JP2023129127A - Ethylene resin composition and molding - Google Patents

Abstract

To provide an ethylene resin with excellent moldability, capable of producing molded articles with excellent mechanical strength (particularly, films).SOLUTION: An ethylene resin composition (Z) includes an ethylene-α-olefin copolymer (A) that satisfies requirements (1)-(6) and a high-pressure low-density polyethylene (B) that satisfies requirements (a)-(c): (1) a density of 890-935 kg/m3; (2) an MFR (190°C, 2.16 kg load) of 1.0-15.0 g/10 min; (3) MT (melt strength)/η*(shear viscosity) of 1.40×10-4-2.90×10-4 g/P; (4) 0.01×10-13×Mw3.4≤η0 (zero shear viscosity)≤4.5×10-13×Mw3.4; (5) -2.0≤Mz/Mw-Mw/Mn≤15; (6) the number of vinyl and other groups of 0.1-1.0/1000C; (a) a density of 915-930 kg/m3; (b) an MFR (190°C, 2.16 kg load) of 0.1-20 g/10 min; and (c) the amount of a component with a molecular weight of 1,000,000 or more being 1.0-20%.SELECTED DRAWING: None

Description

The present invention relates to an ethylene-based resin composition and molded articles, films, multilayer films, and laminates containing the composition.

Ethylene polymers are used in various molding methods and applications, and various properties are required of the ethylene polymers depending on the molding method and application. For example, in T-die molding, neck-in occurs in which the ends of the film shrink toward the center. When neck-in occurs, the film width becomes smaller and the edges of the film become thicker than the center of the film. For this reason, if the neck-in is large, problems such as poor product yield and inability to manufacture a product with a desired width occur. In blow molding, problems such as sagging or breakage of the molten film may occur, and in inflation molding, problems such as shaking or breakage of the molten film may occur. In order to suppress these problems, it is necessary to select an ethylene polymer that has a large melt tension relative to its molecular weight.

In addition, in T-die molding, regular thickness fluctuations that occur in the film drawing direction called draw surging (or draw resonance) may occur, which may cause variations in mechanical strength from place to place due to uneven film thickness. be. In order to stably produce a film with a uniform thickness, it is necessary to avoid surging, but to do this, the resin properties must be such that the degree of strain hardening of the elongational viscosity increases as the strain rate increases. It is believed that

Ethylene polymers without long chain branches obtained using metallocene catalysts have excellent mechanical strength, but have problems with moldability. For example, in T-die molding, neck-in becomes large and surging occurs. High-pressure low-density polyethylene has excellent moldability such as high melt tension and low neck-in, has an elongational viscosity that exhibits strain rate hardening, and does not cause draw-up surging. However, high-pressure low-density polyethylene has a complex long-chain branched structure and is therefore inferior in mechanical strength such as tensile strength, tear strength, or impact strength.

In order to solve these problems, various ethylene polymers having long chain branches introduced therein have been disclosed. Patent Document 1 proposes a composition of an ethylene polymer obtained using a metallocene catalyst and high-pressure low-density polyethylene. However, if the content of high-pressure low-density polyethylene is high, it is expected that mechanical strength such as tensile strength, tear strength, or impact strength will be inferior. Since the improvement in tension is not sufficient, deterioration in formability such as large neck-in is expected.

Further, Patent Document 2 describes an ethylene polymer obtained by solution polymerization in the presence of a catalyst consisting of ethylene bis(indenyl) hafnium dichloride and methylalumoxane, and Patent Document 3 describes an ethylene-based polymer obtained by solution polymerization in the presence of a catalyst consisting of ethylene bis(indenyl) hafnium dichloride and methylalumoxane; Patent Document 4 discloses an ethylene polymer obtained by gas phase polymerization in the presence of a catalyst consisting of (indenyl) zirconium dichloride and methylalumoxane, and an ethylene polymer obtained by solution polymerization in the presence of a constrained geometry catalyst. Patent Document 5 describes an ethylene system obtained by gas phase polymerization in the presence of a catalyst consisting of racemic and meso isomers of Me ₂ Si (2-Me-Ind) ₂ supported on silica and methylalumoxane. Polymers are disclosed. Although it is stated that these ethylene polymers have improved melt tension and superior moldability compared to linear ethylene polymers without long chain branches, the neck-in is still large, so it is difficult to mold them. It is expected that the improvement in sexual performance will be insufficient. Furthermore, unlike high-pressure low-density polyethylene, these ethylene polymers do not exhibit strain rate hardening in elongational viscosity, so it is expected that the take-up surging will not be improved.

Patent Documents 6 and 7 describe ethylene-based polymers in which intrinsic viscosity and weight average molecular weight satisfy a specific relationship, melt tension and shear viscosity satisfy a specific relationship, and zero shear viscosity and weight average molecular weight meet a specific relationship. The combination is disclosed. These ethylene polymers have improved take-up surging and neck-in better than conventional ethylene polymers in which long chain branches are introduced using metallocene catalysts. However, although its mechanical strength is superior to that of high-pressure low-density polyethylene, further improvement in mechanical strength is desired.

Japanese Patent Application Publication No. 7-26079 Japanese Unexamined Patent Publication No. 2-276807 Japanese Patent Application Publication No. 4-213309 International Publication No. 93/08221 Japanese Patent Application Publication No. 8-311260 Japanese Patent Application Publication No. 2006-233207 JP2009-197225A

The present invention relates to an ethylene resin composition that has excellent moldability and can form a film that has particularly excellent mechanical strength compared to conventionally known ethylene polymers, and an ethylene resin composition that can be obtained from the ethylene resin composition. The purpose is to provide films, laminates, etc.

The present invention relates to, for example, the following [1] to [13].
[1]
An ethylene-α-olefin copolymer (A) which is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms and satisfies the following requirements (1) to (6), and the following requirements (a) to (c) including high-pressure low-density polyethylene (B),
The mass fraction (W _A ) of the ethylene-α-olefin copolymer (A) is 40% by mass or more and 90% by mass or less, and the mass fraction (W B ) of the high-pressure low density polyethylene ( _B ) is 10% by mass or more and 60% by mass or less (however, the total of W _A and W _B is 100% by mass).
Ethylene resin composition (Z).
(1) The density is in the range of 890 kg/m ³ or more and 935 kg/m ³ or less.
(2) The melt flow rate (MFR) under a load of 2.16 kg at 190° C. is in the range of 1.0 g/10 minutes or more and 15.0 g/10 minutes or less.
(3) The ratio of the melt tension at 190°C [MT (g)] to the shear viscosity [η ^* (P)] at 200°C and an angular velocity of 1.0 rad/sec [MT/η ^* (g/P)] is It is in the range of 1.40×10 ^-4 or more and 2.90×10 ^-4 or less.
(4) Zero shear viscosity [η ₀ (P)] at 200°C and weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .
0.01×10 ^-13 ×Mw ^3.4 ≦ η ₀ ≦ 4.5×10 ^-13 ×Mw ^3.4 ... (Eq-1)
(5) The number average molecular weight (Mn), weight average molecular weight (Mw), and Z average molecular weight (Mz) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-2) .
-2.0 ≦ Mz/Mw - Mw/Mn ≦ 15 ... (Eq-2)
(6) The total of vinyl, vinylidene, 2-substituted internal olefins, and 3-substituted internal olefins per 1000 carbon atoms (number/1000C) measured by ¹ H-NMR is in the range of 0.1 or more and 1.0 or less. .
(a) The density is in the range of 915 kg/m ³ or more and 930 kg/m ³ or less.
(b) The melt flow rate (MFR) under a load of 2.16 kg at 190° C. is in the range of 0.1 g/10 minutes or more and 20 g/10 minutes or less.
(c) The amount of components with a molecular weight of 1 million or more in the molecular weight distribution curve obtained by GPC measurement is in the range of 1.0% to 20%.

[2]
The ethylene resin composition (Z) of [1] above, wherein the ethylene-α-olefin copolymer (A) further satisfies the following requirement (7).
(7) The following relational expression ( Eq-3) is satisfied.
0.7×10 ^-4 ×Mw ^0.776 ≦[η]≦ 1.65×10 ^-4 ×Mw ^0.776 ...(Eq-3)

[3]
The ethylene resin composition (Z) of [1] or [2] above, wherein the ethylene-α-olefin copolymer (A) further satisfies the following requirement (8).
(8) The ratio Mz/Mw of Z average molecular weight (Mz) to weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) is in the range of 4.0 or more and 25.0 or less.

[4]
The ethylene resin composition (Z) according to any one of [1] to [3] above, wherein the ethylene-α-olefin copolymer (A) further satisfies the following requirement (9).
(9) Multiple peaks are present in the melting curve obtained by differential scanning calorimetry (DSC).

[5]
The ethylene resin composition (Z) according to any one of [1] to [4], wherein the high-pressure low-density polyethylene (B) further satisfies the following requirement (d).
(d) Ratio of phase angle [δ100 (°)] at 200°C and angular velocity of 100 rad/sec to phase angle [δ0.01 (°)] at 200°C and angular velocity of 0.01 rad/sec [δ100/δ0.01] is in the range of 0.46 or more and 0.76 or less.

[6]
The ethylene resin composition according to any one of [1] to [5] above, further comprising a thermoplastic resin (excluding the ethylene-α-olefin copolymer (A) and high-pressure low-density polyethylene (B)). Thing (Z).

[7]
A molded article containing the ethylene resin composition (Z) according to any one of [1] to [6] above.
[8]
A film comprising the ethylene resin composition (Z) according to any one of [1] to [6] above.

[9]
A multilayer film having a layer containing the ethylene resin composition (Z) according to any one of [1] to [6] above.
[10]
A laminate having a layer containing the ethylene resin composition (Z) according to any one of [1] to [6] above.

[11]
The laminate according to [10] above, further comprising a base material layer.
[12]
The laminate of [10] above, further comprising a barrier layer.

[13]
A method for producing a laminate, comprising extrusion laminating the ethylene resin composition (Z) according to any one of [1] to [6] above between a base layer and a barrier layer.

According to the ethylene resin composition (Z) of the present invention, a molded product with excellent moldability (that is, no occurrence of take-up surging in T-die molding and small neck-in) and particularly excellent mechanical strength can be obtained. In particular, films, laminates, and containers made of the laminate can be suitably manufactured.

Further, the ethylene resin composition (Z) of the present invention has excellent adhesive strength when used in an adhesive layer of a laminate.

Hereinafter, the ethylene resin composition (Z) according to the present invention will be specifically explained together with its constituent components, ethylene-α-olefin copolymer (A) and high-pressure low density polyethylene (B).

[Ethylene resin composition (Z)]
[Ethylene-α-olefin copolymer (A)]
The ethylene-α-olefin copolymer (A) is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 6 to 10 carbon atoms. Examples of the α-olefin having 4 to 10 carbon atoms used for copolymerization with ethylene include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.

The ethylene/α-olefin copolymer (A) may contain at least one structural unit derived from biomass-derived ethylene or α-olefin. The monomers of the same type constituting the polymer may be only biomass-derived monomers, only fossil fuel-derived monomers, or may contain both biomass-derived monomers and fossil fuel-derived monomers. Biomass-derived monomers are monomers made from all renewable natural raw materials and their residues, such as those derived from plants or animals, including fungi, yeast, algae, and bacteria. ^-12 , and the biomass carbon concentration (pMC) measured in accordance with ASTM D6866 is about 100 (pMC). Biomass-derived ethylene and α-olefin can be obtained, for example, by conventionally known methods.

It is preferable that the ethylene/α-olefin copolymer (A) contains a structural unit derived from a biomass-derived monomer from the viewpoint of reducing environmental load.
The ethylene-α-olefin copolymer (A) has the properties shown in (1) to (6) below.

(1) The density is in the range of 890 kg/m ³ or more and 935 kg/m ³ or less, preferably 900 kg/m ³ or more and 925 kg/m ³ or less, and more preferably 905 kg/m ³ or more and 922 kg/m ³ or less.

When the density is above the above lower limit, the surface of the film formed from the ethylene resin composition (Z) has little stickiness, and when the density is below the above upper limit, the impact of the film formed from the ethylene resin composition (Z) is low. The strength is good, and the mechanical strength such as heat sealing strength and bag tearing strength of the bag made of the film is good.

The density depends on the α-olefin content of the ethylene-α-olefin copolymer; the lower the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. The α-olefin content of the ethylene-α-olefin copolymer is determined by the composition ratio of α-olefin and ethylene (α-olefin/ethylene) in the polymerization system (e.g., Walter Kaminsky, Makromol.Chem. 193, p. 606 (1992)), an ethylene-α-olefin polymer having a density within the above range can be produced by increasing or decreasing the amount of α-olefin/ethylene.

Measurement of density is performed as follows.
The strand obtained at the time of MFR measurement is heat treated at 100° C. for 30 minutes, further left at room temperature for 1 hour, and then measured using the density gradient tube method.

(2) Melt flow rate (MFR) is 1.0 g/10 minutes or more and 15.0 g/10 minutes or less, preferably 1.0 g/10 minutes or more and 12.0 g/10 minutes or less, more preferably 3.0 g/10 It is in the range of 12.0 g/10 minutes or more.

When the melt flow rate (MFR) is equal to or higher than the lower limit, the shear viscosity of the ethylene resin composition (Z) is not too high and the extrusion load is good. When the melt flow rate (MFR) is below the upper limit, the mechanical strength of the ethylene resin composition (Z) is good.

The melt flow rate (MFR) is strongly dependent on the molecular weight; the smaller the melt flow rate (MFR), the larger the molecular weight, and the larger the melt flow rate (MFR), the smaller the molecular weight. It is also known that the molecular weight of ethylene polymers is determined by the composition ratio of hydrogen and ethylene (hydrogen/ethylene) in the polymerization system (for example, "Catalytic Olefin Polymerization" edited by Kazuo Soga et al. Kodansha Scientific, 1990, p.376). Therefore, by increasing or decreasing hydrogen/ethylene, it is possible to increase or decrease the melt flow rate (MFR) of the ethylene polymer. Melt flow rate (MFR) is measured according to JIS K 7210 at 190° C. and under a load of 2.16 kg.

