Ethylene-based resin composition and molded article

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

[Technical Field]

[0001] The present invention relates to an ethylene-based resin composition, and to a molded article, a film, a multilayer film and a laminate containing the composition. [Background technology]

[0002] Ethylene-based polymers are used in a variety of molding methods and applications, and various properties are required of ethylene-based polymers depending on the molding method and application. For example, in T-die molding, neck-in occurs, in which the film edges shrink toward the center. When neck-in occurs, the film width decreases and the film edges become thicker than the center. Therefore, if neck-in is large, problems such as reduced product yield and inability to produce products with the desired width may occur. In blow molding, problems such as sagging and breakage of the molten film may occur, and in inflation molding, problems such as shaking and breakage of the molten film may occur. To prevent these problems, it is necessary to select an ethylene-based polymer with a high melt tension relative to its molecular weight.

[0003] Furthermore, in T-die molding, a regular variation in thickness occurs in the film's take-up direction, known as draw surging (or draw resonance), which can cause variations in mechanical strength from location to location due to uneven thickness of the film. To stably produce film with a uniform thickness, take-up surging must be avoided, and to achieve this, it is thought that the resin must have properties such that the strain hardening of the elongational viscosity increases with increasing strain rate.

[0004] Ethylene polymers without long-chain branches obtained using metallocene catalysts have excellent mechanical strength, but have problems with moldability. For example, they can exhibit large neck-in and take-up surging during T-die molding. High-pressure low-density polyethylene has excellent moldability, such as high melt tension and small neck-in, and its elongational viscosity exhibits strain rate hardening, preventing take-up surging. However, high-pressure low-density polyethylene has poor mechanical strength, such as tensile strength, tear strength, and impact strength, due to its complex long-chain branching structure.

[0005] In order to solve these problems, various ethylene polymers into which long chain branches have been introduced 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 the mechanical strength such as tensile strength, tear strength, and impact strength will be poor, and if the content of high-pressure low-density polyethylene is low, the improvement in melt tension will be insufficient, and therefore it is expected that the moldability will be deteriorated, such as a large neck-in.

[0006] Patent Document 2 discloses an ethylene polymer obtained by solution polymerization in the presence of a catalyst consisting of ethylenebis(indenyl)hafnium dichloride and methylalumoxane; Patent Document 3 discloses an ethylene polymer obtained by gas-phase polymerization in the presence of a catalyst consisting of ethylenebis(indenyl)zirconium dichloride and methylalumoxane supported on silica; Patent Document 4 discloses an ethylene polymer obtained by solution polymerization in the presence of a constrained geometry catalyst; and Patent Document 5 discloses an ethylene polymer obtained by gas-phase polymerization in the presence of a catalyst consisting of racemic and meso isomers of MeSi(2-Me-Ind) and methylalumoxane supported on silica. These ethylene polymers are described as having improved melt tension and excellent moldability compared to linear ethylene polymers without long chain branches. However, the neck-in remains large, suggesting that the improvement in moldability is insufficient. Furthermore, unlike high-pressure low-density polyethylene, these ethylene polymers do not exhibit strain-rate hardening in elongational viscosity, and therefore are not expected to improve take-up surge.

[0007] Patent Documents 6 and 7 disclose ethylene polymers in which the intrinsic viscosity and the weight-average molecular weight satisfy a specific relationship, the melt tension and the shear viscosity satisfy a specific relationship, or the zero-shear viscosity and the weight-average molecular weight exhibit a specific relationship. These ethylene polymers have improved take-up surging and have improved neck-in compared to conventional ethylene polymers in which long-chain branches are introduced using a metallocene catalyst. However, although the mechanical strength is superior to that of high-pressure low-density polyethylene, further improvement in mechanical strength is desired. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 7-26079 [Patent Document 2] Japanese Patent Application Publication No. 2-276807 [Patent Document 3] Japanese Patent Application Publication No. 4-213309 [Patent Document 4] International Publication No. 93 / 08221 [Patent Document 5] Japanese Patent Application Publication No. 8-311260 [Patent Document 6] Japanese Patent Application Laid-Open No. 2006-233207 [Patent Document 7] Japanese Patent Application Laid-Open No. 2009-197225 Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide an ethylene-based resin composition capable of forming a film having excellent moldability and particularly excellent mechanical strength compared to conventionally known ethylene-based polymers, and a film, a laminate, etc. obtained from the ethylene-based resin composition. [Means for solving the problem]

[0010] The present invention relates to, for example, the following [1] to

[13] . [1] The present invention comprises 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 a high-pressure low-density polyethylene (B) which satisfies the following requirements (a) to (c), The mass fraction (W A ) is 40% by mass or more and 90% by mass or less, and the mass fraction (W B ) is 10 mass% or more and 60 mass% or less (however, W A and W B The total of these is 100% by mass.) Ethylene-based resin composition (Z). (1) Density is 890 kg / m 3 More than 935kg / m 3 It is in the following range: (2) The melt flow rate (MFR) at 190°C under a load of 2.16 kg is in the range of 1.0 g / 10 min to 15.0 g / 10 min. (3) Melt tension at 190°C [MT(g)] and shear viscosity at 200°C and an angular velocity of 1.0 rad / s [η * (P)] and the ratio [MT / η * (g / P) is 1.40 x 10 -4 Over 2.90 x 10 -4 It is in the following range: (4) The zero shear viscosity [η0(P)] at 200°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1). 0.01×10 -13 ×Mw 3.4 ≦η0≦ 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 a GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-2): -2.0 ≦ Mz / Mw - Mw / Mn ≦ 15 (Eq-2) (6) 1 The total of vinyl, vinylidene, di-substituted internal olefin, and tri-substituted internal olefin per 1000 carbon atoms (units / 1000C) measured by H-NMR is in the range of 0.1 to 1.0. (a) Density is 915 kg / m 3 More than 930kg / m 3 It is in the following range: (b) The melt flow rate (MFR) at 190°C under a load of 2.16 kg is in the range of 0.1 g / 10 min or more and 20 g / 10 min or less. (c) The amount of components with a molecular weight of 1,000,000 or more in the molecular weight distribution curve obtained by GPC measurement is in the range of 1.0% to 20%.

[0011] [2] The ethylene-based resin composition (Z) according to [1] above, wherein the ethylene-α-olefin copolymer (A) further satisfies the following requirement (7): (7) The intrinsic viscosity [[η] (dl / g)] measured in decalin at 135°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-3). 0.7×10 -4 ×Mw 0.776 ≦[η]≦ 1.65×10 -4 ×Mw 0.776 (Eq-3)

[0012] [3] The ethylene-based resin composition (Z) according to the above [1] or [2], wherein the ethylene-α-olefin copolymer (A) further satisfies the following requirement (8): (8) The ratio Mz / Mw of the Z-average molecular weight (Mz) to the weight-average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) is in the range of 4.0 or more and 25.0 or less.

[0013] [4] The ethylene resin composition (Z) according to any one of the above [1] to [3], wherein the ethylene-α-olefin copolymer (A) further satisfies the following requirement (9): (9) There are multiple peaks in the melting curve obtained by differential scanning calorimetry (DSC).

[0014] [5] The ethylene resin composition (Z) of any one of [1] to [4] above, wherein the high-pressure low-density polyethylene (B) further satisfies the following requirement (d): (d) The ratio [δ100 / δ0.01] of the phase angle [δ100(°)] at 200°C and an angular velocity of 100 rad / sec to the phase angle [δ0.01(°)] at 200°C and an angular velocity of 0.01 rad / sec is in the range of 0.46 to 0.76.

[0015] [6] The ethylene resin composition (Z) according to any one of the above [1] to [5], further comprising a thermoplastic resin (excluding the above ethylene-α-olefin copolymer (A) and high-pressure low-density polyethylene (B)).

[0016] [7] A molded article comprising the ethylene resin composition (Z) of any one of [1] to [6] above. [8] A film comprising the ethylene resin composition (Z) of any one of [1] to [6] above.

[0017] [9] A multilayer film having a layer containing the ethylene resin composition (Z) of any one of [1] to [6] above.

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

[0018]

[11] The laminate according to

[10] , further comprising a substrate layer.

[12] The laminate according to

[10] , further comprising a barrier layer.

[0019]

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

[0020] The ethylene-based resin composition (Z) of the present invention can be suitably produced into molded articles, particularly films, laminates, and containers made of the laminates, which have excellent moldability (i.e., no take-up surging occurs in T-die molding and neck-in is small) and are particularly excellent in mechanical strength.

[0021] Furthermore, the ethylene resin composition (Z) of the present invention has excellent adhesive strength when used in an adhesive layer of a laminate. DETAILED DESCRIPTION OF THE INVENTION

[0022] The ethylene resin composition (Z) according to the present invention will be specifically described below together with its constituent components, the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B).

[0023] [Ethylene-based 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 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.

[0024] The ethylene-α-olefin copolymer (A) may contain structural units derived from at least one type of biomass-derived ethylene or α-olefin. The same type of monomers constituting the polymer may be composed solely of biomass-derived monomers, solely of fossil fuel-derived monomers, or both of biomass-derived monomers and fossil fuel-derived monomers. Biomass-derived monomers are monomers derived from any renewable natural raw materials and their residues, such as those derived from plants or animals, including fungi, yeast, algae, and bacteria, and contain 1×10 14C isotope as carbon. -12 The biomass carbon concentration (pMC) measured in accordance with ASTM D6866 is about 100 (pMC). Biomass-derived ethylene and α-olefins can be obtained, for example, by conventionally known methods.

[0025] It is preferable from the viewpoint of reducing the environmental load that the ethylene-α-olefin copolymer (A) contains a structural unit derived from a biomass-derived monomer. The ethylene-α-olefin copolymer (A) has the following properties (1) to (6).

[0026] (1) Density is 890 kg / m 3 More than 935kg / m 3 Less than 900 kg / m 3 More than 925kg / m 3 Less than or equal to 905 kg / m 3 More than 922kg / m 3 It is in the following range:

[0027] When the density is equal to or higher than the lower limit, the surface of a film formed from the ethylene-based resin composition (Z) is less sticky, and when the density is equal to or lower than the upper limit, the impact strength of a film formed from the ethylene-based resin composition (Z) is good, and mechanical strengths such as heat seal strength and bag-breaking strength of a bag made from the film are good.

[0028] 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 to ethylene (α-olefin / ethylene) in the polymerization system (for example, Walter Kaminsky, Makromol.Chem. 193, p.606(1992)). Therefore, an ethylene-α-olefin polymer having a density within the above range can be produced by increasing or decreasing the α-olefin / ethylene ratio.

[0029] The density is measured as follows. The strand obtained during MFR measurement is heat treated at 100°C for 30 minutes, and then left at room temperature for 1 hour before measurement by the density gradient tube method.

[0030] (2) The melt flow rate (MFR) is in the range of 1.0 g / 10 min or more and 15.0 g / 10 min or less, preferably 1.0 g / 10 min or more and 12.0 g / 10 min or less, and more preferably 3.0 g / 10 min or more and 12.0 g / 10 min or less.

[0031] When the melt flow rate (MFR) is equal to or higher than the lower limit, the shear viscosity of the ethylene-based resin composition (Z) is not too high and the extrusion load is good.When the melt flow rate (MFR) is equal to or lower than the upper limit, the mechanical strength of the ethylene-based resin composition (Z) is good.

[0032] The melt flow rate (MFR) is strongly dependent on molecular weight; the smaller the MFR, the higher the molecular weight, and the higher the MFR, the lower the molecular weight. It is also known that the molecular weight of an ethylene polymer is determined by the ratio of hydrogen to ethylene (hydrogen / ethylene) in the polymerization system (see, for example, Kazuo Soga et al., Catalytic Olefin Polymerization, Kodansha Scientific, 1990, p. 376). Therefore, the melt flow rate (MFR) of an ethylene polymer can be increased or decreased by increasing or decreasing the hydrogen / ethylene ratio. The melt flow rate (MFR) is measured according to JIS K 7210 at 190°C under a load of 2.16 kg.

[0033] (3) Melt tension [MT(g)] and shear viscosity [η] at 200°C and an angular velocity of 1.0 rad / s * (P) (P is Poise) and the ratio [MT / η * (g / P) is 1.40 x 10 -4 ~2.90×10 -4 , preferably 1.50 x 10 -4 ~2.70×10 -4 , more preferably 1.60 × 10 -4 ~2.45×10 -4 is in the range.

[0034] MT / η * When MT / η is equal to or greater than the lower limit, the ethylene-α-olefin copolymer (A) has a high melt tension relative to its molecular weight, and therefore the ethylene-based resin composition (Z) has excellent moldability. * When is equal to or less than the upper limit, the ethylene resin composition (Z) has excellent mechanical strength.

