polymers of Comparative Examples 2 and 4 in which the light scattering area ratio is smaller than the range specified in the present invention are inferior in slipperiness.

Further, the film containing the polymer of Comparative Example 3 in which the crosslinkability parameter is smaller than the range specified in the present invention is inferior in slipperiness.

Claims (13)

It contains an ethylene-based monomer unit (1) and an α-olefin-based monomer unit (2) having 3 to 20 carbon atoms.
The degree of cross-linking parameter represented by the following equation (i) is 0.70 or more and 0.90 or less.
An ethylene-α-olefin copolymer having a light scattering area ratio of 1.60 or more and 3.60 or less represented by the following formula (ii).

(Wherein, M is .W _M is indicative of the absolute molecular weight of the ethylene -α- olefin copolymer, .g _'M indicating the weight fraction of ethylene -α- olefin copolymer in an absolute molecular weight M, the absolute The intrinsic viscosity ratio at the molecular weight M is shown.)

(In the formula, LS indicates the light scattering area of a solution in which an ethylene-α-olefin copolymer is dissolved in orthodichlorobenzene at a concentration of 2 mg / mL. LS'indicates standard polyethylene NIST1475a in 2 mg orthodichlorobenzene. Indicates the light scattering area of the solution dissolved at a concentration of / mL.) The ethylene-α-olefin copolymer according to claim 1, wherein the degree of cross-linking parameter is 0.70 or more and 0.80 or less. The ethylene-α-olefin copolymer according to claim 1 or 2, wherein the light scattering area ratio is 2.70 or more and 3.00 or less. Claim that the content of the monomer unit (1) is 90% by mass or more and the content of the monomer unit (2) is 10% by mass or less when the total mass is 100% by mass. The ethylene-α-olefin copolymer according to any one of 1 to 3. The ethylene-α-olefin copolymer according to any one of claims 1 to 4, wherein the monomer unit (2) is a monomer unit based on an α-olefin having 4 to 8 carbon atoms. .. The ethylene-ethylene according to any one of claims 1 to 5, wherein the melt flow rate measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N is 0.010 g / 10 minutes or more and 0.2 g / 10 minutes or less. α-olefin copolymer. The ethylene-α-olefin copolymer according to any one of claims 1 to 6, which has a density of 910 kg / m ³ or more and 940 kg / m ^{3 or less.} A method for producing an ethylene-α-olefin copolymer, which comprises an ethylene-based monomer unit (1) and an α-olefin-based monomer unit (2) having 3 to 20 carbon atoms.
A method for producing an ethylene-α-olefin copolymer, which comprises the following steps (a) to (c).
(A) Prepolymerization of ethylene and α-olefin having 3 to 20 carbon atoms in the presence of a catalyst component formed by contacting a metallocene complex, an organic aluminum compound, and a co-catalyst carrier. Step of obtaining a catalyst component (b) A step of contacting an organic aluminum compound with oxygen gas and then contacting with an electron donating compound to obtain a coordination compound (c) The prepolymerization catalyst component and the coordination compound A step of gas-phase polymerization of ethylene and α-olefin having 3 to 20 carbon atoms in the presence of a polymerization catalyst formed by contacting ethylene-α-olefin copolymer to obtain an ethylene-α-olefin copolymer. The method for producing an ethylene-α-olefin copolymer according to claim 8, wherein the co-catalyst carrier is a carrier in which a zinc compound is supported on a fine particle carrier. The ethylene-α-olefin copolymer according to any one of claims 1 to 7 and an ethylene-based polymer containing an ethylene-based monomer unit (however, the ethylene-α-olefin copolymer is An ethylene resin composition containing (different). The melt flow rate measured under the conditions of the ethylene polymer temperature of 190 ° C. and a load of 21.18 N is 0.01 g / 10 minutes or more and 5 g / 10 minutes or less, and the density is 910 kg / m ³ or more and 940 kg / m ³ The ethylene resin composition according to claim 10, which is as follows. The content of the ethylene-α-olefin copolymer is 1% by mass or more and 30% by mass or less with respect to the total content of the ethylene-α-olefin copolymer and the ethylene-based polymer of 100% by mass. , The ethylene-based resin composition according to claim 10 or 11. A film containing the ethylene-α-olefin copolymer according to any one of claims 1 to 7 or the ethylene resin composition according to any one of claims 10 to 12.