(3) The ratio of melt tension [MT (g)] to shear viscosity [η ^* (P)] (P is Poise) at 200°C and angular velocity 1.0 rad/sec [MT/η ^* (g /P)] is 1.40×10 ^-4 to 2.90×10 ^-4 , preferably 1.50×10 ^-4 to 2.70×10 ^-4 , more preferably 1.60×10 ^-4 to It is in the range of 2.45×10 ^-4 .

When MT/η ^* is greater than or equal to the lower limit, the ethylene-α-olefin copolymer (A) has a high melt tension relative to its molecular weight, so the ethylene resin composition (Z) has excellent moldability. When MT/η ^* is below the upper limit, the ethylene resin composition (Z) has excellent mechanical strength.

MT/η ^* depends on the long chain branching content of the ethylene polymer; the higher the long chain branching content, the higher the MT/η ^* , and the lower the long chain branching content, the lower the MT/η ^* . Long chain branching is defined as a branched structure with a length longer than the molecular weight (Me) between entanglement points contained in an ethylene polymer, and the introduction of long chain branching improves the melt properties and moldability of the ethylene polymer. It is known that it changes significantly (for example, Kazuo Matsuura et al., ed., "Polyethylene Technology Reader", Industrial Research Institute, 2001, p. 32, 36).

MT/η ^* can be adjusted by the type of component (A) or solid support (S) of the olefin polymerization catalyst (X), which will be described later. Further, even when the same olefin polymerization catalyst (X) is used, it can be adjusted by changing the polymerization conditions or the polymerization process. For example, by increasing the ethylene partial pressure, MT/η ^* can be lowered. MT/η ^* near the lower limit can be obtained under the manufacturing conditions of Manufacturing Example 2, which will be described later, and MT/η ^* near the upper limit can be obtained under the manufacturing conditions of Manufacturing Example 13, which will be described later.

Melt tension [MT (g)] is measured as follows.
Melt tension (MT) (unit: g) is determined by measuring the stress when stretched at a constant speed. A capillary rheometer is used for the measurement (for example, in the examples described later, a capillary rheometer: Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd. was used). The conditions are: resin temperature 190°C, melting time 6 minutes, barrel diameter 9.55 mmφ, extrusion speed 15 mm/min, winding speed 24 m/min (if the molten filament breaks, reduce the winding speed by 5 m/min) ), the nozzle diameter is 2.095 mmφ, and the nozzle length is 8 mm.

The shear viscosity [η ^* (P)] at 200° C. and an angular velocity of 1.0 rad/sec is measured as follows. Shear viscosity (η ^* ) is measured by measuring the angular velocity [ω (rad/sec)] dispersion of shear viscosity (η ^* ) at a measurement temperature of 200°C in the range of 0.01≦ω≦100. For the measurement, a viscoelasticity measuring device was used (for example, in the examples described later, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used), a parallel plate of 25 mmφ was used as a sample holder, and the sample thickness was set to about 2. .0mm. The number of measurement points is 5 points per digit of ω. The amount of distortion is appropriately selected in the range of 3 to 10% so that torque can be detected within the measurement range and torque is not exceeded.

The sample used for the shear viscosity measurement was prepared using a molding machine (for example, in the examples described later, a press molding machine made by Shinto Metal Industry Co., Ltd. was used), preheating temperature was 190°C, preheating time was 5 minutes, heating temperature was 190°C, and heating was performed using a molding machine. A measurement sample is press-molded to a thickness of 2 mm under the following conditions: 2 minutes, heating pressure 100 kgf/cm ² , cooling temperature 20° C., cooling time 5 minutes, cooling pressure 100 kgf/cm ² .

(4) Zero shear viscosity [η ₀ (P)] at 200°C and weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .

0.01×10 ^-13 ×Mw ^3.4 ≦ η ₀ ≦ 4.5×10 ^-13 ×Mw ^3.4 ... (Eq-1)
Preferably, the following (Eq-1') is satisfied.
0.1×10 ^-13 ×Mw ^3.4 ≦ η ₀ ≦ 3.0×10 ^-13 ×Mw ^3.4 ...(Eq-1')
More preferably, the following (Eq-1") is satisfied.
0.2×10 ^-13 ×Mw ^3.4 ≦ η ₀ ≦ 2.0×10 ^-13 ×Mw ^3.4 ...(Eq-1")

When the zero shear viscosity [η0 (P)] is plotted logarithmically against the weight average molecular weight (Mw), the extensional viscosity does not show strain hardening like a linear ethylene polymer without long chain branching. Resins follow a power law with a slope of 3.4, whereas resins whose elongational viscosity exhibits strain rate hardening, such as high-pressure low-density polyethylene, have a zero shear viscosity [η ₀ (P )] (C Gabriel, H. Munstedt, J. Rheol., 47(3), 619(2003)). If the zero shear viscosity [η ₀ (P)] at 200°C is below the above upper limit, the elongational viscosity of the ethylene polymer exhibits strain rate hardening properties, so the ethylene resin composition (Z) may be withdrawn when molded. Surging does not occur.

The relationship between zero shear viscosity [η ₀ (P)] and weight average molecular weight (Mw) is thought to depend on the content and length of long chain branches in the ethylene polymer. The smaller the long chain branch content and the shorter the long chain branch length, the smaller the zero shear viscosity [η ₀ (P)]. [η ₀ (P)] is considered to be a large value.

The zero shear viscosity [η ₀ (P)] can be adjusted by the type of component (A) or solid support (S) of the olefin polymerization catalyst (X), which will be described later. Furthermore, even when using the same olefin polymerization catalyst (X), it can be adjusted by changing the polymerization conditions or polymerization process. For example, by increasing the ethylene partial pressure, the zero shear viscosity [η ₀ (P)] can be increased. be able to. A zero shear viscosity [η ₀ (P)] near the lower limit is obtained by the production conditions of Production Examples 14 and 15 described later, and a zero shear viscosity [η ₀ (P)] near the upper limit is obtained by the production conditions of Production Example 12 described later. be able to.

Zero shear viscosity [η ₀ (P)] at 200° C. is measured as follows.
At a measurement temperature of 200° C., the angular velocity ω (rad/sec) dispersion of shear viscosity (η ^* ) is measured in the range of 0.01≦ω≦100. A viscoelasticity measuring device was used for the measurement (for example, in the examples described later, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used), a 25 mmφ parallel plate was used as a sample holder, and the sample thickness was set to about 2.5 mm. It is set to 0mm. The number of measurement points is 5 points per digit of ω. The amount of distortion is appropriately selected in the range of 3 to 10% so that torque can be detected within the measurement range and torque is not exceeded.

The sample used for the shear viscosity measurement was prepared using a molding machine (for example, in the examples described later, a press molding machine made by Shinto Metal Industry Co., Ltd. was used), preheating temperature was 190°C, preheating time was 5 minutes, heating temperature was 190°C, and heating was performed using a molding machine. A measurement sample is press-molded to a thickness of 2 mm under the following conditions: 2 minutes, heating pressure 100 kgf/cm ² , cooling temperature 20° C., cooling time 5 minutes, cooling pressure 100 kgf/cm ² .

Zero shear viscosity (η ₀ ) is calculated by fitting the Carreau model of the following formula to an actually measured rheological curve [angular velocity (ω) dispersion of shear viscosity (η ^* )] using the nonlinear least squares method.

η ^* =η ₀ [1+(λω) ^a ] ^(n-1)/a
[λ is a parameter with a time dimension, a is a fitting parameter, and n is a power law index of the material. ]
Note that fitting using the nonlinear least squares method is performed so that d in the following equation is minimized.

[ηexp(ω) represents the actually measured shear viscosity, and ηcalc(ω) represents the shear viscosity calculated from the Carreau model. ]
Weight average molecular weight (Mw) etc. are measured by gel permeation chromatography (GPC) as follows.

A differential refractometer and a capillary viscometer were used as detectors, the column temperature was 145°C, o-dichlorobenzene was used as the mobile phase, the flow rate was 1.0 ml/min, and the sample concentration was 0.1% by weight. , using polystyrene as the standard polymer. In the examples described later, a GPC-viscosity detector (GPC-VISCO) PL-GPC220 manufactured by Agilent is used as a measuring device, two Agilent PLgel Olexis are used as analytical columns, and standard polystyrene is a GPC-viscosity detector (GPC-VISCO) PL-GPC220 manufactured by Tosoh Corporation. I used the one from For molecular weight calculation, the actual viscosity is calculated from the viscometer and refractometer, and the number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw/Mn, Mz) is calculated from the actual measurement universal calibration. /Mw).

(5) The number average molecular weight (Mn), weight average molecular weight (Mw), and Z average molecular weight (Mz) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-2) .

-2.0≦ Mz/Mw - Mw/Mn ≦15 ... (Eq-2)
Preferably, the following relational expression (Eq-2') is satisfied.
-1.5≦ Mz/Mw - Mw/Mn ≦12 ... (Eq-2')
More preferably, the following relational expression (Eq-2'') is satisfied.
-1.0≦ Mz/Mw - Mw/Mn ≦10 ... (Eq-2")

When Mz/Mw-Mw/Mn is large, the molecular weight distribution spreads toward the high molecular weight side, and when Mz/Mw-Mw/Mn is more than the above lower limit, the ethylene resin composition (Z) has poor molten film stability. If it is below the upper limit, the ethylene resin composition (Z) has excellent thin film formability.

Mz/Mw-Mw/Mn can be adjusted by the type of component (A) or solid support (S) of the olefin polymerization catalyst (X) described below, and if the same olefin polymerization catalyst (X) is used. Even if it is, it can be adjusted by the polymerization conditions or polymerization process. Mz/Mw-Mw/Mn near the lower limit can be obtained by the production conditions of Production Example 5, which will be described later, and Mz/Mw-Mw/Mn near the upper limit can be obtained by the polymerization conditions of Production Example 14, which will be described later.

The number average molecular weight (Mn), weight average molecular weight (Mw), and Z average molecular weight (Mz) are measured by the methods described above.

(6) The number of vinyl, vinylidene, 2-substituted internal olefins, and 3-substituted internal olefins measured by ¹ H-NMR satisfies the following relational expression (Eq-3).

0.1≦vinyl+vinylidene+2-substituted internal olefin+3-substituted internal olefin≦1.0
...(Eq-3)
Preferably, the following relational expression (Eq-3') is satisfied.
0.3≦vinyl+vinylidene+2-substituted internal olefin+3-substituted internal olefin≦0.9
...(Eq-3')
More preferably, the following relational expression (Eq-3'') is satisfied.
0.5≦vinyl+vinylidene+2-substituted internal olefin+3-substituted internal olefin≦0.8
...(Eq-3")

The number of vinyl, vinylidene, di-substituted internal olefin, and tri-substituted internal olefin in the polymer is the number per 1000 carbons contained in the polymer, as measured by ¹ H-NMR method. It is known that the production ratio and number of vinyl, vinylidene, 2-substituted internal olefins, and 3-substituted internal olefins increase or decrease depending on the transition metal compound used (H.SAIKI, S.MAKOTO, T.MASAO, S.MORIHIKO, Y.AKIHIRO, J. Polym. Sci., A: Polym. Chem., 38, 4641 (2000)). These can be adjusted by the type of component (A) or solid support (S) of the olefin polymerization catalyst (X), which will be described later. Further, even when the same olefin polymerization catalyst (X) is used, it can be adjusted by changing the polymerization conditions or the polymerization process, and for example, it can be increased or decreased by increasing or decreasing the ethylene partial pressure.

When the number of vinyl + vinylidene + 2-substituted internal olefin + 3-substituted internal olefin is more than the above-mentioned lower limit, long chain branching is likely to occur, the ethylene resin composition (Z) has excellent moldability, and vinyl + vinylidene + 2-substituted internal olefin + 3 When the number of substituted internal olefins is below the above upper limit, the ethylene resin composition (Z) becomes difficult to oxidize the molten film during molding, has excellent heat sealability, and improves the transparency and mechanical strength of the molded product. Excellent in

The numbers of vinyl, vinylidene, di-substituted internal olefins, and tri-substituted internal olefins measured by ¹ H-NMR (500 MHz) were measured using a nuclear magnetic resonance apparatus (for example, in the examples described later, Bruker's AVANCE III ( A cryoprobe type nuclear magnetic resonance apparatus was used.), and the measurement was performed as follows.

The measurement mode is single pulse, pulse width 45°. The number of points is 32k, the observation range is 20 ppm (-6 to 14 ppm), the repetition time is 7 seconds, and the number of integrations is 64. After dissolving 20 mg of the sample in 40.6 ml of orthodichlorobenzene-d, the sample is measured at 120°C.

In the ¹ H-NMR spectrum, the number of double bonds calculated from the signal integral value derived from various double bonds (vinyl, vinylidene, internal olefin) at 4.5 ppm to 5.8 ppm and the total integral value of all ¹ H signals. The relative value of the total carbon number is determined, and the number of various double bonds per 1000 polymer carbons is calculated.

The ethylene-α-olefin copolymer (A) preferably has the characteristics shown in (7) below.

(7) The following relational expression ( Eq-3) is satisfied.

0.7×10 ^-4 ×Mw ^0.776 ≦[η]≦ 1.65×10 ^-4 ×Mw ^0.776 ...(Eq-3)
Preferably, the following (Eq-3') is satisfied.
0.7×10 ^-4 ×Mw ^0.776 ≦[η]≦ 1.40×10 ^-4 ×Mw ^0.776 ...(Eq-3')
More preferably, the following (Eq-3'') is satisfied.
0.8×10 ^-4 ×Mw ^0.776 ≦[η]≦ 1.20×10 ^-4 ×Mw ^0.776 ...(Eq-3")

When long chain branches are introduced into an ethylene polymer, the intrinsic viscosity [[η] (dl/g)] becomes smaller compared to a straight chain ethylene polymer without long chain branches, relative to the molecular weight. is known (for example, Walther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched Polymer II, p. 137 (1999)). Therefore, when the intrinsic viscosity [[η] (dl/g)] is 1.65×10 ^-4 ×Mw ^0.776 or less, the obtained ethylene polymer has many long chain branches, and has good moldability and Excellent fluidity.