[0035] MT / η * depends on the long chain branch content of the ethylene polymer, and the higher the long chain branch content, the lower the MT / η * The lower the long-chain branch content, the greater the MT / η *Long chain branches are defined as branch structures having a length equal to or greater than the molecular weight between entanglement points (Me) contained in an ethylene polymer, and it is known that the introduction of long chain branches significantly changes the melt properties and moldability of ethylene polymers (for example, Kazuo Matsuura et al., eds., "Polyethylene Technology Reader," Kogyo Chosakai, 2001, pp. 32, 36).

[0036] MT / η * can be adjusted by the type of component (A) or solid support (S) of the olefin polymerization catalyst (X) described below. 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, MT / η * The MT / η near the lower limit can be reduced by the manufacturing conditions of Manufacturing Example 2 described later. * The MT / η * can be obtained.

[0037] The melt tension [MT(g)] is measured as follows. The 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 below, a Toyo Seiki Seisakusho Capillograph 1D capillary rheometer is used). The conditions are: resin temperature 190°C, melting time 6 minutes, barrel diameter 9.55 mmφ, extrusion speed 15 mm / min, take-up speed 24 m / min (if the molten filament breaks, the take-up speed is reduced by 5 m / min), nozzle diameter 2.095 mmφ, and nozzle length 8 mm.

[0038] Shear viscosity (η) at 200°C and angular velocity of 1.0 rad / sec * (P)] is measured as follows: Shear viscosity (η * ) is the shear viscosity (η *The angular velocity [ω (rad / sec)] dispersion of the ω is measured in the range of 0.01≦ω≦100. A viscoelasticity measuring device is used for the measurement (for example, in the examples described later, an Anton Paar Physica MCR301 viscoelasticity measuring device is used), a parallel plate with a diameter of 25 mm is used as the sample holder, and the sample thickness is approximately 2.0 mm. Five measurement points are set per ω digit. The strain amount is selected appropriately in the range of 3 to 10% so that the torque can be detected within the measurement range but does not exceed the torque limit.

[0039] The samples used for shear viscosity measurement were prepared using a molding machine (for example, a press molding machine manufactured by Shinto Metal Industries was used in the examples described later) under the following conditions: preheating temperature 190°C, preheating time 5 minutes, heating temperature 190°C, heating time 2 minutes, heating pressure 100 kgf / cm 2 , cooling temperature 20℃, cooling time 5 minutes, cooling pressure 100kgf / cm 2 Under the above conditions, a measurement sample is press-molded to a thickness of 2 mm.

[0040] (4) The zero shear viscosity [η0(P)] at 200°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relationship (Eq-1).

[0041] 0.01×10 -13 ×Mw 3.4 ≦η0≦ 4.5×10 -13 ×Mw 3.4 (Eq-1) Preferably, the following (Eq-1') is satisfied. 0.1×10 -13 ×Mw 3.4 ≦η0≦ 3.0×10 -13 ×Mw 3.4 (Eq-1') More preferably, the following (Eq-1") is satisfied. 0.2×10 -13 ×Mw 3.4 ≦η0≦ 2.0×10 -13 ×Mw 3.4 (Eq-1)

[0042] When the zero-shear viscosity [η(P)] is plotted against the weight-average molecular weight (Mw) on a double logarithmic scale, resins whose extensional viscosity does not exhibit strain hardening, such as linear ethylene polymers without long chain branches, follow a power law with a slope of 3.4, whereas resins whose extensional viscosity exhibits strain rate hardening, such as high-pressure low-density polyethylene, show a zero-shear viscosity [η(P)] lower than the power law (C. Gabriel, H. Munstedt, J. Rheol., 47(3), 619(2003)). When the zero-shear viscosity [η(P)] at 200°C is equal to or lower than the upper limit, the extensional viscosity of the ethylene polymer exhibits strain rate hardening, and therefore, take-up surging does not occur during molding of the ethylene resin composition (Z).

[0043] The relationship between the zero shear viscosity [η0(P)] and the weight average molecular weight (Mw) is considered to depend on the content and length of long chain branches in the ethylene polymer. It is considered that the greater the content of long chain branches and the shorter the length of the long chain branches, the smaller the zero shear viscosity [η0(P)] will be, and the smaller the content of long chain branches and the longer the length of the long chain branches, the larger the zero shear viscosity [η0(P)] will be.

[0044] The zero shear viscosity [η(P)] can be adjusted by the type of component (A) or solid support (S) of the olefin polymerization catalyst (X) described below. Even when the same olefin polymerization catalyst (X) is used, the zero shear viscosity [η(P)] can be adjusted by the polymerization conditions or polymerization process. For example, the zero shear viscosity [η(P)] can be increased by increasing the ethylene partial pressure. The zero shear viscosity [η(P)] near the lower limit can be obtained under the production conditions of Production Examples 14 and 15 described below, and the zero shear viscosity [η(P)] near the upper limit can be obtained under the production conditions of Production Example 12 described below.

[0045] The zero shear viscosity [η0(P)] at 200°C is measured as follows. At a measurement temperature of 200°C, shear viscosity (η *The angular velocity ω (rad / sec) dispersion of the strain is measured in the range of 0.01≦ω≦100. A viscoelasticity measuring device is used for the measurement (for example, in the examples described later, an Anton Paar Physica MCR301 viscoelasticity measuring device is used), a 25 mmφ parallel plate is used as the sample holder, and the sample thickness is approximately 2.0 mm. Five measurement points are set per ω digit. The strain amount is selected appropriately in the range of 3 to 10% so that the torque can be detected within the measurement range but does not exceed the torque.

[0046] The samples used for shear viscosity measurement were prepared using a molding machine (for example, a press molding machine manufactured by Shinto Metal Industries was used in the examples described later) under the following conditions: preheating temperature 190°C, preheating time 5 minutes, heating temperature 190°C, heating time 2 minutes, heating pressure 100 kgf / cm 2 , cooling temperature 20℃, cooling time 5 minutes, cooling pressure 100kgf / cm 2 Under the above conditions, a measurement sample is press-molded to a thickness of 2 mm.

[0047] The zero shear viscosity (η0) is calculated by fitting the Carreau model of the following formula to the measured rheology curve [shear viscosity (η * ) angular velocity (ω) variance.

[0048] η * =η0〔1+(λω) a 〕 (n-1) / a (λ is a parameter with a time dimension, a is a fitting parameter, and n is the power law index of the material.) The fitting by the nonlinear least squares method is performed so that d in the following formula is minimized.

[0049]

number

[0050] (ηexp(ω) represents the measured shear viscosity, and ηcalc(ω) represents the shear viscosity calculated using the Carreau model.) The weight average molecular weight (Mw) and the like are measured by gel permeation chromatography (GPC) as follows.

[0051] The detectors used were a differential refractometer and a capillary viscometer, the column temperature was 145°C, the mobile phase was o-dichlorobenzene, the flow rate was 1.0 ml / min, the sample concentration was 0.1 wt%, and the standard polymer was polystyrene. In the examples described below, the measurement equipment used was an Agilent GPC-viscometer (GPC-VISCO) PL-GPC220, two Agilent PLgel Olexis analytical columns, and a Tosoh polystyrene standard. The molecular weight was calculated by calculating the actual viscosity using the viscometer and refractometer, and the number average molecular weight (Mn), weight average molecular weight (Mw), Z-average molecular weight (Mz), and molecular weight distribution (Mw / Mn, Mz / Mw) were determined using actual universal calibration.

[0052] (5) The number average molecular weight (Mn), weight average molecular weight (Mw), and Z average molecular weight (Mz) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-2).

[0053] -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")

[0054] When Mz / Mw-Mw / Mn is large, the molecular weight distribution is broadened to the high molecular weight side. When Mz / Mw-Mw / Mn is equal to or greater than the lower limit, the ethylene-based resin composition (Z) has excellent melt film stability, and when Mz / Mw-Mw / Mn is equal to or less than the upper limit, the ethylene-based resin composition (Z) has excellent thin film formability.

[0055] The 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 can also be adjusted by the polymerization conditions or polymerization process even when the same olefin polymerization catalyst (X) is used. The Mz / Mw-Mw / Mn near the lower limit can be obtained under the production conditions of Production Example 5 described below, and the Mz / Mw-Mw / Mn near the upper limit can be obtained under the polymerization conditions of Production Example 14 described below.

[0056] The number average molecular weight (Mn), weight average molecular weight (Mw) and Z average molecular weight (Mz) are measured by the methods described above.

[0057] (6) 1 The numbers of vinyl, vinylidene, di-substituted internal olefin, and tri-substituted internal olefin measured by H-NMR satisfy the following relational formula (Eq-3).

[0058] 0.1≦vinyl + vinylidene + disubstituted internal olefin + trisubstituted internal olefin≦1.0 (Eq-3) Preferably, the following relational expression (Eq-3') is satisfied. 0.3≦vinyl + vinylidene + disubstituted internal olefin + trisubstituted internal olefin≦0.9 (Eq-3') More preferably, the following relational expression (Eq-3") is satisfied. 0.5≦vinyl + vinylidene + disubstituted internal olefin + trisubstituted internal olefin≦0.8 (Eq-3)

[0059] The number of vinyl, vinylidene, disubstituted internal olefin, and trisubstituted internal olefin in the polymer is 1This is the number per 1,000 carbon atoms contained in a polymer, as measured by H-NMR. It is known that the production ratio and number of vinyl, vinylidene, disubstituted internal olefins, and trisubstituted 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. Furthermore, even when using the same olefin polymerization catalyst (X), these can be adjusted by the polymerization conditions or polymerization process, for example, by increasing or decreasing the ethylene partial pressure.

[0060] When the number of units of vinyl + vinylidene + di-substituted internal olefin + tri-substituted internal olefin is equal to or greater than the above lower limit, long chain branches are likely to be generated and the ethylene-based resin composition (Z) has excellent moldability. When the number of units of vinyl + vinylidene + di-substituted internal olefin + tri-substituted internal olefin is equal to or less than the above upper limit, the ethylene-based resin composition (Z) has excellent heat-sealability, and the molded product has excellent transparency and mechanical strength because the molten film is less susceptible to oxidation during molding.

[0061] 1 The numbers of vinyl, vinylidene, di-substituted internal olefins, and tri-substituted internal olefins measured by H-NMR (500 MHz) are measured using a nuclear magnetic resonance apparatus (for example, in the examples described later, a Bruker AVANCE III (Cryoprobe) nuclear magnetic resonance apparatus was used) as follows.

[0062] 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 accumulations is 64. 20 mg of sample is dissolved in 0.6 ml of orthodichlorobenzene-d4 and measured at 120°C.

[0063] 1In the H-NMR spectrum, the number of double bonds and total double bonds calculated from the signal integrals derived from various double bonds (vinyl, vinylidene, internal olefin) at 4.5 ppm to 5.8 ppm were 1 The relative value of the total number of carbon atoms calculated from the total integrated value of the H signal is determined, and the number of various double bonds per 1,000 carbon atoms in the polymer is calculated.

[0064] The ethylene-α-olefin copolymer (A) preferably has the properties shown in the following (7).

[0065] (7) The intrinsic viscosity [[η] (dl / g)] measured in decalin at 135°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-3).

[0066] 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)

[0067] It is known that when long chain branches are introduced into an ethylene polymer, the intrinsic viscosity [[η] (dL / g)] becomes smaller relative to the molecular weight compared to a linear ethylene polymer without long chain branches (for example, Walther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched Polymer II, p. 137 (1999)). Therefore, the intrinsic viscosity [[η] (dL / g)] becomes 1.65 × 10-4 ×Mw 0.776 In the following cases, the resulting ethylene polymer has many long chain branches and is excellent in moldability and flowability.

[0068] 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) described below. Even when the same olefin polymerization catalyst (X) is used, the intrinsic viscosity [η] (dl / g) can be adjusted by the polymerization conditions or polymerization process. For example, the intrinsic viscosity [η] (dl / g) can be increased by increasing the ethylene partial pressure. A limiting viscosity [η] (dl / g) near the lower limit can be obtained under the production conditions of Production Example 11 described below, and a limiting viscosity [η] (dl / g) near the upper limit can be obtained under the production conditions of Production Example 12 described below.

[0069] The intrinsic viscosity [[η] (dl / g)] is measured as follows using decalin as a solvent. Approximately 20 mg of the measurement sample is dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135°C. 5 ml of decalin solvent is added to this decalin solution to dilute it, and the specific viscosity ηsp is measured in the same way. This dilution procedure is repeated two more times, and the value of ηsp / C when the concentration (C) is extrapolated to 0 as shown in the formula below is calculated as the limiting viscosity [η] (unit: dl / g).

[0070] [η]=lim(ηsp / C) (C→0) The weight average molecular weight (Mw) is measured as described above. The ethylene-α-olefin copolymer (A) preferably has the properties shown in the following (8).

[0071] (8) The ratio (Mz / Mw) of Z-average molecular weight (Mz) to weight-average molecular weight (Mw) measured by GPC-viscosity detector (GPC-VISCO) is in the range of 4.0 to 25.0, preferably 7.0 to 20.0, and more preferably 10.0 to 18.0. The larger the Mz / Mw, the more high-molecular-weight components there are. The ethylene-based resin composition (Z) has excellent neck-in properties when Mz / Mw is equal to or greater than the lower limit, and has excellent thin-film formability when Mz / Mw is equal to or less than the upper limit.