The intrinsic viscosity [[η] (dl/g)] can be adjusted by the type of component (A) or solid support (S) of the olefin polymerization catalyst (X), which will be described later. Furthermore, even when the same olefin polymerization catalyst (X) is used, it can be adjusted by the polymerization conditions or polymerization process. For example, by increasing the ethylene partial pressure, the intrinsic viscosity [[η] (dl/g)] can be raised. The intrinsic viscosity [[η] (dl/g)] near the lower limit under the production conditions of Production Example 11, which will be described later, was changed to the limiting viscosity [[η] (dl/g)] near the upper limit under the production conditions of Production Example 12, which will be described later. ] can be obtained.

The intrinsic viscosity [[η] (dl/g)] is measured using decalin solvent as follows.
Approximately 20 mg of the sample to be measured is dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135°C. After diluting the decalin solution by adding 5 ml of decalin solvent, the specific viscosity ηsp is measured in the same manner. This dilution operation is repeated two more times, and the value of ηsp/C when the concentration (C) is extrapolated to 0 is determined as the limiting viscosity [η] (unit: dl/g) as shown in the following formula.

[η]=lim(ηsp/C) (C→0)
Weight average molecular weight (Mw) is measured as described above.
The ethylene-α-olefin copolymer (A) preferably has the characteristics shown in (8) below.

(8) The ratio of Z average molecular weight (Mz) to weight average molecular weight (Mw) (Mz/Mw) measured by GPC-viscosity detector method (GPC-VISCO) is 4.0 to 25.0, preferably 7. It is in the range of .0 to 20.0, more preferably 10.0 to 18.0. The larger the Mz/Mw, the higher the amount of high molecular weight components, and the ethylene resin composition (Z) has excellent neck-in when Mz/Mw is above the above-mentioned lower limit, and has poor thin film formability when Mz/Mw is below the above-mentioned upper limit. Excellent in

Mz/Mw can be adjusted depending on the type of component (A) or solid support (S) of the olefin polymerization catalyst (X), which will be described later, and when the same olefin polymerization catalyst (X) is used. However, it can be adjusted by the polymerization conditions or the polymerization process. Mz/Mw near the lower limit can be obtained by the production conditions of Production Example 5, which will be described later, and Mz/Mw near the upper limit can be obtained by the polymerization conditions of Examples 11 and 14, which will be described later.

The ethylene-α-olefin copolymer (A) preferably has the characteristics shown in (9) below.

(9) Multiple peaks are present in the melting curve obtained by differential scanning calorimetry (DSC).
If it has multiple peaks, it has many low melting point components and has excellent heat sealability at low temperatures.
Differential scanning calorimetry (DSC) is carried out as follows using a differential scanning calorimeter (for example, PerkinElmer Diamond DSC was used in the examples described later).

Approximately 5 mg of the sample was packed in an aluminum pan, heated to 200°C at 10°C/min, held at 200°C for 10 minutes, cooled to -30°C at 10°C/min, and then heated to 200°C at 10°C/min. Obtain the endothermic curve when raising the temperature to . The fact that this endothermic curve has two or more peaks means that a plurality of peaks are present in the melting curve obtained by differential scanning calorimetry (DSC).

When the ethylene-α-olefin copolymer (A) has the characteristics shown in (9) above, the ethylene resin composition (Z) of the present invention, when used in the heat seal layer of the laminate, has the following properties: Excellent heat sealability.

[High pressure low density polyethylene (B)]
The high-pressure low-density polyethylene (B) is produced by polymerizing ethylene using a high-pressure radical polymerization method, and has a large number of long chain branches.
The high-pressure low density polyethylene (B) has the properties shown in (a) to (c) below.

(a) Density is in the range of 915 kg/m ³ or more and 930 kg/m ³ or less, preferably 915 kg/m ³ or more and 925 kg/m ³ or less, more preferably 915 kg/m ³ or more and 920 kg/m ^{3 or} less.

When the density is below the upper limit, the low-temperature heat sealability of the film formed from the ethylene resin composition (Z) will be good. It is difficult to produce high-pressure low-density polyethylene whose density is below the lower limit.

(b) Melt flow rate (MFR) is 0.1 g/10 minutes or more and 20 g/10 minutes or less, preferably 0.5 g/10 minutes or more and 10 g/10 minutes or less, more preferably 0.8 g/10 minutes or more.8. It is in the range of 0g/10 minutes or less.

When the melt flow rate (MFR) is equal to or higher than the lower limit, the film formed from the ethylene resin composition (Z) has fewer fish eyes and has a good appearance. When the melt flow rate (MFR) is below the above-mentioned upper limit, the melt tension of the ethylene resin composition (Z) is high and moldability such as molten film stability becomes good.

(c) The amount of components with a molecular weight of 1 million or more in the molecular weight distribution curve obtained by GPC measurement is 1.0% or more and 20% or less, preferably 2.0% or more and 15% or less, and more preferably 4.0% or more13 % or less.

When the amount of components having a molecular weight of 1 million or more in the molecular weight distribution curve obtained by GPC measurement is at least the above lower limit, the ethylene resin composition (Z) has excellent neck-in. When the amount of components having a molecular weight of 1 million or more in the molecular weight distribution curve obtained by GPC measurement is below the above-mentioned upper limit, the ethylene resin composition (Z) has excellent thin film formability.

The amount of components with a molecular weight of 1 million or more in the molecular weight distribution curve obtained by GPC measurement is calculated by measuring using a gel permeation chromatograph under the following conditions. In addition, the following apparatus etc. were used in the Example mentioned later.

[Equipment used]
Measuring device: HLC-8321 GPC/HT type (manufactured by Tosoh Corporation)
Data processing software: Empower 3 (manufactured by Waters)
Column: 2x TSKgel GMH6-HT + 2x TSKgel GMH6-HTL
(Both are 7.5 mmI.D. x 30 cm, manufactured by Tosoh Corporation)
Polystyrene: Monodisperse polystyrene (manufactured by Tosoh Corporation); #3 std set

[Measurement condition]
Column temperature: 140℃
Mobile phase: o-dichlorobenzene (containing 0.025% BHT)
Detector: Differential refractometer Flow rate: 1.0ml/min Sample concentration: 0.1% (w/v)
Injection volume: 400μL
Sampling time interval: 0.5 seconds Column calibration: Polystyrene Molecular weight conversion: PE conversion/general purpose calibration method

From the obtained molecular weight distribution curve, the amount (%) of the component giving a molecular weight of 1,000,000 or more is calculated.
The high-pressure low-density polyethylene (B) preferably has the characteristics shown in (d) below.

(d) Ratio of phase angle [δ100 (°)] at 200°C and angular velocity of 100 rad/sec to phase angle [δ0.01 (°)] at 200°C and angular velocity of 0.01 rad/sec [δ100/δ0.01] is in the range of 0.46 or more and 0.76 or less, preferably 0.46 or more and 0.72 or less, more preferably 0.47 or more and 0.64 or less.

The angular velocity [ω (rad/sec)] dispersion of the phase angle (δ) can be strongly influenced by the content of long chain branches in the ethylene polymer, the length of the long chain branches, and the structure of the long chain branches. known (for example, S. Trinkle, P. Walter, C. Friedrich, Rheol Acta, 41, 103 (2002)). When long chain branches are introduced into the ethylene polymer, δ100/δ0.01 exhibits a larger value than a linear ethylene polymer without long chain branches. Further, the longer the length of the long chain branch introduced or the branched structure with more complicated branching, the larger the value of δ100/δ0.01 is. The ethylene resin composition (Z) has excellent neck-in when δ100/δ0.01 is at least the above-mentioned lower limit, and has good mechanical strength when δ100/δ0.01 is at most the above-mentioned upper limit.

The phase angle [δ100 (°)] at 200° C. and an angular velocity of 100 rad/sec and the phase angle [δ0.01 (°)] at 200° C. and an angular velocity of 0.01 rad/sec are measured as follows.
The angular velocity [ω (rad/sec)] dispersion of the phase angle (δ) at a measurement temperature of 200° C. is measured in the range of 0.01≦ω≦100. A viscoelasticity measuring device was used for the measurement (for example, in the examples described later, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used), a 25 mmφ parallel plate was used as a sample holder, and the sample thickness was set to about 2.5 mm. It is set to 0mm. The number of measurement points is 5 points per digit of ω. The amount of distortion is appropriately selected in the range of 3 to 10% so that torque can be detected within the measurement range and torque is not exceeded.

The sample used for the shear viscosity measurement was prepared using a molding machine (for example, in the examples described later, a press molding machine made by Shinto Metal Industry Co., Ltd. was used), preheating temperature was 190°C, preheating time was 5 minutes, heating temperature was 190°C, and heating was performed using a molding machine. A measurement sample is press-molded to a thickness of 2 mm under the following conditions: 2 minutes, heating pressure 100 kgf/cm ² , cooling temperature 20° C., cooling time 5 minutes, cooling pressure 100 kgf/cm ² .

<Ethylene resin composition (Z)>
The ethylene resin composition (Z) according to the present invention contains the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B), and the ethylene-α-olefin copolymer ( When the sum of the mass fraction (W _A ) of A) and the mass fraction (W B ) of the ethylene-α-olefin copolymer ( _B ) is 100 mass %, W _A is 40 to 90 mass %, W _B is 10 to 60% by mass. W _A is preferably 50 to 85% by weight, more preferably 60 to 75% by weight. Within this range, the ethylene resin composition (Z) has excellent moldability and mechanical strength.

Furthermore, the ethylene resin composition (Z) according to the present invention may consist essentially only of the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). However, it is not limited to this, and in addition to the above ethylene-α-olefin copolymer (A) and the above high-pressure low density polyethylene (B), the above ethylene-α-olefin copolymer (A) and the above It may also contain a thermoplastic resin (hereinafter referred to as "other thermoplastic resin") that is not the high-pressure low-density polyethylene (B). An ethylene resin composition obtained as a thermoplastic resin composition by blending "another thermoplastic resin" with the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). (Z) has excellent moldability and mechanical strength.

The blend ratio of the total of the above ethylene-α-olefin copolymer (A) and the above high-pressure low density polyethylene (B) and “other thermoplastic resin” (ethylene-α-olefin copolymer (A) and The total mass of high-pressure low density polyethylene (B)/mass of other thermoplastic resins is usually 99.9/0.1 to 0.1/99.9, preferably 90/10 to 10/90, More preferably, the ratio is 70/30 to 30/70.

(Other thermoplastic resins)
Other thermoplastic resins include crystalline thermoplastic resins such as polyolefins, polyamides, polyesters, and polyacetals; Plastic resin is used. Polyvinyl chloride is also preferably used.

Specifically, the above polyolefins include ethylene polymers, propylene polymers, butene polymers, 4-methyl-1-pentene polymers, 3-methyl-1-butene polymers, hexene polymers, etc. can be mentioned. Among these, ethylene polymers, propylene polymers, and 4-methyl-1-pentene polymers are preferred; in the case of ethylene polymers, conventional ethylene polymers may be used; Vinyl copolymers may be used, but conventional ethylene-based polymers are more preferred. The ethylene polymer and the propylene polymer may be ethylene polymers and propylene polymers containing biomass-derived monomers, respectively.

The ethylene resin composition (Z) of the present invention may contain weather-resistant stabilizers, heat-resistant stabilizers, antistatic agents, anti-slip agents, anti-blocking agents, antifogging agents, lubricants, Additives such as pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbers, and antioxidants may be blended as necessary.

The total amount of additives is generally 10 parts by mass or less, preferably 1 part by mass or less, and more preferably It is 0.5 part by mass or less.

<Production method of ethylene-α-olefin copolymer (A)>
Next, a method for producing the ethylene-α-olefin copolymer (A) will be explained.
The ethylene-α-olefin copolymer (A) is efficiently produced by polymerizing ethylene and an α-olefin having 4 to 10 carbon atoms in the presence of an olefin polymerization catalyst (X) consisting of the following components: be able to.

[Olefin polymerization catalyst (X)]
The olefin polymerization catalyst (X) contains the following component (A) and solid support (S).

<Component (A)>
Component (A) is a transition metal compound represented by the following formula (1) (hereinafter also referred to as "transition metal compound (1)"). The olefin polymerization catalyst (X) contains at least one transition metal compound (1). That is, as component (A), one type of transition metal compound (1) may be used, or a plurality of types may be used.

In the formula (1), M is a zirconium atom or a hafnium atom, preferably a zirconium atom.
In the formula (1), n is an integer from 1 to 4, preferably 2, selected so that the transition metal compound (1) is electrically neutral.

In the formula (1), each X independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a conjugated diene derivative group, and preferably is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, with chlorine being particularly preferred.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include:
Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butane-2- yl group), tert-butyl group (2-methylpropan-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3 -methylbutyl group), neopentyl group (2,2-dimethylpropyl group), cyamyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2 , 3-dimethylbutyl group, 3,3-dimethylbutyl group, thexyl group (2,3-dimethylbut-2-yl group), linear or branched alkyl group such as 4,4-dimethylpentyl group;
vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl group (prop-1,2-dien-1 -yl group), but-3-en-1-yl group, crotyl group (but-2-en-1-yl group), but-3-en-2-yl group, methallyl group (2-methylallyl group) , but-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl group (3- methylbut-3-en-1-yl group), 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group (3-methylbut-2-en-1-yl group) linear or branched alkenyl groups or unsaturated double bond-containing groups such as
A linear or branched alkynyl group or an unsaturated triple bond-containing group such as an ethynyl group, a prop-2-yn-1-yl group, a propargyl group (prop-1-yn-1-yl group);
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-iso-propylbenzyl group), 2,4,6 Direct aromatic compounds containing aromatic groups such as -tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, and benzhydryl group (diphenylmethyl group) Chain or branched alkyl groups and unsaturated double bond-containing groups;
Cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group;
Phenyl group, tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3, 5,6-tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di- Examples include aromatic substituents such as tert-butylphenyl group, naphthyl group, biphenyl group, tert-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, and ferrocenyl group, preferably methyl group, These are iso-butyl group, neopentyl group, cyamyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, and cumenyl group.

The hydrocarbon group having 1 to 20 carbon atoms may be a halogen-substituted hydrocarbon group in which some or all of the hydrogen atoms of the hydrocarbon group having 1 to 20 carbon atoms are substituted with halogen atoms; Examples include fluoromethyl group, trifluoromethyl group, trichloromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, pentachloroethyl group, pentafluorophenylmethyl group, fluorophenyl group, difluorophenyl group. group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, and preferably pentafluorophenyl group.

Examples of the silicon-containing group include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris( (trimethylsilyl)silyl group, trimethylsilylmethyl group, etc., and trimethylsilylmethyl group is preferred.

Examples of the oxygen-containing group include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group, and benzyloxy group. group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,4,6-trimethylphenoxy group , 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, periodate anion, preferably methoxy group, ethoxy group , iso-propoxy group, and tert-butoxy group.

Examples of the nitrogen-containing group include an amino group, a cyano group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, and a piperidinyl group. group, morpholyl group, pyrrolyl group, bistrifurylimide group, etc.

Examples of the conjugated diene derivative group include a 1,3-butadienyl group, an isoprenyl group (2-methyl-1,3-butadienyl group), a piperylenyl group (1,3-pentadienyl group), and a 2,4-hexadienyl group. , 1,4-diphenyl-1,3-pentadienyl group, cyclopentadienyl group, etc., with 1,3-butadienyl group and 1,3-pentadienyl group being preferred.

In the formula (1), Q is a carbon atom or a silicon atom, preferably a silicon atom.
In the formula (1), R ¹ to R ¹⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, or an oxygen-containing group having 1 to 20 carbon atoms. or a nitrogen-containing group having 1 to 20 carbon atoms, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms as R ¹ to R ¹⁴ include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butan-2-yl group), tert-butyl group (2-methylpropan-2-yl group), iso-butyl group (2-methylpropyl group) , pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), cyamyl group (1,2-dimethylpropyl group), iso- hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, thexyl group (2,3-dimethylbut-2-yl group), Straight-chain or branched alkyl groups such as 4,4-dimethylpentyl groups;
vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl group (prop-1,2-dien-1 -yl group), but-3-en-1-yl group, crotyl group (but-2-en-1-yl group), but-3-en-2-yl group, methallyl group (2-methylallyl group) , but-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl group (3- methylbut-3-en-1-yl group), 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group (3-methylbut-2-en-1-yl group) linear or branched alkenyl groups or unsaturated double bond-containing groups such as
A linear or branched alkynyl group or an unsaturated triple bond-containing group such as an ethynyl group, a prop-2-yn-1-yl group, a propargyl group (prop-1-yn-1-yl group);
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-iso-propylbenzyl group), 2,4,6 -tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group (diphenylmethyl group), pentafluorophenylmethyl group, etc. Straight-chain or branched alkyl groups containing aromatics and unsaturated double bond-containing groups;
Cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group;
Phenyl group, tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3, 5,6-tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di- Aromatic substituents such as tert-butylphenyl group, naphthyl group, biphenyl group, tert-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group;
Fluoromethyl group, trifluoromethyl group, trichloromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, pentachloroethyl group, pentafluorophenylmethyl group, fluorophenyl group, difluorophenyl group, trifluoro Some or all of the hydrogen atoms of the hydrocarbon group having 1 to 20 carbon atoms, such as phenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, are substituted with halogen atoms. a halogen-substituted hydrocarbon group;
Preferably, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec- butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, Cyclooctenyl group, norbornyl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group , 2-phenylethyl group, 3-phenylpropyl group, cinnamyl group, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri -iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, tert-phenyl group, binaphthyl group, phenanthryl group, They are anthracenyl group, ferrocenyl group, and pentafluorophenyl group.

Examples of silicon-containing groups having 1 to 20 carbon atoms as R ¹ to R ¹⁴ include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, and cyclopentadienyl group. Dimethylsilyl group, cyclopentadienyldiphenylsilyl group, indenyldimethylsilyl group, fluorenyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 3 , 5-bis(trimethylsilyl)phenyl group, etc. are preferable, and trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group , 3,5-bis(trimethylsilyl)phenyl group.

The oxygen-containing groups having 1 to 20 carbon atoms as R ¹ to R ¹⁴ include methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyloxy group, benzyloxy group, Phenoxy group, naphthoxy group, tolyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydropyranyl group, furofuryl group, benzofuryl group, dibenzofuryl group, etc., preferably methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, Methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, They are methylfuryl group, benzofuryl group, and dibenzofuryl group.

The nitrogen-containing groups having 1 to 20 carbon atoms as R ¹ to R ¹⁴ include an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, and a dimethyl group. Aminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinyl group Phenyl group, pyrrorylphenyl group, carbazolyl phenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group , indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, etc. , preferably an amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group , julolidinyl group, tetramethyljulolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, and imidazolyl group.

In the formula (1), adjacent substituents among R ¹ to R ⁶ (e.g., R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ ) may be bonded to each other to form a ring which may have a substituent. The ring formed in this case is a saturated hydrocarbon (excluding the hydrocarbon in the indenyl ring) or an unsaturated hydrocarbon which may have a substituent and is condensed to the indenyl ring. ~8-membered rings are preferred. In addition, when a plurality of rings exist, these may be the same or different from each other. Although not particularly limited as long as the effect of the present invention is achieved, the ring is more preferably a 5- or 6-membered ring, and in this case, the combined structure of the ring and the indenyl ring portion of the mother nucleus is, for example, benzoindenyl ring. Examples include a nyl ring, a tetrahydroindacene ring, and a cyclopentatetrahydronaphthalene ring, with benzoindenyl rings and tetrahydroindacene rings being preferred. These rings may have a substituent.

In the formula (1), adjacent substituents among R ⁷ to R ¹² (e.g., R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , and R ¹¹ and R ¹² ) may be bonded to each other to form a ring which may have a substituent. The ring formed in this case is composed of a saturated hydrocarbon (excluding the hydrocarbon in the indenyl ring) or an unsaturated hydrocarbon, which may have a substituent and is condensed to the indenyl ring. A 5- to 8-membered ring is preferred. In addition, when a plurality of rings exist, these may be the same or different from each other. Although not particularly limited as long as the effect of the present invention is achieved, the ring is more preferably a 5- or 6-membered ring, and in this case, the combined structure of the ring and the indenyl ring portion of the mother nucleus is, for example, benzoindenyl ring. Examples include a nyl ring, a tetrahydroindacene ring, a cyclopentatetrahydronaphthalene ring, a tetrahydrofluorene ring, and a fluorene ring, with benzoindenyl rings and tetrahydroindacene rings being preferred. These rings may have a substituent.

In the formula (1), R ¹³ and R ¹⁴ may be bonded to each other to form a ring containing Q, and these rings may have a substituent. The ring formed in this case is preferably a 3- to 8-membered saturated or unsaturated ring which may have a substituent. Although not particularly limited as long as the effect of the present invention is achieved, a 4- to 6-membered ring is preferable. , silacyclopentane (silolane) ring, silacyclohexane (silinane) ring, and silafluorene ring, and cyclopentane ring, silacyclobutane ring, and silacyclopentane ring are preferable. These rings may have a substituent.

Specific examples of the transition metal compound (1) are shown below, but the scope of the present invention is not particularly limited thereto.
For convenience, the ligand structure excluding the portion represented by MXn (metal moiety) of the transition metal compound (1) is 2-indenyl ring portion, 1-indenyl ring portion, indenyl ring portion R ¹ , R ⁶ and R ⁸ substituents, indenyl ring moieties R ² , R ⁵ , R ⁹ and R ¹² substituents, indenyl ring moieties R ³ , R ⁴ , R ¹⁰ and R ¹¹ substituents, 1-indenyl ring moiety R ⁷ substituents, bridging moieties; Divided into seven structures. The abbreviation for the 2-indenyl ring moiety is α, the abbreviation for the 1-indenyl ring moiety is β, the abbreviation for the indenyl ring moiety R ¹ , R ⁶ and R ⁸ is γ, the indenyl ring moiety R ² , R ⁵ , R ⁹ and The abbreviation of the R ¹² substituent is δ, the abbreviation of the indenyl ring moiety R ³ , R ⁴ , R ¹⁰ and R ¹¹ substituents is ε, the abbreviation of the 1-indenyl ring moiety R ⁷ substituent is ζ, the abbreviation of the structure of the bridged part is η, and the abbreviations of each substituent are shown in [Table 1] to [Table 7].

Note that the wavy lines in [Table 1] to [Table 2] above indicate the bonding site with the crosslinked portion.

The R ¹ , R ⁶ and R ⁸ substituents in [Table 3] may be the same or different in combination.

The R ² , R ⁵ , R ⁹ and R ¹² substituents in the above [Table 4] may be the same or different in combination.

The R ³ , R ⁴ , R ¹⁰ and R ¹¹ substituents in [Table 5] may be the same or different in combination.

Specific examples of the metal portion MXn include ZrF ₂ , ZrCl ₂ , ZrBr ₂ , ZrI ₂ , Zr(Me) ₂ , Zr(Bn) ₂ , Zr(Allyl) ₂ , Zr(CH ₂ -tBu) ₂ , Zr(1,3-butadienyl), Zr(1,3-pentadienyl), Zr(2,4-hexadienyl), Zr(1,4-diphenyl-1,3-pentadienyl), Zr(CH ₂ -Si(Me ) ₃ ) ₂ , Zr(OMe) ₂ , Zr(OiPr) ₂ , Zr(NMe ₂ ) ₂ , Zr(OMs) ₂ , Zr(OTs) ₂ , Zr(OTf) ₂ , HfF ₂ , HfCl ₂ , HfBr ₂ , HfI ₂ , Hf(Me) ₂ , Hf(Bn) ₂ , Hf(Allyl) ₂ , Hf(CH ₂ -tBu) ₂ , Hf(1,3-butadienyl), Hf(1,3-pentadienyl), Hf (2,4-hexadienyl), Hf(1,4-diphenyl-1,3-pentadienyl), Hf(CH ₂ -Si(Me) ₃ ) ₂ , Hf(OMe) ₂ , Hf(OiPr) ₂ , Hf( Examples include NMe ₂ ) ₂ , Hf(OMs) ₂ , Hf(OTs) ₂ , Hf(OTf) ₂ and the like. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si(Me) ₃ is a trimethylsilyl group, ОMe is a methoxy group, ОiPr is an iso-propoxy group, NMe ₂ is a dimethylamino group, ОMs is a methanesulfonate group The group ОTs is a p-toluenesulfonate group, and ОTf is a trifluoromethanesulfonate group.

According to the above notation, the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-5 in [Table 2], and the indenyl ring moiety R ¹ , R ⁶ and R ⁸ All substituents are γ-1, 2-indenyl ring moieties R ² and R ⁵ in [Table 3] Both substituents are δ-1, 2-indenyl ring moieties R ³ and R ⁴ in [Table 4] All substituents are ε-1 in [Table 5], 1-indenyl ring moiety R ⁷ substituent is ζ-30 in [Table 6], 1-indenyl ring moiety R ⁹ substituent is in [Table 4] δ-38, 1-indenyl ring part R ¹² The substituent is δ-3 in [Table 4], the crosslinking part is composed of η-20 in [Table 7], and the metal moiety MXn is ZrCl ₂ In the case of , a compound represented by the following formula [6] is exemplified.

Furthermore, the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-2 in [Table 2], and the indenyl ring moiety R ¹ , R ⁶ and R ⁸ are all substituents. The γ-1, 2-indenyl ring moiety R ² and R ⁵ substituents in [Table 3] are both the δ-2, 2-indenyl ring moiety R ³ and R ⁴ substituents in [Table 4] The ε-1, 1-indenyl ring moiety R ⁷ in [Table 5] is composed of a combination of ζ-1 in [Table 6] and the crosslinking part is η-4 in [Table 7], and the metal moiety When MXn is Zr(NMe ₂ ) ₂ , the compound represented by the following formula [7] is exemplified.

In addition, the 2-indenyl ring moiety is the α-3, 1-indenyl ring moiety in [Table 1], and the β-1, 2-indenyl ring moiety in [Table 2] is the R ¹ and R ⁶ substituent. The γ-2, indenyl ring moiety R ² , R ⁵ and R ¹² substituents in [Table 3] are all the δ-1, 1-indenyl ring moiety R 7 substituent in [Table 4] is the R ⁷ substituent in [Table 6]. The ζ-12, 1-indenyl ring moiety R ⁸ substituent is the γ-1, 1-indenyl ring moiety in [Table 3] The R ⁹ substituent is the δ-42, 1-indenyl ring moiety in [Table 4] The R ¹⁰ substituent is ε-3 in [Table 5], the 1-indenyl ring moiety R ¹¹ substituent is ε-12 in [Table 5], and the bridging part is η-31 in [Table 7]. When MXn of the metal part is HfMe ₂ , a compound represented by the following formula [8] is exemplified.

In addition, the 2-indenyl ring moiety is α-1 in [Table 1], and the 1-indenyl ring moiety is β-1, 2-indenyl ring moiety in [Table 2]. Both R ¹ and R ⁶ substituents are [ The γ-1, 2-indenyl ring moiety R ² substituent in [Table 3] is the δ-7, 2-indenyl ring moiety R ³ , R ⁴ , R ¹⁰ and R ¹¹ substituent in [Table 4] ε-1 in [Table 5], 2-indenyl ring moiety R ⁵ substituent is δ-2 in [Table 4], 1-indenyl ring moiety R ⁷ substituent is ζ-1 in [Table 6], The 1-indenyl ring moiety R ⁸ substituent is γ-9 in [Table 3], the 1-indenyl ring moiety R ⁹ and R ¹² substituents are all δ-1 in [Table 4], and the bridging moiety is γ-9 in [Table 3]. 7], and when MXn of the metal moiety is Zr (1,3-pentadienyl), the compound represented by the following formula [9] is exemplified.