[0072] The Mz / Mw can be adjusted by the type of component (A) or solid support (S) of the olefin polymerization catalyst (X) described below, and can also be adjusted by the polymerization conditions or polymerization process even when the same olefin polymerization catalyst (X) is used. Mz / Mw near the lower limit can be obtained under the production conditions of Production Example 5 described below, and Mz / Mw near the upper limit can be obtained under the polymerization conditions of Examples 11 and 14 described below.

[0073] The ethylene-α-olefin copolymer (A) preferably has the properties shown in the following (9).

[0074] (9) There are multiple peaks in the melting curve obtained by differential scanning calorimetry (DSC). If there are multiple peaks, there are many low-melting components and the heat sealability at low temperatures is excellent. Differential scanning calorimetry (DSC) is carried out using a differential scanning calorimeter (for example, Diamond DSC manufactured by PerkinElmer was used in the examples described below) as follows.

[0075] Approximately 5 mg of sample is placed 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 back to 200°C at 10°C / min, obtaining an endothermic curve. If this endothermic curve has two or more peaks, it means that the melting curve obtained by differential scanning calorimetry (DSC) has multiple peaks.

[0076] When the ethylene-α-olefin copolymer (A) has the property as described in the above (9), the ethylene-based resin composition (Z) of the present invention has excellent heat sealability when used in a heat seal layer of a laminate.

[0077] [High-pressure low-density polyethylene (B)] The high-pressure low-density polyethylene (B) is produced by polymerizing ethylene by high-pressure radical polymerization, and has many branched long-chain branches. The high-pressure low-density polyethylene (B) has the following properties (a) to (c).

[0078] (a) Density is 915 kg / m 3 More than 930kg / m 3 Less than or equal to 915 kg / m 3 More than 925kg / m 3 Less than or equal to 915 kg / m 3 More than 920kg / m 3 It is in the following range:

[0079] When the density is equal to or lower than the upper limit, the low-temperature heat sealability of the film formed from the ethylene resin composition (Z) is good. It is difficult to produce a high-pressure low-density polyethylene having a density equal to or lower than the lower limit.

[0080] (b) The melt flow rate (MFR) is in the range of 0.1 g / 10 min or more and 20 g / 10 min or less, preferably 0.5 g / 10 min or more and 10 g / 10 min or less, and more preferably 0.8 g / 10 min or more and 8.0 g / 10 min or less.

[0081] When the melt flow rate (MFR) is equal to or higher than the lower limit, the film formed from the ethylene-based resin composition (Z) has few fisheyes and a good appearance.When the melt flow rate (MFR) is equal to or lower than the upper limit, the ethylene-based resin composition (Z) has high melt tension and good moldability such as melt film stability.

[0082] (c) In the molecular weight distribution curve obtained by GPC measurement, the amount of components with a molecular weight of 1,000,000 or more is in the range of 1.0% to 20%, preferably 2.0% to 15%, more preferably 4.0% to 13%.

[0083] When the amount of components having a molecular weight of 1,000,000 or more in a molecular weight distribution curve obtained by GPC measurement is equal to or greater than the lower limit, the ethylene-based resin composition (Z) has excellent neck-in properties. When the amount of components having a molecular weight of 1,000,000 or more in a molecular weight distribution curve obtained by GPC measurement is equal to or less than the upper limit, the ethylene-based resin composition (Z) has excellent thin film formability.

[0084] The amount of components having a molecular weight of 1,000,000 or more in a molecular weight distribution curve obtained by GPC measurement is calculated by measuring under the following conditions using a gel permeation chromatograph. Note that the following equipment was used in the examples described below.

[0085] [Equipment used] Measuring device: HLC-8321 GPC / HT type (manufactured by Tosoh Corporation) Data processing software: Empower 3 (Waters) Column: 2x TSKgel GMH6-HT + 2x TSKgel GMH6-HTL (Both 7.5 mm I.D. x 30 cm, Tosoh Corporation) Polystyrene: Monodisperse polystyrene (Tosoh Corporation); #3 standard set

[0086] [Measurement conditions] 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 calibration method

[0087] The amount (%) of components with a molecular weight of 1 million or more is calculated from the obtained molecular weight distribution curve. The high-pressure low-density polyethylene (B) preferably has the following properties (d).

[0088] (d) The ratio [δ100 / δ0.01] of the phase angle [δ100 (°)] at 200°C and an angular velocity of 100 rad / sec to the phase angle [δ0.01 (°)] at 200°C and an angular velocity of 0.01 rad / sec is in the range of 0.46 or more and 0.76 or less, preferably 0.46 or more and 0.72 or less, and more preferably 0.47 or more and 0.64 or less.

[0089] The angular velocity [ω (rad / sec)] dispersion of the phase angle (δ) is known to be strongly affected by the content, length, and structure of long-chain branches in an ethylene polymer (for example, S. Trinkle, P. Walter, C. Friedrich, Rheol Acta, 41, 103 (2002)). When long-chain branches are introduced into an ethylene polymer, the δ100 / δ0.01 ratio is larger than that of a linear ethylene polymer without long-chain branches. Furthermore, the longer the introduced long-chain branches are or the more complex the branch structure, the larger the δ100 / δ0.01 ratio. The ethylene resin composition (Z) exhibits excellent neck-in properties when the δ100 / δ0.01 ratio is equal to or greater than the lower limit, and exhibits good mechanical strength when the δ100 / δ0.01 ratio is equal to or less than the upper limit.

[0090] 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 dispersion of the angular velocity [ω (rad / sec)] 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 is used for the measurement (for example, in the examples described below, an Anton Paar Physica MCR301 viscoelasticity measuring device is used), and a 25 mmφ parallel plate is used as the sample holder, with the sample thickness set to approximately 2.0 mm. Five measurement points are set per ω digit. The strain amount is selected appropriately in the range of 3 to 10% so that the torque can be detected within the measurement range but does not exceed the torque limit.

[0091] The samples used for shear viscosity measurement were prepared using a molding machine (for example, a press molding machine manufactured by Shinto Metal Industries was used in the examples described later) under the following conditions: preheating temperature 190°C, preheating time 5 minutes, heating temperature 190°C, heating time 2 minutes, heating pressure 100 kgf / cm 2 , cooling temperature 20℃, cooling time 5 minutes, cooling pressure 100kgf / cm 2 Under the above conditions, a measurement sample is press-molded to a thickness of 2 mm.

[0092] <Ethylene-based resin composition (Z)> The ethylene-based 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 mass fraction (W A ) and the mass fraction (W B ) is 100% by mass, and W A 40 to 90 mass%, W B is 10 to 60 mass%. A is preferably 50 to 85% by mass, more preferably 60 to 75% by mass. Within this range, the ethylene resin composition (Z) has excellent moldability and mechanical strength.

[0093] Furthermore, the ethylene-based resin composition (Z) according to the present invention may consist essentially of the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B), but is not limited thereto, and may contain, in addition to the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B), a thermoplastic resin other than the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) (hereinafter referred to as "another thermoplastic resin"). The ethylene-based resin composition (Z) obtained as a thermoplastic resin composition by blending the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) with the "other thermoplastic resin" has excellent moldability and mechanical strength.

[0094] The blend ratio of the total of the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) to the "other thermoplastic resin" (total mass of the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) / mass of the other thermoplastic resin) is usually 99.9 / 0.1 to 0.1 / 99.9, preferably 90 / 10 to 10 / 90, and more preferably 70 / 30 to 30 / 70.

[0095] (other thermoplastic resins) Other thermoplastic resins that can be used include crystalline thermoplastic resins such as polyolefins, polyamides, polyesters, and polyacetals; and amorphous thermoplastic resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate, polyphenylene oxide, and polyacrylate. Polyvinyl chloride is also preferably used.

[0096] Specific examples of the polyolefin include ethylene polymers, propylene polymers, butene polymers, 4-methyl-1-pentene polymers, 3-methyl-1-butene polymers, and hexene polymers. Among these, ethylene polymers, propylene polymers, and 4-methyl-1-pentene polymers are preferred. In the case of ethylene polymers, they may be conventional ethylene polymers or ethylene-polar group-containing vinyl copolymers, but conventional ethylene polymers are more preferred. The ethylene polymers and propylene polymers may be ethylene polymers and propylene polymers containing biomass-derived monomers, respectively.

[0097] The ethylene resin composition (Z) of the present invention may contain additives such as weather resistance stabilizers, heat resistance stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbers, and antioxidants, as needed, within the scope of not impairing the object of the present invention.

[0098] The total amount of additives added is generally 10 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, per 100 parts by mass of the total of the components other than the additives in the ethylene resin composition (Z).

[0099] <Method for producing ethylene-α-olefin copolymer (A)> Next, the method for producing the ethylene-α-olefin copolymer (A) will be described. The ethylene-α-olefin copolymer (A) can be efficiently produced by polymerizing ethylene and an α-olefin having 4 to 10 carbon atoms in the presence of an olefin polymerization catalyst (X) comprising the following components:

[0100] [Olefin polymerization catalyst (X)] The olefin polymerization catalyst (X) comprises the following component (A) and a solid support (S):

[0101] <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 or more transition metal compounds (1) may be used.

[0102] [ka]

[0103] In the formula (1), M is a zirconium atom or a hafnium atom, and is preferably a zirconium atom. In the formula (1), n ​​is an integer of 1 to 4, preferably 2, selected so that the transition metal compound (1) is electrically neutral.

[0104] In the formula (1), each X is independently 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 is preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0105] The halogen atom includes fluorine, chlorine, bromine and iodine, with chlorine being particularly preferred. Examples of the hydrocarbon group having 1 to 20 carbon atoms include: linear or branched alkyl groups such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl (butan-2-yl), tert-butyl (2-methylpropan-2-yl), isobutyl (2-methylpropyl), pentan-2-yl, 2-methylbutyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), cyamyl (1,2-dimethylpropyl), isohexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl (2,3-dimethylbut-2-yl), and 4,4-dimethylpentyl; Vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl group (propa-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), buta-1,3-dienyl group, pentaerythritol group, linear or branched alkenyl groups or unsaturated double bond-containing groups such as pent-4-en-1-yl, pent-3-en-1-yl, pent-2-en-1-yl, iso-pentenyl (3-methylbut-3-en-1-yl), 2-methylbut-3-en-1-yl, pent-4-en-2-yl, and prenyl (3-methylbut-2-en-1-yl); linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl, prop-2-yn-1-yl, and propargyl (prop-1-yn-1-yl) groups; linear or branched alkyl groups containing aromatic groups and unsaturated double bond-containing groups, such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-isopropylbenzyl group), 2,4,6-tri-isopropylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, and benzhydryl group (diphenylmethyl group); cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cycloheptatrienyl, norbornyl, norbornenyl, 1-adamantyl, and 2-adamantyl; Aromatic substituents such as phenyl, tolyl (methylphenyl), xylyl (dimethylphenyl), mesityl (2,4,6-trimethylphenyl), cumenyl (isopropylphenyl), duralyl (2,3,5,6-tetramethylphenyl), 2,6-di-isopropylphenyl, 2,4,6-tri-isopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, naphthyl, biphenyl, ter-phenyl, binaphthyl, acenaphthalenyl, phenanthryl, anthracenyl, pyrenyl, and ferrocenyl groups Among these, preferred are a methyl group, an isobutyl group, a neopentyl group, a cyamyl group, a benzyl group, a phenyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group.

[0106] 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 have been substituted with halogen atoms, and examples thereof include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a pentachloroethyl group, a pentafluorophenylmethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, and a bistrifluoromethylphenyl group, with a pentafluorophenyl group being preferred.

[0107] Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, and a trimethylsilylmethyl group, and preferably a trimethylsilylmethyl group.

[0108] Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a benzyloxy group, a methoxymethoxy group, a phenoxy group, a 2,6-dimethylphenoxy group, a 2,6-di-isopropylphenoxy group, a 2,6-di-tert-butylphenoxy group, a 2,4,6-trimethylphenoxy group, a 2,4,6-tri-isopropylphenoxy group, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetoxy group, a perchlorate anion, and a periodate anion, and preferred are a methoxy group, an ethoxy group, an isopropoxy group, and a tert-butoxy group.

[0109] 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, a piperidinyl group, a morpholyl group, a pyrrolyl group, and a bistriflylimide group.

[0110] 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), a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group, and a cyclopentadienyl group, and preferably a 1,3-butadienyl group or a 1,3-pentadienyl group.

[0111] In the formula (1), Q is a carbon atom or a silicon atom, and is preferably a silicon atom. In the formula (1), R 1 ~R 14 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, and are preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group having 1 to 20 carbon atoms.