The transition metal compound (1) can be produced using a conventionally known method, and the production method is not particularly limited.
The substituted indene compound as a starting material can be produced by a known method, and the production method is not particularly limited. Examples of known manufacturing methods include "Oganometallics 1994, 13, 954.", "Oganometallics 2006, 25, 1217.", Japanese Patent Publication No. 2006-509059, and "Bioorg.Med.Chem. 2008, 16, 7399." ”, WO2009/080216 Publication, "Oganometallics 2011, 30, 5744.", Special Publication No. 2011-500800, "Oganometallics 2012, 31, 4962.", "Chem. Eur. J. 2012, 18 , 4174.'', special JP 2012-012307, JP 2012-121882, JP 2014-196319, JP 2014-513735, JP 2015-063495, JP 2016-501952, JP 2019 Examples include the manufacturing method disclosed in JP-A-059933 and the like.

Known methods for producing the transition metal compound (1) and the precursor compound (ligand) include, for example, "Macromolecules 2001, 34, 2072.", "Macromolecules 2003, 36, 9325.", "Organometallics 2004, 23". , 5332.'', ``Eur. J. Inorg. Chem. 2005, 1003.'', and ``Eur. J. Inorg. Chem. 2009, 1759.''.

Further, in the transition metal compound (1), the indenyl ring portion bonded to the central metal exists in two directions (front surface and back surface) with the crosslinked portion in between. Therefore, when a plane of symmetry does not exist in the 2-indenyl ring moiety, two types of structural isomers exist, as shown by the following general formula [10a] or [10b], for example.

Similarly, even when the substituents R ¹³ and R ¹⁴ of the crosslinking portion are not the same, two types of structural isomers exist, as shown by the following general formula [11a] or [11b], for example.

Purification and fractionation of these structural isomer mixtures, or selective production of structural isomers can be performed by known methods, and the production method is not particularly limited. In addition to the method for producing the transition metal compound (1), known production methods include JP-A-10-109996, "Oganometallics 1999, 18, 5347.", "Oganometallics 2012, 31, 4340." ”, and the manufacturing method disclosed in Japanese Patent Publication No. 2011-502192.

Note that within the range of the transition metal compound (1), one type of transition metal compound may be used alone, two or more types may be used in combination, a mixture of structural isomers may be used, and structural isomers may be used. may be used alone, or a mixture of two or more structural isomers may be used. As described above, according to the present invention, an ethylene polymer having a large number of long chain branches introduced with high catalytic activity can be produced by using only the transition metal compound (1) as a transition metal compound constituting an olefin polymerization catalyst. However, one or more transition metal compounds other than the transition metal compound (1) may be used in combination as the transition metal compound to the extent that this effect is not impaired. At this time, the transition metal compound (1) may be in any of the above embodiments.

<Solid carrier (S)>
The solid carrier (S) contained in the olefin polymerization catalyst (X) is an inorganic compound or an organic compound, and is a granular or particulate solid.

Examples of the inorganic compound used as the solid support (S) include porous oxides, solid aluminoxane compounds, inorganic chlorides, clays, clay minerals, and ion exchange layered compounds.

Examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO and ThO ₂ , or a composite or mixture containing these, specifically are natural or synthetic zeolites, SiO ₂ --MgO, SiO ₂ --Al ₂ O ₃ , SiO ₂ --TiO ₂ , SiO ₂ --V ₂ O ₅ , SiO ₂ --Cr ₂ O ₃ and SiO ₂ --TiO ₂ --MgO, etc. is used. Among these, those containing SiO ₂ as a main component are preferred.

Note that the above porous oxide contains a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg(NO ₃ ) Carbonates, sulfates, nitrates, and oxide components such as ₂ , Al(NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O may be contained.

The properties of such porous oxides vary depending on the type and manufacturing method, but as a solid support (S), the particle size is usually 0.2 to 300 μm, preferably 1 to 200 μm, and the specific surface area is The pore volume is usually in the range of 50 to 1200 m ² /g, preferably 100 to 1000 m ² /g, and the pore volume is preferably in the range of 0.3 to 30 cm ³ /g. Such a carrier is used after being fired at, for example, 100 to 1000°C, preferably 150 to 700°C, if necessary.

The solid aluminoxane compounds include aluminoxanes having a structure represented by the following general formula (S-a), aluminoxanes having a structure represented by the following general formula (S-b), and aluminoxane having a structure represented by the following general formula (S-c). Examples include aluminoxane having a structure consisting of a repeating unit represented by the above formula and a repeating unit represented by the following general formula (Sd).

In the above formulas (S-a) to (S-d), R ^e is each independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group Examples include hydrocarbon groups such as , octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, and ethylphenyl group, with methyl group, ethyl group, and isobutyl group being preferred, and methyl group being particularly preferred. preferable. Further, a part of R ^e may be substituted with a halogen atom such as chlorine or bromine, and the halogen content may be 40% by weight or less based on R ^e . In the above formulas (Sc) and (Sd), a straight line on which one side is not connected to an atom indicates a bond with another atom not shown.

In the formulas (S-a) and (S-b), r represents an integer of 2 to 500, preferably 6 to 300, particularly preferably 10 to 100. In the formulas (S-c) and (S-d), s and t each represent an integer of 1 or more. r, s and t are selected such that the aluminoxane remains substantially solid under the reaction environment used.

Unlike conventionally known carriers for olefin polymerization catalysts, the solid aluminoxane compound does not contain inorganic solid components such as silica or alumina, or organic polymer components such as polyethylene or polystyrene, and is a solid material containing an alkyl aluminum compound as the main component. It has become. "Solid state" means that the aluminoxane component remains substantially solid under the reaction environment in which it is used. More specifically, when preparing an olefin polymerization catalyst (e.g. ethylene polymerization catalyst) by bringing the component (A) and an aluminoxane component into contact as described below, and using the prepared olefin polymerization catalyst The aluminoxane component maintains a substantially solid state during polymerization (eg, suspension polymerization) of olefin (eg, ethylene).

Visual confirmation is the easiest way to determine whether the aluminoxane component is in a solid state, but visual confirmation is often difficult, for example, during polymerization. In that case, it is possible to judge from, for example, the properties of the polymer powder obtained after polymerization and the state of adhesion to the reactor. On the other hand, as long as the polymer powder has good properties and is less likely to adhere to the reactor, even if some of the aluminoxane component is eluted under the polymerization environment, this does not depart from the spirit of the present invention. Indices for determining the properties of the polymer powder include bulk density, particle shape, surface shape, degree of presence of amorphous polymer, etc., but polymer bulk density is preferred from the quantitative viewpoint. The bulk density is usually 0.01 to 0.9, preferably 0.05 to 0.6, more preferably 0.1 to 0.5.

The dissolution rate of the solid aluminoxane compound in n-hexane maintained at a temperature of 25° C. is usually in the range of 0 to 40 mol%, preferably 0 to 20 mol%, particularly preferably 0 to 10 mol%. .

The above dissolution rate was determined by adding 2 g of solid aluminoxane compound carrier to 50 ml of n-hexane kept at 25°C, stirring for 2 hours, and then separating the solution part using a G-4 glass filter. It is determined by measuring the aluminum concentration in this filtrate. Therefore, the dissolution rate is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of aluminoxane used.

As the solid aluminoxane compound, any known solid aluminoxane can be used without restriction, and for example, the solid polyaluminoxane composition described in International Publication No. 2014/123212 can also be used. Known manufacturing methods include, for example, JP-A No. 7-42301, JP-A 6-220126, JP-A 6-220128, JP-A 11-140113, JP-A 11-310607, and JP-A-11-310607. Examples include manufacturing methods described in JP-A No. 2000-38410, JP-A No. 2000-95810, and International Publication No. 2010/55652.

The average particle size of the solid aluminoxane compound is generally in the range of 0.01 to 50,000 μm, preferably 0.1 to 1,000 μm, particularly preferably 1 to 200 μm. The average particle diameter of the solid aluminoxane compound is determined by observing the particles with a scanning electron microscope, measuring the particle diameters of 100 or more particles, and averaging them by weight. First, the particle diameter d of each particle is determined by the following formula by measuring the length of a particle image between two parallel lines in both the horizontal and vertical directions.

Particle diameter d = ((horizontal length) ² + (vertical length) ² ) ^0.5
Next, the weight average particle diameter of the solid aluminoxane compound is determined by the following formula using the particle diameter d and the number of particles n determined above.
Average particle diameter = Σnd ⁴ /Σnd ³
The solid aluminoxane compound preferably has a specific surface area of 50 to 1000 m ² /g, preferably 100 to 800 m ² /g, and a pore volume of 0.1 to 2.5 cm ³ /g.

Examples of the inorganic halides include MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ and the like. The inorganic halide may be used as it is, or after being pulverized using a ball mill or a vibration mill. Alternatively, an inorganic halide may be dissolved in a solvent such as alcohol and then precipitated into fine particles using a precipitating agent.

Clay is usually composed mainly of clay minerals. Further, an ion-exchangeable layered compound is a compound having a crystal structure in which surfaces constituted by ionic bonds or the like are stacked in parallel with each other with weak bonding force, and the ions contained therein can be exchanged. Most clay minerals are ion exchange layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural ones, and artificially synthesized ones can also be used.

In addition, as the clay, clay mineral or ion exchange layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. I can give an example.

Such clays and clay minerals include kaolin, bentonite, Kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, Ummo group, montmorillonite group, vermiculite, Ryokudei group, palygorskite, kaolinite, nacrite, and dickite. , halloysite, etc., and examples of ion-exchange layered compounds include α-Zr(HAsO ₄ ) ₂ ·H ₂ O, α-Zr(HPO ₄ ) ₂ , α-Zr(KPO ₄ ) ₂ ·3H ₂ O, α-Ti(HPO ₄ ) ₂ , α-Ti(HAsO ₄ ) ₂ ·H ₂ O, α-Sn(HPO ₄ ) ₂ ·H ₂ O, γ-Zr(HPO ₄ ) ₂ , γ-Ti(HPO ₄ ) ₂ , γ-Ti(NH ₄ PO ₄ ) ₂ ·H ₂ O, and other crystalline acid salts of polyvalent metals.

Such clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc/g or more with a radius of 20 Å or more measured by mercury intrusion method, and 0.3 to 5 cc/g. Particularly preferred. Here, the pore volume is measured in a pore radius range of 20 to 3×10 ⁴ Å by mercury intrusion method using a mercury porosimeter. When a carrier having a radius of 20 Å or more and a pore volume smaller than 0.1 cc/g is used as a carrier, it tends to be difficult to obtain high polymerization activity.

It is also preferable to subject clays and clay minerals to chemical treatments. As the chemical treatment, any of surface treatment to remove impurities adhering to the surface, treatment to affect the crystal structure of clay, etc. can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. Acid treatment not only removes surface impurities but also increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay, resulting in changes in the structure of the clay. Furthermore, salt treatment and organic substance treatment can form ionic complexes, molecular complexes, organic derivatives, etc., and change the surface area and interlayer distance.

The ion-exchangeable layered compound may be a layered compound in which the interlayers are expanded by utilizing ion exchangeability and exchanging exchangeable ions between the layers with other large bulky ions. These bulky ions play the role of pillars that support the layered structure and are usually called pillars. Furthermore, the introduction of another substance between the layers of a layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ , and B(OR) ₃ . R is a hydrocarbon group, etc.), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O(OCOCH ₃ ) ₆ ] ⁺ , etc. etc. These compounds may be used alone or in combination of two or more. In addition, when intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ , Ge(OR) ₄ etc. It is also possible to coexist colloidal inorganic compounds such as SiO ₂ and SiO 2 . Further, examples of pillars include oxides generated by intercalating the metal hydroxide ions between layers and then heating and dehydrating the metal hydroxide ions.

Clay, clay minerals, and ion-exchange layered compounds may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Alternatively, it may be used after newly adding and adsorbing water or after being heated and dehydrated. Furthermore, one type may be used alone or two or more types may be used in combination.

Examples of the organic compound used as the solid carrier (S) include granular or fine particulate solids having a particle size in the range of 10 to 300 μm. Specific examples of the organic compound include, for example, a polymer produced mainly from an olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or vinylcyclohexane; Examples include polymers and reactants produced mainly of styrene and divinylbenzene, and granular or fine particulate solids made of modified products thereof.
The solid carrier (S) is preferably a porous oxide from the viewpoint of preventing foreign matter during molding.

<Component (C)>
The olefin polymerization catalyst (X) may preferably further contain a component (C), where the component (C) is an organometallic compound (c-1) represented by the following general formulas (3) to (5), At least one compound selected from the group consisting of an organoaluminumoxy compound (c-2) and a compound (c-3) that reacts with component (A) to form an ion pair.

R ^a _m Al (OR ^b ) _n H _p X _q ...(3)
In formula (3), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, X represents a halogen atom, m is 0<m≦3, and n is 0≦n. <3, p is a number of 0≦p<3, q is a number of 0≦q<3, and m+n+p+q=3.

M ^a AlR ^a ₄ ...(4)
In formula (4), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 or more and 15 or less carbon atoms.

R ^a _r M ^b R ^b _s X _t ...(5)
In formula (5), R ^a and R ^b each independently represent a hydrocarbon group having 1 or more and 15 or less carbon atoms, M ^b is selected from Mg, Zn and Cd, and X represents a halogen atom, r is 0<r≦2, s is 0≦s≦1, t is 0≦t≦1, and r+s+t=2.

Among the organometallic compounds (c-1), those represented by the formula (3) are preferred, and specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctyl Aluminum, trialkylaluminum such as tri2-ethylhexylaluminum;
Dialkyl aluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide;
Alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide;
Dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride , an alkyl aluminum hydride such as di-sec-nonyl aluminum hydride;
Dialkyl aluminum alkoxides such as dimethyl aluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, and diisobutyl aluminum ethoxide are exemplified.

Examples of the formula (4) include lithium aluminum hydride; examples of the formula (5) include dialkylzinc compounds described in JP-A No. 2003-171412; It can also be used in combination with other compounds.

The organoaluminumoxy compound (c-2) is preferably an organoaluminumoxy compound prepared from trialkylaluminum or tricycloalkylaluminum, and particularly preferably an aluminoxane prepared from trimethylaluminum or triisobutylaluminum, such as methylaluminoxane. . Such organoaluminumoxy compounds may be used alone or in combination of two or more.

Examples of the compound (c-3) that reacts with the component (A) to form an ion pair include those disclosed in Japanese Patent Publication No. 1-501950, Japanese Patent Application Publication No. 1-502036, Japanese Patent Application Laid-Open No. 3-179005, Lewis acids, ionic compounds, borane compounds and carborane compounds, as well as heteropoly compounds and isopoly compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704 and US5321106, etc. etc. can be used.

When the olefin polymerization catalyst (X) is used in combination with an organoaluminumoxy compound such as methylaluminoxane as a cocatalyst component, it not only exhibits extremely high polymerization activity toward olefin compounds, but also reacts with active hydrogen in the solid carrier. Component (C) preferably contains at least an organoaluminumoxy compound (c-2), since a solid carrier component containing a promoter component can be easily prepared.

<How to use each component and order of addition>
Olefin polymerization catalyst (X) can be prepared by mixing and contacting component (A) and component (S) and optionally component (C) in an inert hydrocarbon.

As for the method of bringing each component into contact, focusing on the order of contact, for example,
(i) A method of bringing component (A) into contact with component (S). (ii) A method of bringing component (S) into contact with component (C) and then contacting component (A). (iii) A method of bringing component (A) into contact with component (A). (C) and then contacting component (S); (iv) method of contacting component (S) with component (C) and then contacting a mixture of component (A) and component (C);
(v) Examples include a method of contacting component (S) with component (C), further contacting component (C), and then contacting a mixture of component (A) and component (C). When multiple types of component (C) are used, the components (C) may be the same or different. Among the above methods, (i), (ii) and (iii) are preferred.

In each of the methods shown in the above-mentioned contact order form, in the step involving contact between component (S) and component (C), and the step involving contact between component (S) and component (A), component (G) By allowing these to coexist, fouling during the polymerization reaction is suppressed and the particle properties of the resulting polymer are improved. As component (G), a compound having a polar functional group can be used, and nonionic surfactants are preferred, such as polyalkylene oxide blocks, higher aliphatic amides, polyalkylene oxides, polyalkylene oxide alkyl ethers, etc. , alkyldiethanolamine, polyoxyalkylenealkylamine, glycerin fatty acid ester, and N-acylamino acid are more preferred. These may be used alone or in combination of two or more.

Examples of the solvent used in the preparation of the olefin polymerization catalyst (X) include inert hydrocarbon solvents, specifically aliphatic solvents such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Hydrocarbons, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, etc. can be mentioned.

In the contact between component (C) and component (S), the reaction site in component (C) and the reaction site in component (S) are chemically bonded, and component (C) and component (S) are bonded together. ) is formed. The contact time between component (C) and component (S) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is usually -50 to 200°C, preferably -20 to 120°C. It will be held in If component (C) and component (S) are brought into initial contact rapidly, component (S) will collapse due to the reaction heat and reaction energy, and the morphology of the resulting solid catalyst component will deteriorate, making it difficult to use it for polymerization. In many cases, continuous operation becomes difficult due to poor polymer morphology. Therefore, in the initial stage of contact between component (C) and component (S), in order to suppress the reaction heat generation, the contact is carried out at a lower temperature, or the reaction heat generation is controlled and the reaction is carried out at a rate that can maintain the initial contact temperature. It is preferable. The same applies to the case where the component (C) and the component (S) are brought into contact with each other, and then the component (C) is brought into contact with each other. The contact weight ratio between component (C) and component (S) (weight of component (C)/weight of component (S)) can be selected arbitrarily, but the higher the contact weight ratio, the more component (A) ) can be brought into contact with each other, and the catalytic activity per weight of the solid catalyst component can be improved.

The contact weight ratio of component (C) and component (S) [=weight of component (C)/weight of component (S)] is preferably 0.05 to 3.0, particularly preferably 0.1 to 2. .0.
When the contact material of component (C) and component (S) is brought into contact with component (A), the contact time is usually 1 minute to 20 hours, preferably 1 minute to 10 hours, and the contact temperature is is usually in the range of -50 to 200°C, preferably -50 to 100°C.

Component (C-1) has a molar ratio [(C-1)/M] of component (C-1) and all transition metal atoms (M) in component (A) of usually 0.01 to 100, 000, preferably 0.05 to 50,000.

Component (C-2) has a molar ratio [(C-2)/M] of component (C-2) (in terms of aluminum atoms) and all transition metal atoms (M) in component (A) of usually 10. 500,000, preferably 20 to 100,000.

Component (C-3) has a molar ratio [(C-3)/M] between component (C-3) and all transition metal atoms (M) in component (A), which is usually 1 to 10, preferably It is used in an amount of 1 to 5.
Note that the ratio of component (C) to all transition metal atoms (M) in component (A) can be determined by inductively coupled plasma optical emission spectrometry (ICP analysis). For ethylene polymerization, the olefin polymerization catalyst (X) can be used as it is, but it can also be used after prepolymerizing an olefin to this olefin polymerization catalyst to form a prepolymerized catalyst (XP).

The prepolymerization catalyst (XP) can be prepared by prepolymerizing ethylene, etc., usually in an inert hydrocarbon solvent, in the presence of the olefin polymerization catalyst (X), and can be prepared by batch, semi-continuous, or continuous method. It can be carried out in any of the following methods, and it can be carried out under reduced pressure, normal pressure or increased pressure. Furthermore, it is desirable to produce the prepolymerized catalyst (XP) by prepolymerization in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g, per 1 g of solid catalyst component.

After the prepolymerized catalyst (XP) produced in an inert hydrocarbon solvent is separated from the suspension, it may be suspended again in an inert hydrocarbon and ethylene may be introduced into the resulting suspension. Alternatively, ethylene may be introduced after drying.

The prepolymerization temperature is -20 to 80°C, preferably 0 to 60°C, and the prepolymerization time is about 0.5 to 100 hours, preferably about 1 to 50 hours. Preferably, an olefin containing ethylene as a main component is used in the prepolymerization.

As for the form of the solid catalyst component used in the prepolymerization, those already mentioned can be used without limitation. Further, component (C) is used as necessary, and the organometallic compound (c-1) represented by the above formula (3) is preferably used. When component (C) is used, component (C) has a molar ratio (Al/M) of aluminum atoms (Al) in component (C) and transition metal atoms (M) in component (A). , 0.1 to 10,000, preferably 0.5 to 5,000.

The concentration of the olefin polymerization catalyst (X) in the prepolymerization system is preferably 1 to 1000 g/liter, more preferably 10 to 500 g/liter in terms of olefin polymerization catalyst/polymerization volume ratio. At the time of prepolymerization, the above-mentioned component (G) may be present in order to suppress fouling or improve particle properties.

In addition, in order to improve the fluidity of the prepolymerized catalyst (XP) and suppress the generation of heat spots, sheeting, and polymer lumps during polymerization, component (G) is brought into contact with the prepolymerized catalyst (XP) that has been generated by prepolymerization. You may let them.

The temperature at which the component (G) is brought into contact is usually -50 to 50°C, preferably -20 to 50°C, and the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 10 hours. .
When bringing the olefin polymerization catalyst (X) into contact with the component (G), the component (G) is added in an amount of 0.1 to 20 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the olefin polymerization catalyst (X). It is used in an amount of 3 to 10 parts by weight, more preferably 0.4 to 5 parts by weight.

The mixed contact between the olefin polymerization catalyst (X) and the component (G) can be carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include those mentioned above.
In the method for producing an ethylene polymer according to the present invention, a dried prepolymerized catalyst (XP) (hereinafter also referred to as "dried prepolymerized catalyst") can be used as the olefin polymerization catalyst (X). . Drying of the prepolymerized catalyst (XP) is usually performed after removing hydrocarbons as a dispersion medium from the obtained suspension of the prepolymerized catalyst by filtration or the like.

Drying of the prepolymerized catalyst (XP) is carried out by maintaining the prepolymerized catalyst (XP) at a temperature of 70° C. or less, preferably in the range of 20 to 50° C., under the flow of an inert gas. The amount of volatile components in the obtained dry prepolymerized catalyst is desirably 2.0% by weight or less, preferably 1.0% by weight or less. The lower the amount of volatile components in the dry prepolymerized catalyst, the better, and there is no particular lower limit, but it is practically 0.001% by weight. The drying time is usually 1 to 48 hours, depending on the drying temperature.

Since the dry prepolymerized catalyst has excellent fluidity, it can be stably supplied to the polymerization reactor. Further, when the dry prepolymerized catalyst is used, the solvent used for suspension does not need to be included in the gas phase polymerization system, so that stable polymerization can be performed.

[Production method of ethylene polymer]
Next, a method for producing an ethylene polymer according to the present invention will be described. An ethylene polymer is obtained by polymerizing ethylene (homopolymerization or copolymerization) in the presence of the olefin polymerization catalyst (X) described above. By using the olefin polymerization catalyst (X), it is possible to efficiently produce a low-density ethylene copolymer with high polymerization activity, excellent moldability and mechanical strength, and many long chain branches. . The ethylene polymer of the present invention refers to a polymer containing 10 mol% or more of ethylene.

In the present invention, polymerization can be carried out by any liquid phase polymerization method such as solution polymerization or suspension polymerization or gas phase polymerization method, but in suspension polymerization method and gas phase polymerization method, the prepolymerization catalyst (XP) is used. It is preferable to use

Specific examples of inert hydrocarbon media used in liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. Moreover, in the liquid phase polymerization method, the olefin itself can also be used as a solvent.

When polymerizing ethylene using the above catalyst for olefin polymerization, component (A) is usually 1 x 10 ^-12 to 1 x 10 ^-1 mol, preferably 1 x 10 ^-8 to 1 mol per liter of reaction volume. It is used in an amount of 1×10 ⁻² mol. In addition, component (C) is used, and in particular, an organoaluminum compound represented by formula (3) in (c-1) is preferably used.

Further, the polymerization temperature of ethylene using the prepolymerization catalyst (XP) is usually in the range of -50 to +200°C, preferably 0 to 170°C, particularly preferably 60 to 170°C. The polymerization pressure is usually normal pressure to 100 kgf/cm ² , preferably normal pressure to 50 kgf/cm ² , and the polymerization reaction can be carried out in any of the batch, semi-continuous, and continuous methods. I can do it. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

The molecular weight of the resulting polymer can be controlled by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Generally, the more low molecular weight components there are, the more they adhere to the walls of the polymerization reactor and the stirring blades, which may put a load on the cleaning process and lead to a decrease in productivity. During polymerization, component (G) can be present for the purpose of suppressing fouling or improving particle properties.

Further, in the present invention, the monomers supplied together with ethylene to the copolymerization reaction are one or more monomers selected from α-olefins having 4 to 10 carbon atoms, preferably α-olefins having 6 to 10 carbon atoms. Specific examples of α-olefins having 4 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene. Further, monomers other than ethylene and α-olefin having 4 to 10 carbon atoms may or may not be supplied as long as the effects of the present invention are not impaired.

<Production method of high-pressure low-density polyethylene (B)>
The high-pressure low-density polyethylene (B) used in the present invention is produced by polymerizing ethylene using a high-pressure radical polymerization method. For example, ethylene monomer is radically polymerized at a pressure in the range of 500 to 3,500 kgf/cm ² G, at a polymerization temperature in the range of 100 to 400°C, using oxygen or an organic peroxide as a polymerization initiator, and in an autoclave type or tubular type. It can be produced in a reactor. Furthermore, as the high-pressure low-density polyethylene (B), commercially available high-pressure low-density polyethylene can be used. As specific examples, requirements (a) to ( c) and optionally one that satisfies requirement (d) can be selected.

The high-pressure low-density polyethylene (B) may contain a structural unit derived from biomass-derived ethylene. The ethylene constituting the polymer may be solely biomass-derived ethylene, only fossil fuel-derived ethylene, or may contain both biomass-derived ethylene and fossil fuel-derived ethylene. Biomass-derived ethylene is a monomer made from all renewable natural raw materials and their residues, including fungi, yeast, algae, and bacteria, derived from plants or animals, and their residues. ^-12 , and the biomass carbon concentration (pMC) measured in accordance with ASTM D6866 is about 100 (pMC). Biomass-derived ethylene can be obtained, for example, by a conventionally known method.
It is preferable that the high-pressure low-density polyethylene (B) contains a structural unit derived from a biomass-derived monomer from the viewpoint of reducing environmental load.

<Production method of ethylene resin composition (Z)>
The ethylene resin composition (Z) can be produced by melt-kneading the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B), or can be produced by melt-kneading the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). - It can also be produced by dry blending pellets of olefin copolymer (A) and pellets of high-pressure low-density polyethylene (B). When producing by melt-kneading, a continuous extruder or an internal kneader can be used. Examples include devices such as a single screw extruder, a twin screw extruder, a mixing roll, a Banbury mixer, and a kneader. Among these, it is preferable to use a single-screw extruder and/or a twin-screw extruder from the viewpoint of economy, processing efficiency, etc.

When performing the above melt kneading and dry blending, in addition to the above ethylene-α-olefin copolymer (A) and the above high-pressure low density polyethylene (B), the above “other thermoplastic resin” may be blended. . Further, in addition to or in place of the "other thermoplastic resin", the "additive" described above may be further blended.

The order in which the "other thermoplastic resin" and the "additive" are added is not particularly limited. For example, the above-mentioned "other thermoplastic resin" and the above-mentioned "additive" are simultaneously blended with one or both of the above-mentioned ethylene-α-olefin copolymer (A) and the above-mentioned high-pressure low-density polyethylene (B). Alternatively, the ethylene-α-olefin copolymer (A) and the high-pressure low density polyethylene (B) may be kneaded and then added.

[Molded object, film, laminate]
By processing the ethylene resin composition (Z) of the present invention, a molded article with excellent moldability and mechanical strength, preferably a film, and more preferably a laminate comprising the film, can be obtained. .