[0112] R 1 ~R 14 Examples of the hydrocarbon group having 1 to 20 carbon atoms as the alkyl group include linear or branched alkyl groups such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl (butan-2-yl), tert-butyl (2-methylpropan-2-yl), isobutyl (2-methylpropyl), pentan-2-yl, 2-methylbutyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), cyamyl (1,2-dimethylpropyl), isohexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl (2,3-dimethylbut-2-yl), and 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 (propa-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), buta-1,3-dienyl group, pentaerythritol group, linear or branched alkenyl groups or unsaturated double bond-containing groups such as pent-4-en-1-yl, pent-3-en-1-yl, pent-2-en-1-yl, iso-pentenyl (3-methylbut-3-en-1-yl), 2-methylbut-3-en-1-yl, pent-4-en-2-yl, and prenyl (3-methylbut-2-en-1-yl); linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl, prop-2-yn-1-yl, and propargyl (prop-1-yn-1-yl) groups; linear or branched alkyl groups containing aromatic groups and unsaturated double bond-containing groups, such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-isopropylbenzyl group), 2,4,6-tri-isopropylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group (diphenylmethyl group), and pentafluorophenylmethyl group; cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cycloheptatrienyl, norbornyl, norbornenyl, 1-adamantyl, and 2-adamantyl; aromatic substituents such as phenyl, tolyl (methylphenyl), xylyl (dimethylphenyl), mesityl (2,4,6-trimethylphenyl), cumenyl (isopropylphenyl), duralyl (2,3,5,6-tetramethylphenyl), 2,6-di-isopropylphenyl, 2,4,6-tri-isopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, naphthyl, biphenyl, tert-phenyl, binaphthyl, acenaphthalenyl, phenanthryl, anthracenyl, pyrenyl, and ferrocenyl; halogen-substituted hydrocarbon groups in which some or all of the hydrogen atoms of the hydrocarbon groups having 1 to 20 carbon atoms have been substituted with halogen atoms, such as a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a pentachloroethyl group, a pentafluorophenylmethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, and a bistrifluoromethylphenyl group; and preferably a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, a 1-octyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an allyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclooctenyl group, a norbornyl group, a bicyclo[2.2.2]octan-1-yl group, a 1-adamantyl group, a 2-adamantyl group, or a 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-isopropylphenyl group, 2,4,6-tri-isopropylphenyl 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, anthracenyl group, ferrocenyl group, and pentafluorophenyl group.

[0113] R 1 ~R 14 Preferred examples of the silicon-containing group having 1 to 20 carbon atoms as the aryl group include a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, a cyclopentadienyldimethylsilyl group, a cyclopentadienyldiphenylsilyl group, an indenyldimethylsilyl group, a fluorenyldimethylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-isopropylsilylphenyl group, and a 3,5-bis(trimethylsilyl)phenyl group, and examples thereof include a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-isopropylsilylphenyl group, and a 3,5-bis(trimethylsilyl)phenyl group.

[0114] R 1 ~R14 Examples of the oxygen-containing group having 1 to 20 carbon atoms as the alkyl group include a methoxy group, an ethoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a tert-butoxy group, a prenyloxy group, a benzyloxy group, a phenoxy group, a naphthoxy group, a toluyloxy group, an iso-propylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, a biphenyloxy group, a binaphthyloxy group, an allyloxymethyl group, a benzyloxymethyl group, a phenoxymethyl group, a methoxyethyl group, a methoxyallyl group, a benzyloxyallyl group, a phenoxyallyl group, a dimethoxymethyl group, a dioxolanyl group, a tetramethyldioxolanyl group, a dioxanyl group, a dimethyldioxanyl group, a methoxyphenyl group, an iso-propoxyphenyl group, an aryloxy group, an aryloxymethyl group, a ... Examples thereof include an allyloxyphenyl group, a phenoxyphenyl group, a methylenedioxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a tetrahydropyranyl group, a furofuryl group, a benzofuryl group, and a dibenzofuryl group, and preferred are a methoxy group, an isopropoxy group, a tert-butoxy group, an allyloxy group, a phenoxy group, a dimethoxymethyl group, a dioxolanyl group, a methoxyphenyl group, an isopropoxyphenyl group, an allyloxyphenyl group, a phenoxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a benzofuryl group, and a dibenzofuryl group.

[0115] R 1 ~R 14Examples of the nitrogen-containing group having 1 to 20 carbon atoms as the aryl group 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, a dimethylaminomethyl group, a benzylaminomethyl group, a pyrrolidinylmethyl group, a dimethylaminoethyl group, a pyrrolidinylethyl group, a dimethylaminopropyl group, a pyrrolidinylpropyl group, a dimethylaminoallyl group, a pyrrolidinylallyl group, an aminophenyl group, a dimethylaminophenyl group, a 3,5-dimethyl-4-dimethylaminophenyl group, a 3,5-di-iso-propyl-4-dimethylaminophenyl group, a julolidinyl group, a tetramethyljulolidinyl group, a pyrrolidinylphenyl group, a pyrrolylphenyl group, a carbazolylphenyl group, a di-tert-butylcarbazolyl group, a Examples thereof include a zolylphenyl group, a pyrrolyl group, a pyridyl group, a quinolyl group, a tetrahydroquinolyl group, an isoquinolyl group, a tetrahydro-isoquinolyl group, an indolyl group, an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzimidazolyl group, an oxazolyl group, an oxazolidinyl group, and a benzoxazolyl group, and preferred are an amino group, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a dimethylaminophenyl group, a 3,5-dimethyl-4-dimethylaminophenyl group, a 3,5-di-isopropyl-4-dimethylaminophenyl group, a julolidinyl group, a tetramethyljulolidinyl group, a pyrrolidinylphenyl group, a pyrrolyl group, a pyridyl group, a carbazolyl group, and an imidazolyl group.

[0116] In the formula (1), R 1 ~R 6 Adjacent substituents (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. In this case, the ring formed is preferably a 5- to 8-membered ring which is fused to the indenyl ring moiety and which is made of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring moiety) or an unsaturated hydrocarbon which may have a substituent. When multiple rings are present, these may be the same or different. Although not particularly limited as long as the effects of the present invention are achieved, the ring is more preferably a 5- or 6-membered ring. In this case, examples of the structure formed by combining the ring and the indenyl ring moiety of the mother nucleus include a benzoindenyl ring, a tetrahydroindacene ring, and a cyclopentatetrahydronaphthalene ring, with a benzoindenyl ring and a tetrahydroindacene ring being preferred. These rings may have a substituent.

[0117] In the formula (1), R 7 ~R 12 Adjacent substituents (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. In this case, the ring formed is preferably a 5- to 8-membered ring fused to the indenyl ring moiety and made of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring moiety) or an unsaturated hydrocarbon which may have a substituent. When multiple rings are present, these may be the same or different. Although not particularly limited as long as the effects of the present invention are achieved, the ring is more preferably a 5- or 6-membered ring. In this case, examples of the structure formed by combining the ring and the indenyl ring moiety of the mother nucleus include a benzoindenyl ring, a tetrahydroindacene ring, a cyclopentatetrahydronaphthalene ring, a tetrahydrofluorene ring, and a fluorene ring, with a benzoindenyl ring and a tetrahydroindacene ring being preferred. These rings may have a substituent.

[0118] In the formula (1), R13 and R 14 may be bonded to each other to form a ring containing Q, and these rings may have a substituent. In this case, the ring formed is preferably a 3- to 8-membered saturated or unsaturated ring which may have a substituent. There are no particular limitations as long as the effects of the present invention are achieved, but a 4- to 6-membered ring is preferred. In this case, examples of the structure combined with Q include a cyclobutane ring, a cyclopentane ring, a fluorene ring, a silacyclobutane (siletane) ring, a silacyclopentane (silorane) ring, a silacyclohexane (silinane) ring, and a silafluorene ring, and a cyclopentane ring, a silacyclobutane ring, and a silacyclopentane ring are preferred. These rings may have a substituent.

[0119] Specific examples of the transition metal compound (1) are shown below, but the scope of the present invention is not particularly limited by these. For convenience, the ligand structure excluding the portion represented by MXn (metal portion) of the transition metal compound (1) is represented by the 2-indenyl ring portion, the 1-indenyl ring portion, the indenyl ring portion R 1 , R 6 and R 8 Substituent, indenyl ring moiety R 2 , R 5 , R 9 and R 12 Substituent, indenyl ring moiety R 3 , R 4 , R 10 and R 11 Substituent, 1-indenyl ring moiety R 7 The structure of the substituent and the bridged portion is divided into seven parts. The abbreviation for the 2-indenyl ring portion is α, the abbreviation for the 1-indenyl ring portion is β, and the indenyl ring portion R 1 , R 6 and R 8 The abbreviation for the substituent is γ, and the indenyl ring portion is R 2 , R 5 , R 9 and R 12 The abbreviation of the substituent is δ, and the indenyl ring portion is R 3 , R 4 , R 10 and R 11 The abbreviation for the substituent is ε, and the 1-indenyl ring moiety is R7 The abbreviation for the substituent is ζ, the abbreviation for the structure of the crosslinked portion is η, and the abbreviations for each substituent are shown in [Table 1] to [Table 7].

[0120] [Table 1]

[0121] [Table 2]

[0122] The wavy lines in Tables 1 and 2 indicate the bonding sites with the crosslinked moieties.

[0123] [Table 3]

[0124] R in Table 3 1 , R 6 and R 8 The substituents in any combination may be the same or different from one another.

[0125] [Table 4]

[0126] R in Table 4 2 , R 5 , R 9 and R 12 The substituents in any combination may be the same or different from one another.

[0127] [Table 5]

[0128] R in Table 5 3 , R 4 , R 10 and R 11The substituents in any combination may be the same or different from one another.

[0129] [Table 6]

[0130] [Table 7]

[0131] Specific examples of the metal moiety MXn include ZrF2, ZrCl2, ZrBr2, ZrI2, Zr(Me)2, Zr(Bn)2, Zr(Allyl)2, Zr(CH2-tBu)2, Zr(1,3-butadienyl), Zr(1,3-pentadienyl), Zr(2,4-hexadienyl), Zr(1,4-diphenyl-1,3-pentadienyl), Zr(CH2-Si(Me)3)2, Zr(OMe)2, Zr(OMiPr)2, Zr(NMe2)2, Zr(OMs)2, Zr(OTs)2, Zr( OTf), HfF, HfCl, HfBr, HfI, Hf(Me), Hf(Bn), Hf(Allyl), Hf(CH-tBu), Hf(1,3-butadienyl), Hf(1,3-pentadienyl), Hf(2,4-hexadienyl), Hf(1,4-diphenyl-1,3-pentadienyl), Hf(CH-Si(Me)), Hf(OMe), Hf(OiPr), Hf(NMe), Hf(OMs), Hf(OTs), Hf(OTf), 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, OMe is a methoxy group, OMe is an isopropoxy group, NMe2 is a dimethylamino group, OMs is a methanesulfonate group, OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

[0132] 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 8All of the substituents are the γ-1,2-indenyl ring moiety R in [Table 3] 2 and R 5 All of the substituents are the δ-1,2-indenyl ring moiety R in [Table 4] 3 and R 4 The substituents are all ε-1,1-indenyl ring moiety R in [Table 5] 7 The substituent is ζ-30, 1-indenyl ring moiety R in [Table 6] 9 The substituent is δ-38 in [Table 4], 1-indenyl ring moiety R 12 When the substituent is δ-3 in [Table 4], the bridging portion is η-20 in [Table 7], and the metal portion MXn is ZrCl2, the compound represented by the following formula [6] is exemplified.

[0133] [ka]

[0134] In addition, 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 All of the substituents are the γ-1,2-indenyl ring moiety R in [Table 3] 2 and R 5 All of the substituents are the δ-2,2-indenyl ring moiety R in [Table 4] 3 and R 4 The substituents are all ε-1,1-indenyl ring moiety R in [Table 5] 7 When the substituent is ζ-1 in [Table 6], the bridging portion is η-4 in [Table 7], and the metal portion MXn is Zr(NMe2)2, the compound represented by the following formula [7] is exemplified.

[0135] [ka]

[0136] In addition, the 2-indenyl ring moiety is α-3 in [Table 1], and the 1-indenyl ring moiety is β-1 in [Table 2], and the 2-indenyl ring moiety R 1and R 6 The substituents are all γ-2 in [Table 3], the indenyl ring moiety R 2 , R 5 and R 12 All of the substituents are the δ-1,1-indenyl ring moiety R in [Table 4] 7 The substituent is the ζ-12, 1-indenyl ring moiety R in [Table 6] 8 The substituent is the γ-1,1-indenyl ring moiety R in [Table 3] 9 The substituent is δ-42 in [Table 4], 1-indenyl ring moiety R 10 The substituent is the ε-3,1-indenyl ring moiety R in [Table 5] 11 When the substituent is ε-12 in [Table 5], the bridging portion is η-31 in [Table 7], and the metal portion MXn is HfMe2, the compound represented by the following formula [8] is exemplified.