The ethylene resin composition (Z) of the present invention is processed by general film molding, sheet molding, blow molding, injection molding, extrusion molding, and the like. Examples of film molding include extrusion lamination molding, T-die film molding, and inflation molding (air cooling, water cooling, multistage cooling, high-speed processing). Although the obtained film can be used as a single layer, it can be provided with various functions by forming a multilayer film. The molding method used in that case includes a coextrusion method. On the other hand, bonding lamination methods such as extrusion lamination and dry lamination allow lamination with paper or barrier films (aluminum foil, vapor deposited film, coating film, etc.) that are difficult to coextrude. It is possible to produce high-performance products by multilayering blow molding, injection molding, and extrusion molding using coextrusion methods in the same way as film molding.

Molded objects obtained by processing the ethylene resin composition (Z) of the present invention include films, sheets, blown infusion bags, blown bottles, gasoline tanks, extruded tubes, pipes, wire coverings, and tear-off caps. Examples include injection molded products such as daily necessities, fibers, and large molded products by rotational molding.

Furthermore, the film obtained by processing the ethylene resin composition (Z) of the present invention can be used for liquid packaging bags, liquid soup packaging bags, liquid paper containers, laminated fabrics, special shaped liquid packaging bags (standing pouches, etc.). ), standard bags, heavy bags, wrap films, sugar bags, oil packaging bags, various packaging films such as food packaging, protection films, infusion bags, agricultural materials, back-in-boxes, semiconductor materials, pharmaceuticals, foods, etc. It is suitable for clean films used in packaging. Moreover, the above-mentioned film can also be used as a multilayer film by laminating it with a base material such as nylon, polyester, or polyolefin film.

The laminate containing the ethylene resin composition (Z) of the present invention in at least one layer will be described in more detail below.
Examples of layers other than the above layers constituting the laminate include a base layer and a barrier layer.

Examples of the base material used as the base layer include films of polyamide, polyester, polypropylene, polyethylene, ethylene/vinyl alcohol copolymer, and the like. Preferably, the film is a stretched film. Other examples include paper and paper base materials in which polyethylene is coated on paper. Printing or various coatings may be applied to these base materials as necessary. Moreover, various pretreatments such as corona treatment, flame treatment, plasma treatment, ultraviolet treatment, and anchor coating treatment may be performed as necessary.

Specific examples of base materials include paper such as high-quality paper, kraft paper, thin paper, Kent paper, cellophane, woven fabric, non-woven fabric, stretched nylon, unstretched nylon, special nylon (MXD6, etc.), K-nylon (polyvinylidene fluoride coat). Nylon base materials such as oriented PET (polyethylene terephthalate), unoriented PET (polyethylene terephthalate), K-PET (polyethylene terephthalate), oriented polypropylene (OPP), unoriented polypropylene (CPP), K-PP, coextruded films Examples include polypropylene base materials such as PP, LDPE film, LLDPE film, EVA film, stretched LDPE film, and stretched HDPE film.

Examples of the barrier substrate used as the barrier layer include metal foil, a thermoplastic resin film coated with a metal or an inorganic substance, and a thermoplastic resin film coated with a barrier coating. Examples of the thermoplastic resin film include stretched nylon, stretched PET (polyethylene terephthalate), stretched polypropylene (OPP), and unstretched polypropylene (CPP).

Some of the raw materials for the laminate, such as the base material and the barrier base material, may include an ethylene polymer and a propylene polymer containing a biomass-derived monomer.
In the present invention, the metal foil is a metal foil made of aluminum, gold, silver, iron, copper, nickel, or an alloy containing these as main components. A thermoplastic resin film on which a metal is vapor-deposited is a film in which a metal such as aluminum or silicon is vapor-deposited on the surface of a film made of polyester, polyamide, or the like. The thermoplastic resin film deposited with an inorganic substance is a thermoplastic resin film deposited with silica or alumina. Barrier coating refers to coating a film surface with a barrier resin such as polyvinyl alcohol or polyvinylidene chloride.

The base material layer is used, for example, as a printing base material. On the other hand, barrier substrates are not typically used as printing substrates.
Specific configurations of the laminate in the present invention are illustrated below, but are not limited thereto.

The PE laminate in the following structure means that ethylene resin is laminated by extrusion lamination. The ethylene resin used in at least one PE laminate in each configuration is the ethylene resin composition (Z) of the present invention.

When PE laminate using the ethylene-based resin composition (Z) of the present invention is used as an adhesive layer adjacent to an aluminum evaporation layer or aluminum foil of an aluminum evaporation film, the PE laminate has a high adhesive strength with the aluminum evaporation layer or aluminum foil. Excellent in

Coextrusion laminate (acid copolymer/PE laminate) refers to laminating two layers of acid copolymer and ethylene resin by coextrusion lamination, where the acid copolymer is adjacent to the aluminum foil. Examples of acid copolymers include ethylene-acrylic copolymers (EAA), ethylene-methacrylic acid copolymers (EMAA), and ethylene-acrylic ester copolymers (EEA, EMA, EMMA, etc.). The film used for the innermost layer (on the opposite side of the stretched base film) is a thermoplastic resin film, and it is preferable to use a propylene resin film or an ethylene resin film.

Stretched nylon/adhesive/PE laminated (1)/PE laminated (2),
Paper/PE laminate,
Stretched polypropylene/adhesive/PE laminate (1)/aluminum foil/adhesive/film or PE laminate (2),
Stretched polypropylene/adhesive/PE laminate (1)/aluminum vapor deposited film (the aluminum vapor deposited layer is adjacent to the PE laminate (1) layer),
Stretched polypropylene/adhesive/PE laminate (1)/aluminum vapor deposited film/adhesive/film or PE laminate (2) (the aluminum vapor deposited layer is adjacent to the PE laminate (1) layer),
Stretched polypropylene/adhesive/extruded laminate (1)/inorganic vapor deposited film,
Stretched polypropylene/adhesive/PE laminate (1)/inorganic vapor-deposited film/adhesive/film or PE laminate (2),
Stretched polyethylene terephthalate/adhesive/extruded laminate (1)/aluminum foil/adhesive/film or PE laminate (2),
Stretched polyethylene terephthalate/adhesive/extruded laminate (1)/aluminum vapor deposited film/adhesive/film or PE laminate (2) (the aluminum vapor deposited layer is adjacent to the PE laminate (1) layer),
Stretched polyethylene terephthalate/adhesive/PE laminate (1)/inorganic vapor-deposited film,
Stretched polyethylene terephthalate/adhesive/PE laminate (1)/inorganic vapor-deposited film/adhesive/film or PE laminate (2),
PE lamination (1) / paper / PE lamination (2) / aluminum foil / coextrusion lamination (acid copolymer / PE lamination (3)),
PE laminate (1) / paper / PE laminate (2) / aluminum foil / adhesive / polyethylene terephthalate / adhesive / film or PE laminate (3),
PE laminate (1) / paper / PE laminate (2) / aluminum vapor deposited film / adhesive / film or PE laminate (3),
PE laminate (1) / Paper / PE laminate (2) / Inorganic vapor deposited film / Adhesive / Film or PE laminate (3)

Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to the description of the following examples.

[Measurement or evaluation method]
In the following Examples, etc., various physical properties of the ethylene-α-olefin copolymer, etc. were measured by the methods described in [Detailed Description of the Invention] and The following evaluation method was adopted as the evaluation method in which the

Extrusion laminate evaluation :
[Neck in]
The ethylene resin composition was extrusion laminated onto a 50 g/m ² kraft paper as a base material under the following conditions using a Sumitomo Heavy Industries laminator having an extruder with a diameter of 65 mm and a T-die with a die width of 500 mm.

・Air gap: 130mm
・Resin temperature under die: 320℃
・Take-up speed: 80m/min ・Film thickness: 20μm
When the width of the T-die is L ₀ and the width of the film laminated on kraft paper at each take-up speed is L, the neck-in was calculated from L ₀ -L.

[Take-back surging]
Using a Sumitomo Heavy Industries laminator having an extruder with a diameter of 65 mm and a T-die with a die width of 500 mm, the ethylene resin composition was applied onto a 50 g/m ² kraft paper as a base material with an air gap of 130 mm and a resin temperature below the die. Extrusion lamination was performed at 320°C. The extrusion rate was set so that the film thickness was 20 μm when the take-off speed was 80 m/min. Also, increase the pulling speed and measure the neck-in five times at a pulling speed of 150 m/min, and if a value that is ±1.5 mm or more from the average neck-in value is measured two or more times. It was determined that surging occurred in the transaction.

[Aluminum bond strength ratio]
Using a Sumitomo Heavy Industries laminator having an extruder with a diameter of 65 mm and a T-die with a die width of 500 mm, the ethylene resin composition was heated between the base material and the aluminum vapor-deposited film at a resin temperature under the die of 320°C and a take-up speed of 150 m/min. Extrusion lamination was carried out under these conditions to obtain a film thickness of 15 μm. The base material is a stretched polyethylene terephthalate film with a thickness of 12 μm (product name: Emblet (registered trademark), manufactured by Unitika Co., Ltd.), and a two-component curing urethane anchor coating agent is applied to one side (the ethylene resin composition layer side). I used the one I made. As the aluminum vapor-deposited film, ML PET (trade name, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) with a thickness of 12 μm was used. The extrusion laminated ethylene resin composition is in contact with the aluminum surface. The obtained extruded laminate film was cut into strips with a width of 15 mm, and the adhesive strength between the obtained ethylene-based resin composition layer and the aluminum vapor-deposited film layer was determined by performing T-peeling at a peeling speed of 300 mm/min. The obtained peel strength and the peel strength similarly obtained using high-pressure process LDPE (high-pressure process low-density polyethylene, Suntech (registered trademark)-LD "L1850A" manufactured by Asahi Kasei Corporation) instead of the ethylene-based resin composition. (LDPE) was defined as the AL adhesive strength ratio.
AL adhesive strength ratio = peel strength / peel strength (LDPE)

[Trousers tear strength]
Using a Sumitomo Heavy Industries laminator having an extruder with a diameter of 65 mm and a T-die with a die width of 500 mm, the ethylene resin composition was applied onto a 50 g/m2 kraft paper as a base material with an air gap of 130 mm and a resin temperature under the die of 320 mm. ℃ and a take-up speed of 80 m/min, extrusion lamination was carried out to a film thickness of 20 μm. In accordance with JIS K7128-1, the obtained laminate was cut into a piece having a width of 50 mm and a length of 150 mm, a 75 mm incision was made in the center of the width, and the tear strength was measured at a speed of 200 mm/min.

[Raw materials used]
The transition metal compounds and component (G) used in the production examples are as follows.
Transition metal compound (A-1): dimethylsilylene (2-indenyl) (4-(3,5-di-tert-butyl-4-methoxyphenyl)-7-methoxy-1-indenyl) zirconium dichloride [JP 2019 It was synthesized by the method described in JP-A-059933. ]
Transition metal compound (B-1): dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride [Synthesized based on the method described in Japanese Patent No. 5455354. ]
Transition metal compound (B-2): isopropylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride [synthesized based on the method described in JP-A-4-69394 . ]
Component (G-1): Lauryl diethanolamine (manufactured by Kao Corporation)
Ingredient (G-2): Emulgen (registered trademark) 108 (manufactured by Kao Corporation)

<Synthesis of prepolymerization catalyst (XP-1)>
Silica manufactured by Fuji Silysia Co., Ltd. (average particle size 70 μm, specific surface area 340 m ² /g, pore volume 1.3 cm ³ /g) was placed in a reactor equipped with a stirrer with an internal volume of 270 L under a nitrogen atmosphere as a solid carrier (S). , fired at 250°C) was suspended in 77L of toluene and then cooled to 0 to 5°C. To this suspension, 20.4 L of a toluene solution of methylaluminoxane (3.5 mol/L in terms of Al atoms) was added dropwise as component (C) over 30 minutes. At this time, the temperature in the system was maintained at 0 to 5°C. Subsequently, the reaction was carried out at 0 to 5°C for 30 minutes, and then the temperature was raised to 95 to 100°C over about 1.5 hours, and then the reaction was continued at 95 to 100°C for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant liquid was removed by decantation, and the mixture was further washed twice with toluene to prepare a toluene slurry having a total volume of 58.0 L. When a part of the obtained slurry component was sampled and its concentration was examined, it was found that the slurry concentration was 248.0 g/L and the Al concentration was 1.21 mol/L.

Next, 6.1 L of the toluene slurry obtained above and 21.9 L of toluene were charged into a reactor equipped with a stirrer and having an internal volume of 114 L that was sufficiently purged with nitrogen. After adding 5.4 L of the solution and contacting it for 1 hour at a system internal temperature of 20 to 25°C, the supernatant liquid was removed by decantation, and after washing twice with hexane, a slurry with a total volume of 30.9 L was prepared. . While adjusting the temperature of the resulting slurry to 10 to 15°C, 3.1 L of a 0.92M hexane solution of diisobutylaluminum hydride was added, and ethylene gas was started to be supplied at a flow rate of 0.74 kg/hr to add 1-hexene. After adding 34.3 mL, the temperature was started to rise, and while adjusting the system temperature to 32 to 38 °C, 34.3 mL of 1-hexene was added 5 times every hour, and after starting the ethylene supply, the temperature was increased to 6. When the amount of ethylene supplied reached 4.5 kg after a period of time, the ethylene supply was stopped. Thereafter, the inside of the system was sufficiently purged with nitrogen, the supernatant liquid was removed by decantation, and the system was washed four times with hexane to prepare a slurry having a total volume of 21.9 L. While maintaining the obtained slurry at 35 to 40° C., 6.1 L of a 10 g/L hexane solution of component (G-1) was added, and the slurry was kept in contact for 2 hours. The entire amount of the obtained slurry was inserted into an evaporative dryer with an internal volume of 43 L and equipped with a stirrer under a nitrogen atmosphere, and the pressure inside the dryer was reduced to -68 kPaG over about 60 minutes. Vacuum drying was performed for 3 hours to remove hexane and volatile components in the prepolymerized catalyst components. The pressure was further reduced to -100 kPaG, and when it reached -100 kPaG, it was vacuum dried for 8 hours to obtain 6.2 kg of prepolymerized catalyst (XP-1). A portion of the obtained prepolymerized catalyst (XP-1) was sampled and the composition was examined, and it was found that 0.56 mg of Zr atoms were contained per 1 g of the prepolymerized catalyst component.