[0137] [ka]

[0138] In addition, the 2-indenyl ring moiety is the α-1 in [Table 1], and the 1-indenyl ring moiety is the β-1,2-indenyl ring moiety R in [Table 2]. 1 and R 6 All of the substituents are the γ-1,2-indenyl ring moiety R in [Table 3] 2 The substituent is the δ-7, 2-indenyl ring moiety R in [Table 4] 3 , R 4 , R 10 and R 11 The substituents are all the ε-1,2-indenyl ring moiety R in [Table 5]. 5 The substituent is the δ-2,1-indenyl ring moiety R in [Table 4] 7 The substituent is the ζ-1,1-indenyl ring moiety R in [Table 6] 8 The substituent is the γ-9,1-indenyl ring moiety R in [Table 3] 9 and R 12 When the substituents are all composed of a combination of δ-1 in [Table 4], the bridging portion is composed of a combination of η-29 in [Table 7], and the metal portion MXn is Zr(1,3-pentadienyl), the compound represented by the following formula [9] is exemplified.

[0139] [ka]

[0140] The transition metal compound (1) can be produced by any 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 production methods include those described in "Organometallics 1994, 13,954," "Organometallics 2006, 25, 1217," JP-A-2006-509059, "Bioorg.Med.Chem. 2008, 16, 7399," WO2009 / 080216, "Organometallics 2011, 30, 5744," JP-A-2011-500800, "Organometallics 2012, 31, 4962," and "Chem.Eur.J. 2012,18,4174.", JP 2012-012307 A, JP 2012-121882 A, JP 2014-196319 A, JP 2014-513735 A, JP 2015-063495 A, JP 2016-501952 A, JP 2019-059933 A, and the like.

[0141] Known methods for producing the transition metal compound (1) and the precursor compound (ligand) are described, for example, in "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."

[0142] In addition, the transition metal compound (1) has two faces (front and back) of the indenyl ring moiety that is bonded to the central metal across the bridge. Therefore, when the 2-indenyl ring moiety does not have a symmetrical plane, two structural isomers, for example, represented by the following general formula [10a] or [10b], exist.

[0143] [ka]

[0144] Similarly, the substituent R of the bridging portion 13 and R 14 are not identical, there exist two structural isomers represented by the following general formula [11a] or [11b].

[0145] [ka]

[0146] Purification and separation 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. Known production methods include those exemplified as the production method for the transition metal compound (1), as well as production methods disclosed in JP-A-10-109996, "Organometallics 1999, 18, 5347," "Organometallics 2012, 31, 4340," and JP-A-2011-502192.

[0147] Within the scope of the transition metal compound (1), the transition metal compound may be used alone or in combination of two or more, or a structural isomer mixture may be used, or a structural isomer may be used alone or in combination of two or more. As described above, according to the present invention, an ethylene polymer having many long-chain branches introduced therein can be produced with high catalytic activity by using only the transition metal compound (1) as the transition metal compound constituting the olefin polymerization catalyst. However, as long as this effect is not impaired, one or more transition metal compounds other than the transition metal compound (1) may be used in combination as the transition metal compound. In this case, the transition metal compound (1) may be in any of the above-mentioned embodiments.

[0148] <Solid Carrier (S)> The solid support (S) contained in the olefin polymerization catalyst (X) is an inorganic or organic compound, and is a granular or fine particle solid.

[0149] Examples of inorganic compounds used as the solid support (S) include porous oxides, solid aluminoxane compounds, inorganic chlorides, clays, clay minerals, and ion-exchange layered compounds.

[0150] The porous oxides that can be used include SiO2, Al2O3, MgO, ZrO, TiO2, BO3, CaO, ZnO, BaO, and ThO2, as well as composites or mixtures containing these, specifically natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-VO5, SiO2-Cr2O3, and SiO2-TiO2-MgO. Of these, those containing SiO2 as the main component are preferred.

[0151] The porous oxide may contain small amounts of carbonates, sulfates, nitrates, and oxides such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O.

[0152] The properties of such porous oxides vary depending on the type and production 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 usually 50 to 1200 m 2 / g, preferably 100 to 1000m 2 / g, and the pore volume is typically 0.3 to 30 cm 3 / g range. Such a carrier is calcined, for example, at 100 to 1000°C, preferably 150 to 700°C, as needed, before use.

[0153] Examples of the solid aluminoxane compound include an aluminoxane having a structure represented by the following general formula (Sa), an aluminoxane having a structure represented by the following general formula (Sb), and an aluminoxane having a structure comprising a repeating unit represented by the following general formula (Sc) and a repeating unit represented by the following general formula (Sd).

[0154] [ka]

[0155] In the above formulas (Sa) to (Sd), R e are each independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specific examples thereof include hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, isopropenyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclohexyl, cyclooctyl, phenyl, tolyl, and ethylphenyl groups, with methyl, ethyl, and isobutyl being preferred, and methyl being particularly preferred. e A part of the halogen atoms is substituted with halogen atoms such as chlorine and bromine, and the halogen content is R eIn the above formulas (Sc) and (Sd), a line that is not connected to an atom on one side represents a bond to another atom that is not shown.

[0156] In the formulas (Sa) and (Sb), r represents an integer of 2 to 500, preferably 6 to 300, and particularly preferably 10 to 100. In the formulas (Sc) and (Sd), s and t each represent an integer of 1 or greater. r, s, and t are selected so that the aluminoxane can be maintained in a substantially solid state in the reaction environment in which it is used.

[0157] Unlike conventionally known olefin polymerization catalyst supports, the solid aluminoxane compound does not contain inorganic solid components such as silica or alumina, or organic polymer components such as polyethylene or polystyrene, but is a solidified product of an alkylaluminum compound as the main component. The term "solid" means that the aluminoxane component maintains a substantially solid state under the reaction environment in which it is used. More specifically, the aluminoxane component maintains a substantially solid state when the component (A) is contacted with the aluminoxane component to prepare an olefin polymerization catalyst (e.g., an ethylene polymerization catalyst) as described below, and when the prepared olefin polymerization catalyst is used to polymerize an olefin (e.g., ethylene) (e.g., suspension polymerization).

[0158] Visual confirmation is the simplest method for determining whether the aluminoxane component is in a solid state; however, visual confirmation is often difficult, for example, during polymerization. In such cases, it can be determined, for example, from the properties of the polymer powder obtained after polymerization and the state of adhesion to the reactor. Conversely, if the polymer powder has good properties and little adhesion to the reactor, even if a portion of the aluminoxane component leaches out to a certain extent under the polymerization environment, this does not deviate from the spirit of the present invention. Examples of indicators for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the presence of amorphous polymers, but polymer bulk density is preferred from the viewpoint of quantitative determination. The bulk density is typically 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

[0159] The solubility of the solid aluminoxane compound in n-hexane maintained at 25° C. is usually in the range of 0 to 40 mol %, preferably 0 to 20 mol %, and particularly preferably 0 to 10 mol %.

[0160] The dissolution rate can be determined by adding 2 g of the solid aluminoxane compound carrier to 50 ml of n-hexane kept at 25°C, stirring for 2 hours, separating the solution using a G-4 glass filter, and measuring the aluminum concentration in the filtrate. Therefore, the dissolution rate is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms equivalent to 2 g of the aluminoxane used.

[0161] The solid aluminoxane compound can be any known solid aluminoxane without limitation, and can be, for example, the solid polyaluminoxane composition described in International Publication No. 2014 / 123212. Known production methods include those described in JP-B-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000-38410, JP-A-2000-95810, and International Publication No. 2010 / 55652.

[0162] The average particle diameter of the solid aluminoxane compound is generally in the range of 0.01 to 50,000 μm, preferably 0.1 to 1,000 μm, and 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 the weight values. First, the particle diameter d of each particle is determined by measuring the length of a particle image between two parallel lines in the horizontal and vertical directions, and then using the following formula:

[0163] Particle size d = ((horizontal length) 2 +(vertical length) 2 ) 0.5 Next, the weight average particle size of the solid aluminoxane compound is calculated by the following formula using the particle size d calculated above and the number of particles n. Average particle diameter=Σnd 4 / Σnd 3 The solid aluminoxane compound has a specific surface area of ​​50 to 1000 m 2 / g, preferably 100 to 800m 2 / g, and the pore volume is 0.1 to 2.5 cm 3 / g is desirable.

[0164] Examples of the inorganic halide include MgCl, MgBr, MnCl, and MnBr. The inorganic halide may be used as is, or may be used after being pulverized using a ball mill or a vibration mill. Alternatively, the inorganic halide may be dissolved in a solvent such as alcohol and then precipitated into fine particles using a precipitating agent.

[0165] Clay is usually composed mainly of clay minerals. Ion-exchangeable layered compounds are compounds with a crystalline structure in which planes formed by ionic bonds or the like are stacked parallel to one another with weak bonding forces, and the ions they contain are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and synthetic compounds can also be used.

[0166] Examples of clays, clay minerals, or ion-exchangeable layered compounds include clays, clay minerals, and ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl2 type, and CdI2 type.

[0167] Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchange layered compounds include crystalline acid salts of polyvalent metals such as α-Zr(HAsO)·H0, α-Zr(HPO), α-Zr(KPO 3H0, α-Ti(HPO), α-Ti(HAsO)·H0, α-Sn(HPO), H0, γ-Zr(HPO), γ-Ti(HPO,), and γ-Ti(NHPO).

[0168] Such clays, clay minerals, or ion-exchange layered compounds preferably have a pore volume of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, of pores with a radius of 20 Å or more measured by mercury intrusion porosimetry. Here, the pore volume is measured by mercury intrusion porosimetry using a mercury porosimeter, and is preferably 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g. 4 When a support having a pore volume of less than 0.1 cc / g with a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.

[0169] It is also preferable to subject clay and clay minerals to chemical treatment. Chemical treatments include surface treatments that remove impurities from the surface and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic 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 crystalline structure. Alkali treatment destroys the crystalline structure of the clay, resulting in structural changes. Furthermore, salt treatment and organic treatment form ionic complexes, molecular complexes, organic derivatives, etc., which can change the surface area and interlayer distance.

[0170] The ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with other large, bulky ions. Such bulky ions act as supports supporting the layered structure and are usually called pillars. 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 TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (R is a hydrocarbon group, etc.), and [Al 13 O4(OH) 24 ] 7+ , [Zr4(OH) 14 ] 2+ , [Fe3O(OCOCH3)6] + Examples of the metal hydroxide ions include those mentioned above. These compounds can be used alone or in combination of two or more. When intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, and colloidal inorganic compounds such as SiO2 can also be present. Examples of the pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them with heat.

[0171] The clay, clay mineral, and ion-exchange layered compound may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Further, they may be used after newly adsorbing water or after being subjected to heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more kinds.

[0172] 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 polymers mainly composed of olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or polymers and reactants mainly composed of vinylcyclohexane, styrene, and divinylbenzene, and granular or fine particulate solids composed of modified products thereof. As the solid carrier (S), a porous oxide is preferable from the viewpoint of preventing foreign matters during molding.

[0173] <Component (C)> The olefin polymerization catalyst (X) may preferably further contain a component (C). The component (C) is at least one compound selected from the group consisting of an organometallic compound (c-1) represented by the following general formulas (3) to (5), an organoaluminum oxy compound (c-2), and a compound (c-3) that reacts with the component (A) to form an ion pair.

[0174] 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 a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3.

[0175] M a ​a 4···(4) In formula (4), M a indicates Li, Na, or K, and R a represents a hydrocarbon group having 1 to 15 carbon atoms.

[0176] R a r M b R b s X t ···(5) In formula (5), R a and R b each independently represents a hydrocarbon group having 1 to 15 carbon atoms, M b is selected from Mg, Zn and Cd, X represents a halogen atom, and r is 0 <r≦2、sは0≦s≦1、tは0≦t≦1であり、かつr+s+t=2である。

[0177] Among the organometallic compounds (c-1), those represented by the formula (3) are preferred, specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and dimethylaluminum bromide; Alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide; Alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; alkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride, and di-sec-nonylaluminum hydride; Dialkylaluminum alkoxides such as dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, and diisobutylaluminum ethoxide Examples include:

[0178] Examples of the formula (4) include lithium aluminum hydride, and examples of the formula (5) include dialkylzinc compounds described in JP-A-2003-171412, and these can also be used in combination with phenol compounds.

[0179] The organoaluminum oxy compound (c-2) is preferably an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum, and particularly preferably an aluminoxane prepared from trimethylaluminum or triisobutylaluminum, such as methylaluminoxane. Such organoaluminum oxy compounds may be used alone or in combination of two or more.

[0180] Examples of the compound (c-3) that reacts with the component (A) to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds, as well as heteropoly compounds and isopoly compounds, as described in, for example, JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Pat. No. 5,321,106.

[0181] In the olefin polymerization catalyst (X), when an organoaluminum oxy compound such as methylaluminoxane is used in combination as a co-catalyst component, not only does the catalyst exhibit extremely high polymerization activity for olefin compounds, but also the co-catalyst component reacts with active hydrogen in the solid support to easily prepare a solid support component containing the co-catalyst component. For these reasons, it is preferable that component (C) contains at least an organoaluminum oxy compound (c-2).

[0182] <Instructions and order of addition of each ingredient> The olefin polymerization catalyst (X) can be prepared by mixing and contacting the components (A) and (S), and optionally the component (C), in an inert hydrocarbon.

[0183] As a method for contacting each component, when paying attention to the order of contact, for example, (i) A method of contacting component (S) with component (A). (ii) A method in which component (S) is contacted with component (C) and then with component (A). (iii) A method in which component (A) is contacted with component (C) and then with component (S). (iv) A method of contacting component (S) with component (C) and then contacting a mixture of component (A) and component (C); (v) A method of contacting component (S) with component (C), further contacting with component (C), and then contacting with 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. Of the above methods, (i), (ii) and (iii) are preferred.

[0184] In each of the methods showing the contact order form described above, in the step involving contact of component (S) with component (C) and the step involving contact of component (S) with component (A), the presence of component (G) suppresses fouling during the polymerization reaction and improves the particle properties of the resulting polymer. As component (G), a compound having a polar functional group can be used, and nonionic surfactants are preferred, with polyalkylene oxide blocks, higher aliphatic amides, polyalkylene oxides, polyalkylene oxide alkyl ethers, alkyldiethanolamines, polyoxyalkylene alkylamines, glycerin fatty acid esters, and N-acylamino acids being more preferred. These may be used alone or in combination of two or more.

[0185] The solvent used in preparing the olefin polymerization catalyst (X) may be an inert hydrocarbon solvent, and specific examples thereof include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof.

[0186] When components (C) and (S) are contacted, a reactive site in component (C) reacts with a reactive site in component (S) to chemically bond them, forming a contact product of components (C) and (S). The contact time between components (C) and (S) is typically 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is typically −50 to 200°C, preferably −20 to 120°C. If the initial contact between components (C) and (S) is rapid, the heat generated by the reaction and the reaction energy can cause component (S) to collapse, deteriorating the morphology of the resulting solid catalyst component. When used in polymerization, this can often result in poor polymer morphology, making continuous operation difficult. Therefore, it is preferable to initially contact components (C) and (S) at a lower temperature to suppress the heat generated by the reaction, or to control the heat generated by the reaction and react at a rate that maintains the initial contact temperature. This also applies when components (C) and (S) are first contacted and then component (C) is contacted. The contact weight ratio of component (C) to component (S) (weight of component (C) / weight of component (S)) can be selected arbitrarily, but a higher contact weight ratio allows a larger amount of component (A) to be contacted, thereby improving the catalytic activity per weight of the solid catalyst component.

[0187] The contact weight ratio of component (C) to 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 product of component (C) and component (S) is contacted with component (A), the contact time is usually 1 minute to 20 hours, preferably 1 minute to 10 hours, and the contact temperature is usually within the range of -50 to 200°C, preferably -50 to 100°C.

[0188] Component (C-1) is used in an amount such that the molar ratio of component (C-1) to the total transition metal atoms (M) in component (A) [(C-1) / M] is generally 0.01 to 100,000, preferably 0.05 to 50,000.

[0189] Component (C-2) is used in an amount such that the molar ratio [(C-2) / M] of component (C-2) (in terms of aluminum atoms) to the total transition metal atoms (M) in component (A) is generally 10 to 500,000, and preferably 20 to 100,000.

[0190] Component (C-3) is used in an amount such that the molar ratio of component (C-3) to the total transition metal atoms (M) in component (A) [(C-3) / M] is generally 1 to 10, preferably 1 to 5. The ratio of component (C) to the total transition metal atoms (M) in component (A) can be determined by inductively coupled plasma atomic emission spectrometry (ICP analysis). For ethylene polymerization, the olefin polymerization catalyst (X) can be used as is, but it can also be used after prepolymerizing an olefin on this olefin polymerization catalyst to form a prepolymerization catalyst (XP).

[0191] The prepolymerization catalyst (XP) can be prepared by prepolymerizing ethylene or the like in the presence of the olefin polymerization catalyst (X), usually in an inert hydrocarbon solvent, and can be carried out in any of a batch system, a semi-continuous system, and a continuous system, and can be carried out under reduced pressure, normal pressure, or increased pressure. Furthermore, it is desirable to produce the prepolymerization catalyst (XP) in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, and more preferably 0.2 to 500 g per 1 g of the solid catalyst component by prepolymerization.

[0192] The prepolymerized catalyst (XP) produced in the inert hydrocarbon solvent may be separated from the suspension and then resuspended in the inert hydrocarbon, and ethylene may be introduced into the resulting suspension. Alternatively, the suspension may be dried and then ethylene may be introduced.

[0193] 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. For the prepolymerization, an olefin containing ethylene as the main component is preferably used.

[0194] The form of the solid catalyst component used in the prepolymerization can be any of those already mentioned above without any limitations. If necessary, component (C) is used, and the organometallic compound (c-1) represented by the above formula (3) is preferably used. When component (C) is used, component (C) is used in an amount such that the molar ratio (Al / M) of the aluminum atom (Al) in component (C) to the transition metal atom (M) in component (A) is 0.1 to 10,000, preferably 0.5 to 5,000.

[0195] The concentration of the olefin polymerization catalyst (X) in the prepolymerization system is usually 1 to 1,000 g / L, preferably 10 to 500 g / L, in terms of the volume ratio of catalyst for olefin polymerization / polymerization. During the prepolymerization, the above-mentioned component (G) may be present together for the purpose of suppressing fouling or improving particle properties.

[0196] Furthermore, for the purpose of improving the fluidity of the prepolymerized catalyst (XP) and suppressing the occurrence of heat spots, sheeting, and polymer lumps during polymerization, the prepolymerized catalyst (XP) may be brought into contact with component (G) once produced by prepolymerization.

[0197] The temperature when contacting the component (G) 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 the olefin polymerization catalyst (X) is contacted with the component (G), the component (G) is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 0.4 to 5 parts by weight, per 100 parts by weight of the olefin polymerization catalyst (X).

[0198] The olefin polymerization catalyst (X) and component (G) can be mixed and contacted in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include those similar to 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 a "dried prepolymerized catalyst") can be used as the olefin polymerization catalyst (X). Drying of the prepolymerized catalyst (XP) is usually carried out after removing the hydrocarbon dispersant from the obtained suspension of the prepolymerized catalyst by filtration or the like.

[0199] The prepolymerized catalyst (XP) is dried by maintaining the prepolymerized catalyst (XP) at a temperature of 70°C or less, preferably in the range of 20 to 50°C, under a flow of inert gas. The amount of volatile components in the obtained dried prepolymerized catalyst is desirably 2.0% by weight or less, preferably 1.0% by weight or less. The amount of volatile components in the dried prepolymerized catalyst is better as it is smaller, and there is no particular lower limit, but in practice it is 0.001% by weight. The drying time is usually 1 to 48 hours, depending on the drying temperature.

[0200] The dry prepolymerized catalyst has excellent fluidity and can be stably supplied to a polymerization reactor. Furthermore, the use of the dry prepolymerized catalyst makes it possible to carry out stable polymerization because the solvent used for suspension does not need to be entrained in the gas-phase polymerization system.

[0201] [Method of producing ethylene polymer] Next, the method for producing an ethylene polymer according to the present invention will be described. An ethylene polymer is obtained by polymerizing (homopolymerizing or copolymerizing) ethylene in the presence of the above-mentioned olefin polymerization catalyst (X). By using the olefin polymerization catalyst (X), it is possible to efficiently produce a low-density ethylene copolymer having numerous long-chain branches, which has high polymerization activity, excellent moldability and mechanical strength. The ethylene polymer of the present invention refers to a polymer containing 10 mol % or more of ethylene.

[0202] In the present invention, polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method, but in the suspension polymerization method and the gas phase polymerization method, it is preferable to use the above-mentioned prepolymerization catalyst (XP).

[0203] Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, etc.; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, etc., and mixtures thereof. In the liquid phase polymerization method, the olefin itself can also be used as the solvent.

[0204] When ethylene is polymerized using the above olefin polymerization catalyst, component (A) is usually added in an amount of 1×10 per liter of reaction volume. -12 ~1×10 -1 mol, preferably 1 x 10 -8 ~1×10 -2 In addition, component (C) is used, and the organoaluminum compound represented by formula (3) in (c-1) is particularly preferably used.

[0205] 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., and particularly preferably 60 to 170° C. The polymerization pressure is usually in the range of normal pressure to 100 kgf / cm. 2 , preferably normal pressure to 50 kgf / cm 2 The polymerization reaction can be carried out in any of batch, semi-continuous and continuous systems. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0206] The molecular weight of the resulting polymer can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. Generally, the higher the amount of low-molecular-weight components, the greater the adhesion to the reactor walls and agitator blades, which can increase the burden on cleaning processes and reduce productivity. Component (G) can be present during polymerization to suppress fouling or improve particle properties.

[0207] In the present invention, the monomer supplied together with ethylene to the copolymerization reaction is 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. In addition, monomers other than ethylene and α-olefins having 4 to 10 carbon atoms may or may not be supplied within a range that does not impair the effects of the present invention.

[0208] <Method for producing high-pressure low-density polyethylene (B)> The high-pressure low-density polyethylene (B) used in the present invention is produced by polymerizing ethylene by high-pressure radical polymerization. For example, ethylene monomer is polymerized at a pressure of 500 to 3500 kgf / cm 2 The high-pressure low-density polyethylene (B) can be produced by radical polymerization using oxygen or an organic peroxide as a polymerization initiator in an autoclave or tubular reactor at a polymerization temperature in the range of 100 to 400°C. Commercially available high-pressure low-density polyethylenes can be used. Specific examples include Suntec (registered trademark) LD manufactured by Asahi Kasei Corporation, Mirason (registered trademark) manufactured by Mitsui Dow Polychemicals Co., Ltd., and Novatec (registered trademark) LD manufactured by Japan Polyethylene Co., Ltd., which satisfy requirements (a) to (c) and, optionally, requirement (d).

[0209] The high-pressure low-density polyethylene (B) may contain structural units derived from biomass-derived ethylene. The ethylene constituting the polymer may be solely biomass-derived ethylene, solely fossil fuel-derived ethylene, or both biomass-derived ethylene and fossil fuel-derived ethylene. Biomass-derived ethylene is a monomer obtained from any renewable natural raw material or its residue, such as a plant-derived or animal-derived material, including fungi, yeast, algae, and bacteria, and contains 1×10 14C isotope as carbon. -12The 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 from the viewpoint of reducing the environmental load that the high-pressure low-density polyethylene (B) contains a structural unit derived from a biomass-derived monomer.

[0210] <Method for producing ethylene-based resin composition (Z)> The ethylene-based resin composition (Z) can be produced by melt-kneading the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B), or by dry-blending pellets of the ethylene-α-olefin copolymer (A) with pellets of the high-pressure low-density polyethylene (B). When produced by melt-kneading, a continuous extruder or an internal kneader can be used. Examples of suitable devices include a single-screw extruder, a twin-screw extruder, a mixing roll, a Banbury mixer, and a kneader. Of these, it is preferable to use a single-screw extruder and / or a twin-screw extruder from the viewpoints of economy, processing efficiency, and the like.

[0211] When the melt-kneading and dry-blending are carried out, the "other thermoplastic resin" may be blended in addition to the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). In addition to the "other thermoplastic resin," or instead of the "other thermoplastic resin," the "additive" may be further blended.

[0212] The order of adding the "other thermoplastic resin" and the "additive" is not particularly limited. For example, the "other thermoplastic resin" and the "additive" may be blended simultaneously with one or both of the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B), or may be added after kneading the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B).

[0213] [Molded body, film, laminate] By processing the ethylene resin composition (Z) of the present invention, a molded article having excellent moldability and mechanical strength, preferably a film, and more preferably a laminate comprising the film, can be obtained.

[0214] The ethylene-based resin composition (Z) of the present invention can be processed by general film molding, sheet molding, blow molding, injection molding, extrusion molding, etc. Film molding methods include extrusion lamination molding, T-die film molding, and inflation molding (air cooling, water cooling, multi-stage cooling, high-speed processing). The obtained film can be used as a single layer, but by forming it into a multilayer, various additional functions can be imparted. Examples of molding methods used in this case include coextrusion. On the other hand, lamination molding methods such as extrusion lamination molding and dry lamination can be used to laminate with paper or barrier films (aluminum foil, vapor-deposited film, coating film, etc.) that are difficult to coextrude. The production of high-performance products by multilayering using blow molding, injection molding, and extrusion molding and coextrusion is possible, just like film molding.