<Synthesis of prepolymerization catalyst (XP-2)>
Silica manufactured by Fuji Silysia Co., Ltd. (average particle size 70 μm, specific surface area 340 m ² /g, pore volume 1.3 cm ³ /g) was placed in a reactor equipped with a stirrer with an internal volume of 270 L under a nitrogen atmosphere as a solid carrier (S). , fired at 250°C) was suspended in 77L of toluene and then cooled to 0 to 5°C. To this suspension, 20.4 L of a toluene solution of methylaluminoxane (3.5 mol/L in terms of Al atoms) was added dropwise as component (C) over 30 minutes. At this time, the temperature in the system was maintained at 0 to 5°C. Subsequently, the reaction was carried out at 0 to 5°C for 30 minutes, and then the temperature was raised to 95 to 100°C over about 1.5 hours, and then the reaction was continued at 95 to 100°C for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant liquid was removed by decantation, and the mixture was further washed twice with toluene to prepare a toluene slurry having a total volume of 58.0 L. When a part of the obtained slurry component was sampled and its concentration was examined, it was found that the slurry concentration was 248.0 g/L and the Al concentration was 1.21 mol/L.

Next, 6.1 L of the toluene slurry obtained above and 22.7 L of toluene were charged into a reactor equipped with a stirrer and having an internal volume of 114 L that was sufficiently purged with nitrogen. After adding 1.5 L of the solution and 3.1 L of 8 mM toluene solution of transition metal compound (B-2) and contacting the system at an internal temperature of 70 to 75°C for 1 hour, the supernatant liquid was removed by decantation, and hexane was removed. After washing twice using the slurry, a total volume of 29.8 L of slurry was prepared. While adjusting the temperature of the obtained slurry to 35 to 40° C., 4.0 L of a 0.92M hexane solution of diisobutylaluminum hydride was added, and supply of ethylene gas was started at a flow rate of 795.4 L/hr. Five hours after the start of ethylene supply, when the ethylene supply amount reached 3,980 L, ethylene supply was stopped. Thereafter, the inside of the system was sufficiently purged with nitrogen, the supernatant liquid was removed by decantation, and the system was washed four times with hexane to prepare a slurry having a total volume of 21.7 L. While maintaining the obtained slurry at 35 to 40° C., 3.8 L of a 10 mg/mL hexane solution of component (G-2) was added, and the slurry was kept in contact for 2 hours. The entire amount of the obtained slurry was inserted into an evaporative dryer with an internal volume of 43 L and equipped with a stirrer under a nitrogen atmosphere, and the pressure inside the dryer was reduced to -68 kPaG over about 60 minutes. Vacuum drying was performed for 3 hours to remove hexane and volatile components in the prepolymerized catalyst components. The pressure was further reduced to -100 kPaG, and when the pressure reached -100 kPaG, vacuum drying was performed for 8 hours to obtain 6.1 kg of prepolymerized catalyst (XP-2). A portion of the obtained prepolymerized catalyst (XP-2) was sampled and the composition was examined, and it was found that 0.52 mg of Zr atoms were contained per 1 g of the prepolymerized catalyst component.

<Production of ethylene-α-olefin copolymer>
[Manufacture example 2]
(Production of ethylene-α-olefin copolymer (A-2))
Ethylene polymers were produced by a gas phase polymerization process using a fluidized bed gas phase polymerization reactor. After introducing 24 kg of spherical ethylene polymer particles with an average particle size of 900 μm into the reactor and supplying nitrogen to form a fluidized bed, ethylene, Hydrogen, 1-hexene, prepolymerized catalyst, and Electrostripper (registered trademark) EA (manufactured by Kao Corporation) were continuously supplied. The polymerization reaction product was continuously extracted from the reactor and dried in a drying device to obtain a powder of ethylene-α-olefin copolymer (A-2).

[Production Examples 3, 4, 6, 7, 11 to 16]
(Production of ethylene-α-olefin copolymers (A-3), (A-4), (A-6), (A-7), (A-11) to (a-16))
An ethylene-α-olefin copolymer powder was obtained in the same manner as Production Example 2 except that the polymerization conditions were changed as shown in Table 8. Note that Table 8 lists Chemistat (registered trademark) 2500 (manufactured by Sanyo Chemical Industries, Ltd.) as a component that was not used in Production Example 2.

[Manufacture example 1]
(Production of ethylene-α-olefin copolymer (A-1))
In a two-stage polymerization process in which the fluidized bed type gas phase polymerization reactor used in Production Example 2 was used as the first stage reactor, and in addition, the fluidized bed type gas phase polymerization reactor with an internal volume of 0.6 m3 was used as the second stage reactor, ethylene-based A polymer was produced. Two-stage polymerization means that the polymerization reaction product obtained in the first-stage polymerization reactor is continuously discharged to the second-stage polymerization reactor, and the polymerization reaction is carried out in the second-stage polymerization reactor as well. 24 kg of spherical ethylene polymer particles having an average particle size of 900 μm were introduced into the first stage polymerization reactor in advance. This was supplied with nitrogen to form a fluidized bed. Ethylene, hydrogen, 1-hexene, prepolymerization catalyst, and electrostripper EA were continuously supplied to both the first-stage polymerization reactor and the second-stage polymerization reactor under the polymerization conditions shown in Table 8 so as to maintain a steady state. However, the prepolymerization catalyst and electrostripper EA were supplied only to the first stage polymerization reactor. The polymerization reaction product obtained by the two-stage polymerization obtained in the second-stage polymerization reactor was continuously extracted from the second-stage polymerization reactor and dried in a drying device to obtain an ethylene-α-olefin copolymer powder.

[Production Examples 5, 8 to 10]
(Production of ethylene-α-olefin copolymers (A-5), (A-8) to (A-10))
An ethylene-α-olefin copolymer powder was obtained in the same manner as in Production Example 1 except that the polymerization conditions were changed as shown in Table 8.

<Measurement of physical properties of polymer>
[Ethylene-α-olefin copolymer (A-1)]
The powder of the ethylene-α-olefin copolymer (A-1) obtained in Production Example 1 was extruded using a twin-screw co-directional 46 mmφ extruder manufactured by Ikegai Co., Ltd. at a set temperature of 200°C and a screw rotation speed of 300 rpm. After melt-kneading under the following conditions, the mixture was extruded into strands and cut to obtain pellets. Physical properties were measured using the obtained pellet as a measurement sample. The measurement results are shown in Table 9.

[Ethylene-α-olefin copolymer (A-2) to (a-16)]
Changing the ethylene-α-olefin copolymer (A-1) to any of the ethylene-α-olefin copolymers (A-2) to (a-16) obtained in Production Examples 2 to 16, respectively. Pellets were prepared and the physical properties were measured in the same manner as for measuring the physical properties of the ethylene-α-olefin copolymer (A-1) except for the above. The measurement results are shown in Table 9.

[Ethylene-α-olefin copolymer (a-17)]
Physical properties were measured for Ultzex 15150J manufactured by Prime Polymer Co., Ltd. The measurement results are shown in Table 9.

[High pressure low density polyethylene (B-1)]
Physical properties were measured for Suntech-LD "L1850A" manufactured by Asahi Kasei Corporation. The measurement results are shown in Table 10.

[High pressure low density polyethylene (b-2)]
Physical properties were measured for Suntec-LD "M1920" manufactured by Asahi Kasei Corporation. The measurement results are shown in Table 10.

<Manufacture of ethylene resin composition>
[Example 1]
75% by mass of the obtained ethylene-α-olefin copolymer (A-1) pellets and 25% by mass of high-pressure low density polyethylene (B-1) pellets were dry blended, and extrusion lamination evaluation was performed. went. The evaluation results are shown in Table 11.

[Example 2]
50% by mass of the obtained ethylene-α-olefin copolymer (A-1) pellets and 50% by mass of high-pressure low density polyethylene (B-1) pellets were dry blended, and extrusion lamination evaluation was performed. went. The evaluation results are shown in Table 11.

[Example 3]
75% by mass of the obtained ethylene-α-olefin copolymer (A-2) pellets and 25% by mass of high-pressure low density polyethylene (B-1) pellets were dry blended, and extrusion lamination evaluation was performed. went. The evaluation results are shown in Table 11.

[Example 4]
50% by mass of the obtained ethylene-α-olefin copolymer (A-2) pellets and 50% by mass of high-pressure low density polyethylene (B-1) pellets were dry blended, and extrusion lamination evaluation was performed. went. The evaluation results are shown in Table 11.

[Example 5]
50% by mass of the obtained ethylene-α-olefin copolymer (A-3) pellets and 50% by mass of high-pressure low density polyethylene (B-1) pellets were dry blended, and extrusion lamination evaluation was performed. went. The evaluation results are shown in Table 11.

[Comparative example 1]
75% by mass of ethylene-α-olefin copolymer (a-17) pellets and 25% by mass of high-pressure low density polyethylene (B-1) pellets were dry blended and extrusion lamination evaluation was performed. The evaluation results are shown in Table 11.

[Comparative example 2]
75% by mass of ethylene-α-olefin copolymer (a-17) pellets and 25% by mass of high-pressure low density polyethylene (b-2) pellets were dry blended, and extrusion lamination was evaluated. The evaluation results are shown in Table 11.

[Comparative example 3]
Extrusion lamination was evaluated using high-pressure low-density polyethylene (B-1). The evaluation results are shown in Table 11.

[Comparative example 4]
Using the obtained pellets of ethylene-α-olefin copolymer (a-16), extrusion lamination was evaluated. The evaluation results are shown in Table 11.

Claims (13)

An ethylene-α-olefin copolymer (A) which is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms and satisfies the following requirements (1) to (6), and the following requirements (a) to (c) including high-pressure low-density polyethylene (B),
The mass fraction (W _A ) of the ethylene-α-olefin copolymer (A) is 40% by mass or more and 90% by mass or less, and the mass fraction (W B ) of the high-pressure low density polyethylene ( _B ) is 10% by mass or more and 60% by mass or less (however, the total of W _A and W _B is 100% by mass).
Ethylene resin composition (Z).
(1) The density is in the range of 890 kg/m ³ or more and 935 kg/m ³ or less.
(2) The melt flow rate (MFR) under a load of 2.16 kg at 190° C. is in the range of 1.0 g/10 minutes or more and 15.0 g/10 minutes or less.
(3) The ratio of the melt tension at 190°C [MT (g)] to the shear viscosity [η ^* (P)] at 200°C and an angular velocity of 1.0 rad/sec [MT/η ^* (g/P)] is It is in the range of 1.40×10 ^-4 or more and 2.90×10 ^-4 or less.
(4) Zero shear viscosity [η ₀ (P)] at 200°C and weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .
0.01×10 ^-13 ×Mw ^3.4 ≦ η ₀ ≦ 4.5×10 ^-13 ×Mw ^3.4 ... (Eq-1)
(5) The number average molecular weight (Mn), weight average molecular weight (Mw), and Z average molecular weight (Mz) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-2) .
-2.0 ≦ Mz/Mw - Mw/Mn ≦ 15 ... (Eq-2)
(6) The total of vinyl, vinylidene, 2-substituted internal olefins, and 3-substituted internal olefins per 1000 carbon atoms (number/1000C) measured by ¹ H-NMR is in the range of 0.1 or more and 1.0 or less. .
(a) The density is in the range of 915 kg/m ³ or more and 930 kg/m ³ or less.
(b) The melt flow rate (MFR) under a load of 2.16 kg at 190° C. is in the range of 0.1 g/10 minutes or more and 20 g/10 minutes or less.
(c) The amount of components with a molecular weight of 1 million or more in the molecular weight distribution curve obtained by GPC measurement is in the range of 1.0% to 20%. The ethylene resin composition (Z) according to claim 1, wherein the ethylene-α-olefin copolymer (A) further satisfies the following requirement (7).
(7) The following relational expression ( Eq-3) is satisfied.
0.7×10 ^-4 ×Mw ^0.776 ≦[η]≦ 1.65×10 ^-4 ×Mw ^0.776 ...(Eq-3) The ethylene resin composition (Z) according to claim 1 or 2, wherein the ethylene-α-olefin copolymer (A) further satisfies the following requirement (8).
(8) The ratio Mz/Mw of Z average molecular weight (Mz) to weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) is in the range of 4.0 or more and 25.0 or less. The ethylene resin composition (Z) according to any one of claims 1 to 3, wherein the ethylene-α-olefin copolymer (A) further satisfies the following requirement (9).
(9) Multiple peaks are present in the melting curve obtained by differential scanning calorimetry (DSC). The ethylene resin composition (Z) according to any one of claims 1 to 4, wherein the high-pressure low density polyethylene (B) further satisfies the following requirement (d).
(d) Ratio of phase angle [δ100 (°)] at 200°C and angular velocity of 100 rad/sec to phase angle [δ0.01 (°)] at 200°C and angular velocity of 0.01 rad/sec [δ100/δ0.01] is in the range of 0.46 or more and 0.76 or less. The ethylene resin according to any one of claims 1 to 5, further comprising a thermoplastic resin (excluding the ethylene-α-olefin copolymer (A) and high-pressure low-density polyethylene (B)). Composition (Z). A molded article comprising the ethylene resin composition (Z) according to any one of claims 1 to 6. A film comprising the ethylene resin composition (Z) according to any one of claims 1 to 6. A multilayer film having a layer containing the ethylene resin composition (Z) according to any one of claims 1 to 6. A laminate having a layer containing the ethylene resin composition (Z) according to any one of claims 1 to 6. The laminate according to claim 10, further comprising a base material layer. The laminate according to claim 10, further comprising a barrier layer. A method for producing a laminate, comprising extrusion laminating the ethylene resin composition (Z) according to any one of claims 1 to 6 between a base layer and a barrier layer.