[0215] Examples of molded articles obtained by processing the ethylene-based resin composition (Z) of the present invention include films, sheets, blown infusion bags, blown bottles, gasoline tanks, extrusion-molded tubes, pipes, electric wire coatings, tear-off caps, injection-molded articles such as daily necessities, fibers, and large-sized rotational moldings.

[0216] Furthermore, films obtainable by processing the ethylene-based resin composition (Z) of the present invention are suitable for various packaging films such as packaging bags for liquids, liquid soup bags, liquid paper containers, laminated raw materials, specially shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy-duty bags, cling film, sugar bags, oily food packaging bags, food packaging films, protective films, infusion bags, agricultural materials, bag-in-boxes, clean films used for packaging semiconductor materials, pharmaceuticals, foods, etc. The above films can also be used as multilayer films by being bonded to a substrate such as nylon, polyester, or polyolefin film.

[0217] 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-mentioned layers that make up the laminate include a substrate layer and a barrier layer.

[0218] Examples of substrates used as the substrate layer include films of polyamide, polyester, polypropylene, polyethylene, ethylene-vinyl alcohol copolymer, etc. The film is preferably a stretched film. Other examples include paper substrates and paper substrates coated with polyethylene. These substrates may be printed or coated as needed. Furthermore, they may be pretreated as needed with various pretreatments such as corona treatment, flame treatment, plasma treatment, ultraviolet treatment, and anchor coating treatment.

[0219] Specific examples of the substrate include paper such as fine paper, kraft paper, tissue paper, and Kent paper, cellophane, woven fabric, nonwoven fabric, nylon-based substrates such as oriented nylon, unoriented nylon, special nylon (MXD6, etc.), and K-nylon (polyvinylidene fluoride coated), polypropylene-based substrates such as oriented PET (polyethylene terephthalate), unoriented PET (polyethylene terephthalate), K-PET (polyethylene terephthalate), oriented polypropylene (OPP), unoriented polypropylene (CPP), K-PP, and co-extruded PP film, LDPE film, LLDPE film, EVA film, oriented LDPE film, and oriented HDPE film.

[0220] Barrier substrates used as barrier layers include metal foils, thermoplastic resin films vapor-deposited with metals or inorganic materials, and thermoplastic resin films with barrier coatings. Thermoplastic resin films include oriented nylon, oriented polyethylene terephthalate (PET), oriented polypropylene (OPP), and non-oriented polypropylene (CPP).

[0221] A part of the raw materials of the laminate, such as the substrate and the barrier substrate, may contain an ethylene-based polymer or a propylene-based polymer containing a biomass-derived monomer. In the present invention, metal foil refers to metal foil such as aluminum, gold, silver, iron, copper, nickel, or an alloy containing any of these as a main component. Metal-vapor-deposited thermoplastic resin film refers to a film in which a metal such as aluminum or silicon is vapor-deposited on the surface of a film such as polyester or polyamide. Inorganic-vapor-deposited thermoplastic resin film refers to a thermoplastic resin film in which silica or alumina is vapor-deposited. Barrier coating refers to coating a film surface with a barrier resin such as polyvinyl alcohol or polyvinylidene chloride.

[0222] The substrate layer is used, for example, as a printing substrate, whereas the barrier substrate is not typically used as a printing substrate. Specific examples of the laminate structure of the present invention are shown below, but the present invention is not limited to these.

[0223] In the following compositions, PE laminate means that an ethylene-based resin is laminated by extrusion lamination. The ethylene-based resin used in at least one PE laminate in each composition is the ethylene-based resin composition (Z) of the present invention.

[0224] When a PE laminate using the ethylene-based resin composition (Z) of the present invention is used as an adhesive layer adjacent to the aluminum vapor-deposited layer or aluminum foil of an aluminum vapor-deposited film, the PE laminate has excellent adhesive strength to the aluminum vapor-deposited layer or aluminum foil.

[0225] Coextrusion lamination (acid copolymer / PE laminate) refers to the lamination of two layers of an acid copolymer and an ethylene-based resin by coextrusion lamination, with the acid copolymer adjacent to the aluminum foil. Examples of acid copolymers include ethylene-acrylic copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), and ethylene-acrylic acid ester copolymer (EEA, EMA, EMMA, etc.). The film used for the innermost layer (opposite the stretched substrate film) is a thermoplastic resin film, and a propylene-based resin film or an ethylene-based resin film is preferred.

[0226] Stretched nylon / adhesive / PE lamination (1) / PE lamination (2), Paper / PE laminate, Oriented polypropylene / adhesive / PE laminate (1) / aluminum foil / adhesive / film or PE laminate (2), Stretched polypropylene / adhesive / PE lami (1) / aluminum vapor deposition film (the aluminum vapor deposition layer is adjacent to the PE lami (1) layer), Oriented polypropylene / adhesive / PE lami (1) / aluminum vapor deposition film / adhesive / film or PE lami (2) (the aluminum vapor deposition layer is adjacent to the PE lami (1) layer), Stretched polypropylene / adhesive / extrusion lamination (1) / inorganic vapor deposition film, Oriented polypropylene / adhesive / PE laminate (1) / inorganic vapor deposition film / adhesive / film or PE laminate (2), Stretched polyethylene terephthalate / adhesive / extrusion lamination (1) / aluminum foil / adhesive / film or PE lamination (2), Stretched polyethylene terephthalate / adhesive / extrusion laminate (1) / aluminum vapor deposition film / adhesive / film or PE laminate (2) (the aluminum vapor deposition layer is adjacent to the PE laminate (1) layer), Stretched polyethylene terephthalate / adhesive / PE lamination (1) / inorganic vapor deposition film, Stretched polyethylene terephthalate / adhesive / PE laminate (1) / inorganic vapor deposition film / adhesive / film or PE laminate (2), PE laminate (1) / paper / PE laminate (2) / aluminum foil / co-extrusion laminate (acid copolymer / PE laminate (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 deposition film / adhesive / film or PE laminate (3), PE laminate (1) / Paper / PE laminate (2) / Inorganic vapor deposition film / Adhesive / Film or PE laminate (3) [Example]

[0227] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to the following examples.

[0228] [Measurement or evaluation method] In the following examples, various physical properties of ethylene-α-olefin copolymers and the like were measured by the methods described in [Mode for Carrying Out the Invention], and the following methods were used as evaluation methods not described in [Mode for Carrying Out the Invention].

[0229] Extrusion Laminate Evaluation : [Neck-in] The ethylene-based resin composition was laminated on a substrate of 50 g / m2 using a laminator manufactured by Sumitomo Heavy Industries, Ltd., equipped with a 65 mmφ extruder and a T-die with a die width of 500 mm. 2 The laminate was extrusion laminated onto kraft paper under the following conditions.

[0230] Air gap: 130mm Resin temperature below the die: 320℃ Take-up speed: 80m / min Film thickness: 20 μm When the width of the T-die is L0 and the width of the film laminated on the kraft paper at each take-up speed is L, the neck-in was calculated by L0 - L.

[0231] [Pick-up surging] The ethylene-based resin composition was laminated on a substrate of 50 g / m2 using a laminator manufactured by Sumitomo Heavy Industries, Ltd., equipped with a 65 mmφ extruder and a T-die with a die width of 500 mm. 2 The film was extrusion laminated onto kraft paper at an air gap of 130 mm and a resin temperature below the die of 320°C. The extrusion rate was set so that the film thickness would be 20 μm at a take-up speed of 80 m / min. The take-up speed was increased, and neck-in was measured five times at a take-up speed of 150 m / min. If two or more measurements showed a difference of ±1.5 mm from the average neck-in value, take-up surging was deemed to have occurred.

[0232] [Aluminum adhesive strength ratio] The ethylene-based resin composition was extrusion laminated between the substrate and the aluminum vapor-deposited film to a thickness of 15 μm using a laminator manufactured by Sumitomo Heavy Industries, Ltd., equipped with a 65 mm diameter extruder and a 500 mm wide T-die, under conditions of a resin temperature below the die of 320°C and a take-up speed of 150 m / min. The substrate was a 12 μm thick stretched polyethylene terephthalate film (trade name: Emblett®, manufactured by Unitika Ltd.) coated on one side (the ethylene-based resin composition layer side) with a two-component curing urethane anchor coating agent. The aluminum vapor-deposited film was a 12 μm thick ML PET (manufactured by Mitsui Chemicals Tohcello, Inc.). The extrusion-laminated ethylene-based resin composition was in contact with the aluminum surface. The resulting extrusion-laminated film was cut into 15 mm wide strips, and the adhesive strength between the resulting ethylene-based resin composition layer and the aluminum vapor-deposited film layer was measured by T-peel at a peel speed of 300 mm / min. The ratio of the determined peel strength to the peel strength (LDPE) determined in the same manner using high-pressure LDPE (high-pressure low-density polyethylene, Suntec (registered trademark)-LD "L1850A" manufactured by Asahi Kasei Corporation) instead of the ethylene-based resin composition was defined as the AL adhesive strength ratio. AL adhesive strength ratio = peel strength / peel strength (LDPE)

[0233] [Trouser tear strength] The ethylene-based resin composition was extrusion laminated onto a 50 g / m kraft paper substrate to a film thickness of 20 μm using a laminator manufactured by Sumitomo Heavy Industries, Ltd., equipped with a 65 mmφ extruder and a 500 mm wide T-die, under conditions of an air gap of 130 mm, a resin temperature below the die of 320°C, and a take-up speed of 80 m / min. The resulting laminate was cut into a piece 50 mm wide and 150 mm long, a 75 mm slit was made in the center of the width, and the tear strength was measured at a speed of 200 mm / min according to JIS K7128-1.

[0234] [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 [synthesized by the method described in JP 2019-059933 A.] 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] Ingredient (G-1): Lauryldiethanolamine (Kao Corporation) Ingredient (G-2): Emulgen (registered trademark) 108 (Kao Corporation)

[0235] <Synthesis of prepolymerization catalyst (XP-1)> A 270 L reactor equipped with a stirrer was placed under a nitrogen atmosphere using silica (average particle size 70 μm, specific surface area 340 m) manufactured by Fuji Silysia Ltd. as a solid carrier (S). 2 / g, pore volume 1.3cm 310 kg of methylaluminoxane (3.5 mol / L in terms of Al atoms, calcined at 250°C) was suspended in 77 L of toluene and then cooled to 0-5°C. 20.4 L of a toluene solution of methylaluminoxane (component (C)) (3.5 mol / L in terms of Al atoms) was added dropwise to this suspension over 30 minutes. The temperature of the system was maintained at 0-5°C. After the reaction was continued at 0-5°C for 30 minutes, the temperature was raised to 95-100°C over approximately 1.5 hours and then continued at 95-100°C for 4 hours. The temperature was then lowered to room temperature, the supernatant liquid was removed by decantation, and the mixture was washed twice with toluene to prepare a toluene slurry with a total volume of 58.0 L. A portion of the resulting slurry component was sampled and its concentration was examined; the slurry concentration was 248.0 g / L and the Al concentration was 1.21 mol / L.

[0236] Next, 6.1 L of the toluene slurry obtained above and 21.9 L of toluene were charged into a 114 L reactor equipped with a stirrer and thoroughly purged with nitrogen. 5.4 L of an 8 mM toluene solution of transition metal compound (A-1) was added, and the mixture was allowed to contact for 1 hour at a system temperature of 20 to 25 ° C. After the supernatant was removed by decantation and the mixture was washed twice with hexane, a total volume of 30.9 L of slurry was prepared. While adjusting the temperature of the resulting slurry to 10 to 15 ° C, 3.1 L of a 0.92 M hexane solution of diisobutylaluminum hydride was added, and ethylene gas was started at a flow rate of 0.74 kg / hr. After adding 34.3 mL of 1-hexene, the temperature was increased. While adjusting the system temperature to 32 to 38 ° C, 34.3 mL of 1-hexene was added every hour for a total of five times. 6 hours after the start of ethylene supply, the ethylene supply was stopped when the ethylene supply amount reached 4.5 kg. The system was then thoroughly purged with nitrogen, the supernatant was removed by decantation, and the mixture was washed four times with hexane to prepare a total volume of 21.9 L of slurry. While maintaining the resulting slurry at 35–40°C, 6.1 L of a 10 g / L hexane solution of component (G-1) was added and allowed to contact for 2 hours. The entire resulting slurry was placed in a 43 L internal volume evaporator equipped with a stirrer under a nitrogen atmosphere. The pressure inside the evaporator was reduced to −68 kPaG over approximately 60 minutes. Once the pressure reached −68 kPaG, the mixture was vacuum dried for approximately 4.3 hours to remove hexane and volatiles from the prepolymerized catalyst components. The pressure was further reduced to −100 kPaG, and once the pressure reached −100 kPaG, the mixture was vacuum dried for 8 hours to obtain 6.2 kg of prepolymerized catalyst (XP-1). A portion of the resulting prepolymerized catalyst (XP-1) was sampled and its composition was analyzed, revealing that it contained 0.56 mg of Zr atoms per gram of prepolymerized catalyst components.

[0237] <Synthesis of prepolymerization catalyst (XP-2)> A 270 L reactor equipped with a stirrer was placed under a nitrogen atmosphere using silica (average particle size 70 μm, specific surface area 340 m) manufactured by Fuji Silysia Ltd. as a solid carrier (S). 2 / g, pore volume 1.3cm 310 kg of methylaluminoxane (3.5 mol / L in terms of Al atoms, calcined at 250°C) was suspended in 77 L of toluene and then cooled to 0-5°C. 20.4 L of a toluene solution of methylaluminoxane (component (C)) (3.5 mol / L in terms of Al atoms) was added dropwise to this suspension over 30 minutes. The temperature of the system was maintained at 0-5°C. After the reaction was continued at 0-5°C for 30 minutes, the temperature was raised to 95-100°C over approximately 1.5 hours and then continued at 95-100°C for 4 hours. The temperature was then lowered to room temperature, the supernatant liquid was removed by decantation, and the mixture was washed twice with toluene to prepare a toluene slurry with a total volume of 58.0 L. A portion of the resulting slurry component was sampled and its concentration was examined; the slurry concentration was 248.0 g / L and the Al concentration was 1.21 mol / L.

[0238] Next, 6.1 L of the toluene slurry obtained above and 22.7 L of toluene were charged into a 114 L reactor equipped with a stirrer and thoroughly purged with nitrogen. 1.5 L of an 8 mM toluene solution of transition metal compound (B-1) and 3.1 L of an 8 mM toluene solution of transition metal compound (B-2) were added, and the mixture was allowed to react at a system temperature of 70-75 °C for 1 hour. The supernatant was then removed by decantation, and the mixture was washed twice with hexane to prepare a total volume of 29.8 L of slurry. The resulting slurry was adjusted to 35-40 °C, and 4.0 L of a 0.92 M hexane solution of diisobutylaluminum hydride was added. Ethylene gas was then supplied at a flow rate of 795.4 L / hr. Five hours after the start of ethylene supply, the ethylene supply was stopped when the ethylene supply reached 3,980 L. The system was then thoroughly purged with nitrogen, the supernatant was removed by decantation, and the mixture was washed four times with hexane to prepare a 21.7 L slurry. While maintaining the resulting slurry at 35-40°C, 3.8 L of a 10 mg / mL hexane solution of component (G-2) was added and allowed to react for 2 hours. The entire resulting slurry was placed in a 43 L agitator-equipped evaporator under a nitrogen atmosphere. The pressure inside the evaporator was reduced to -68 kPaG over approximately 60 minutes. Once the pressure reached -68 kPaG, the mixture was vacuum dried for approximately 4.3 hours to remove hexane and volatiles from the prepolymerized catalyst components. The pressure was further reduced to -100 kPaG, and once the pressure reached -100 kPaG, the mixture was vacuum dried for 8 hours to obtain 6.1 kg of prepolymerized catalyst (XP-2). A portion of the resulting prepolymerized catalyst (XP-2) was sampled and its composition was analyzed, revealing that it contained 0.52 mg of Zr atoms per gram of prepolymerized catalyst components.

[0239] <Production of ethylene-α-olefin copolymer> [Manufacturing Example 2] (Production of ethylene-α-olefin copolymer (A-2)) An ethylene polymer was produced by a gas-phase polymerization process using a fluidized-bed gas-phase polymerization reactor. 24 kg of spherical ethylene polymer particles with an average particle size of 900 μm was introduced into the reactor in advance, and nitrogen was supplied to form a fluidized bed. Ethylene, hydrogen, 1-hexene, a prepolymerization catalyst, and Electrostripper (registered trademark) EA (Kao Corporation) were then continuously supplied to achieve a steady state under the polymerization conditions shown in Table 8. The polymerization product was continuously withdrawn from the reactor and dried in a dryer to obtain a powder of ethylene-α-olefin copolymer (A-2).

[0240] [Manufacturing 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 in Production Example 2, except that the polymerization conditions were changed as shown in Table 8. Table 8 lists Chemistat (registered trademark) 2500 (manufactured by Sanyo Chemical Industries, Ltd.) as a component that was not used in Production Example 2.

[0241] [Manufacturing Example 1] (Production of ethylene-α-olefin copolymer (A-1)) An ethylene polymer was produced by a two-stage polymerization process using the fluidized-bed gas-phase polymerization reactor used in Production Example 2 as the upstream reactor and a fluidized-bed gas-phase polymerization reactor with an internal volume of 0.6 m3 as the downstream reactor. Two-stage polymerization refers to the continuous withdrawal of the polymerization product obtained in the upstream polymerization reactor into the downstream polymerization reactor, with the upstream polymerization reaction continuing in the downstream polymerization reactor. 24 kg of spherical ethylene polymer particles with an average particle size of 900 μm were introduced into the upstream polymerization reactor. Nitrogen was supplied to form a fluidized bed. Ethylene, hydrogen, 1-hexene, a prepolymerization catalyst, and an electrostripper EA were continuously supplied to both the upstream and downstream polymerization reactors so that a steady state was achieved under the polymerization conditions shown in Table 8. However, the prepolymerization catalyst and electrostripper EA were supplied only to the upstream polymerization reactor. The polymerization product obtained by the two-stage polymerization in the latter-stage polymerization reactor was continuously withdrawn from the latter-stage polymerization reactor and dried in a dryer to obtain an ethylene-α-olefin copolymer powder.

[0242] [Manufacturing Examples 5, 8-10] (Production of Ethylene-α-Olefin Copolymers (A-5), (A-8) to (A-10)) 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.

[0243] <Measurement of polymer properties> [Ethylene-α-olefin copolymer (A-1)] The powder of ethylene-α-olefin copolymer (A-1) obtained in Production Example 1 was melt-kneaded using a 46 mm diameter twin-screw co-rotating extruder manufactured by Ikegai Corporation at a set temperature of 200°C and a screw rotation speed of 300 rpm, then extruded into a strand shape and cut to obtain pellets. The obtained pellets were used as measurement samples and their physical properties were measured. The measurement results are shown in Table 9.

[0244] [Ethylene-α-olefin copolymers (A-2) to (a-16)] Pellets were prepared and their properties were measured in the same manner as in the measurement of the physical properties of the ethylene-α-olefin copolymer (A-1), except that the ethylene-α-olefin copolymer (A-1) was replaced with any of the ethylene-α-olefin copolymers (A-2) to (a-16) obtained in Production Examples 2 to 16. The measurement results are shown in Table 9.

[0245] [Ethylene-α-olefin copolymer (a-17)] The physical properties of Ultzex ​​15150J manufactured by Prime Polymer Co., Ltd. were measured. The measurement results are shown in Table 9.

[0246] [High-pressure low-density polyethylene (B-1)] The physical properties of Suntech-LD "L1850A" manufactured by Asahi Kasei Corporation were measured. The measurement results are shown in Table 10.

[0247] [High-pressure low-density polyethylene (b-2)] The physical properties of Suntech-LD "M1920" manufactured by Asahi Kasei Corporation were measured. The measurement results are shown in Table 10.

[0248] <Production of ethylene-based resin composition> [Example 1] The pellets of the obtained ethylene-α-olefin copolymer (A-1) were dry-blended with 75% by mass of the pellets of the high-pressure low-density polyethylene (B-1) at 25% by mass, and then subjected to extrusion lamination evaluation. The evaluation results are shown in Table 11.

[0249] [Example 2] 50% by mass of the pellets of the obtained ethylene-α-olefin copolymer (A-1) and 50% by mass of the pellets of the high-pressure low-density polyethylene (B-1) were dry-blended, and then subjected to extrusion lamination evaluation. The evaluation results are shown in Table 11.

[0250] [Example 3] 75% by mass of the pellets of the obtained ethylene-α-olefin copolymer (A-2) and 25% by mass of the pellets of the high-pressure low-density polyethylene (B-1) were dry-blended, and then subjected to extrusion lamination evaluation. The evaluation results are shown in Table 11.

[0251] [Example 4] 50% by mass of the pellets of the obtained ethylene-α-olefin copolymer (A-2) and 50% by mass of the pellets of the high-pressure low-density polyethylene (B-1) were dry-blended, and then subjected to extrusion lamination evaluation. The evaluation results are shown in Table 11.

[0252] [Example 5] 50% by mass of the pellets of the obtained ethylene-α-olefin copolymer (A-3) and 50% by mass of the pellets of the high-pressure low-density polyethylene (B-1) were dry-blended, and then subjected to extrusion lamination evaluation. The evaluation results are shown in Table 11.

[0253] [Comparative Example 1] 75% by mass of pellets of ethylene-α-olefin copolymer (a-17) and 25% by mass of pellets of high-pressure low-density polyethylene (B-1) were dry-blended, and extrusion lamination evaluation was performed. The evaluation results are shown in Table 11.

[0254] Comparative Example 2 75% by mass of pellets of ethylene-α-olefin copolymer (a-17) and 25% by mass of pellets of high-pressure low-density polyethylene (b-2) were dry-blended, and extrusion lamination evaluation was performed. The evaluation results are shown in Table 11.

[0255] Comparative Example 3 Using high-pressure low-density polyethylene (B-1), extrusion lamination evaluation was carried out. The evaluation results are shown in Table 11.

[0256] Comparative Example 4 The pellets of the ethylene-α-olefin copolymer (a-16) were used to perform extrusion lamination evaluation. The evaluation results are shown in Table 11.

[0257]

Table 8-1

[0258]

Table 8-2

[0259]

Table 9-1

[0260]

Table 9-2

[0261]

Table 10

[0262]

Table 11

Claims

1. The present invention comprises 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 a high-pressure low-density polyethylene (B) which satisfies the following requirements (a) to (c), The mass fraction (W A ) is 40% by mass or more and 90% by mass or less, and the mass fraction (W B ) is 10 mass % or more and 60 mass % or less (provided that W A and W B The total of these is 100% by mass.) Ethylene-based resin composition (Z). (1) Density is 890 kg / m 3 More than 935kg / m 3 It is in the following range: (2) The melt flow rate (MFR) at 190° C. under a load of 2.16 kg is in the range of 1.0 g / 10 min or more and 15.0 g / 10 min or less. (3) Melt tension [MT (g)] at 190 ° C. and shear viscosity [η * (P)] and the ratio [MT / η * (g / P)] is 1.40 × 10 -4 The above is 2.90 x 10 -4 It is in the following range: (4) Zero shear viscosity at 200 ° C [η 0 (P)] and the weight average molecular weight (Mw) measured by a 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 a GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-2): -2.0 ≦ Mz / Mw - Mw / Mn ≦ 15 ... (Eq-2) (6) 1 The total of vinyl, vinylidene, di-substituted internal olefin, and tri-substituted internal olefin per 1000 carbon atoms (units / 1000C) measured by H-NMR is in the range of 0.1 to 1.

0. (a) Density is 915 kg / m 3 More than 930kg / m 3 It is in the following range: (b) The melt flow rate (MFR) at 190°C under a load of 2.16 kg is in the range of 0.1 g / 10 min or more and 20 g / 10 min or less. (c) The amount of components having a molecular weight of 1,000,000 or more in a molecular weight distribution curve obtained by GPC measurement is in the range of 1.0% to 20%.

2. The ethylene-based resin composition (Z) according to claim 1, wherein the ethylene-α-olefin copolymer (A) further satisfies the following requirement (7): (7) The intrinsic viscosity [η] (dl / g) measured in decalin at 135°C and the weight average molecular weight (Mw) measured by a GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-3): 0.7×10 -4 ×Mw 0.776 ≦[η]≦ 1.65×10 -4 ×Mw 0.776 ・・・(Eq-3)

3. The ethylene-based 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 the Z-average molecular weight (Mz) to the weight-average molecular weight (Mw) measured by a GPC-viscosity detector method (GPC-VISCO) is in the range of 4.0 to 25.

0.

4. The ethylene-based 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) There are multiple peaks in the melting curve obtained by differential scanning calorimetry (DSC).

5. The ethylene-based 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) The ratio [δ100 / δ0.01] of the phase angle [δ100 (°)] at 200°C and an angular velocity of 100 rad / sec to the phase angle [δ0.01 (°)] at 200°C and an angular velocity of 0.01 rad / sec is in the range of 0.46 or more and 0.76 or less.

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

7. A molded article comprising the ethylene-based resin composition (Z) according to any one of claims 1 to 6.

8. A film comprising the ethylene-based resin composition (Z) according to any one of claims 1 to 6.

9. A multilayer film having a layer comprising the ethylene-based resin composition (Z) according to any one of claims 1 to 6.

10. A laminate having a layer comprising the ethylene-based resin composition (Z) according to any one of claims 1 to 6.

11. The laminate according to claim 10, further comprising a substrate layer.

12. The laminate according to claim 10, further comprising a barrier layer.

13. A method for producing a laminate, comprising extrusion laminating the ethylene-based resin composition (Z) according to any one of claims 1 to 6 between a substrate layer and a barrier layer.

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