Ethylene-alpha-olefin copolymer, thermoplastic resin composition, film, and laminate

Abstract

The present invention provides an ethylene-α-olefin copolymer which is excellent in moldability and particularly excellent in mechanical strength compared with the prior art. The copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms satisfies the following conditions (1) to (7). (1) The density is 890 to 925 kg / m 3 ; (2) The MFR (190°C, 2.16 kg load) is 3.0 to 15.0 g / 10 minutes; (3) The MT (melt tension) / η * (shear viscosity) is 1.40 x 10 ‑4 to 2.90 x 10 ‑4 g / P; (4) 0.01 x 10 ‑13 x Mw 3.4 ≤ η0 (zero shear viscosity) ≤ 4.5 x 10 ‑13 x Mw 3.4 ; (5) -2.0 ≤ Mz / Mw - Mw / Mn ≤ 15; (6) The number of ethylene groups and the like is 0.1 to 1.0 per 1000C; and (7) The DSC melting curve has multiple peaks.

Description

TECHNICAL FIELD

[0001] The present application relates to an ethylene-α-olefin copolymer and a thermoplastic resin composition containing the same, and a film comprising the same, a laminate comprising the film. BACKGROUND

[0002] Ethylene-based polymers are used in a variety of molding methods and uses, and depending on the molding method and use, various properties are required for the ethylene-based polymers. For example, a neck-in phenomenon in which the film end portion is retracted toward the center occurs in T-die molding. Once the neck-in occurs, the film width becomes small, and the film end portion becomes thicker than the film center portion. Therefore, if the neck-in is large, the yield of the product becomes poor, or a product of the intended width cannot be produced. In hollow molding, sometimes, a poor situation such as a melt film sagging or breaking occurs, and in blow molding, sometimes, a poor situation such as a melt film being unstable or breaking occurs. In order to avoid these poor situations, an ethylene-based polymer having a large melt tension with respect to the molecular weight needs to be selected.

[0003] In addition, in T-die molding, sometimes, a regular thickness variation in the draw direction of the film, which is called draw resonance, occurs, and the mechanical strength can deviate at each thickness unevenness of the film. It can be considered that in order to stably produce a film having a uniform film thickness, the draw resonance must be avoided, but for this, a resin property in which the strain hardening degree of the elongational viscosity increases with an increase in the strain rate is required.

[0004] An ethylene-based polymer obtained using a metallocene catalyst, which has no long chain branch, has excellent mechanical strength, but has a problem in moldability. For example, the neck-in increases in T-die molding, or the draw resonance occurs. A high-pressure low-density polyethylene has a large melt tension, and has excellent moldability in terms of the neck-in and the like, and the elongational viscosity shows a strain rate hardening property, and the draw resonance does not occur. However, the high-pressure low-density polyethylene has a complex long chain branch structure, and thus has poor mechanical strength such as tensile strength, tear strength, or impact resistance.

[0005] In order to solve such a problem, various ethylene-based polymers into which a long chain branch is introduced have been developed. Patent Literature 1 proposes a composition of an ethylene-based polymer obtained using a metallocene catalyst and a high-pressure low-density polyethylene. However, in a case where the content of the high-pressure low-density polyethylene is large, it is expected that the mechanical strength such as the tensile strength, the tear strength, or the impact resistance is poor, and in a case where the content of the high-pressure low-density polyethylene is small, it is expected that the moldability in terms of the neck-in and the like is poor due to an insufficient increase in the melt tension.

[0006] Further, Patent Literature 2 discloses an ethylene-based polymer obtained by solution polymerization in the presence of a catalyst composed of ethylenebis(indenyl)hafnium dichloride and methylaluminoxane; Patent Literature 3 discloses an ethylene-based polymer obtained by gas phase polymerization in the presence of a catalyst composed of ethylenebis(indenyl)zirconium dichloride supported on silica and methylaluminoxane; Patent Literature 4 discloses an ethylene-based polymer obtained by solution polymerization in the presence of a constrained geometry catalyst; and Patent Literature 5 discloses an ethylene-based polymer obtained by gas phase polymerization in the presence of a catalyst composed of racemic and meso isomers of Me2Si(2-Me-Ind)2 supported on silica and methylaluminoxane. It is described that these ethylene-based polymers have improved melt tension and excellent moldability as compared with linear ethylene-based polymers having no long chain branching, but the shrinkage is still large, and thus it is expected that they are not sufficient in terms of improvement of moldability. Further, these ethylene-based polymers, unlike high-pressure low-density polyethylene, do not exhibit strain rate solidification in elongational viscosity, and thus it is expected that draw resonance is not improved.

[0007] Patent Literatures 6, 7, 8 and 9 disclose ethylene-based polymers or ethylene-based resin compositions in which the intrinsic viscosity and the weight average molecular weight satisfy a specific relationship, or 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-based polymers have improved draw resonance, and the shrinkage in T-die molding or the blow molding property is improved as compared with existing ethylene-based polymers into which long chain branching is introduced using a metallocene catalyst. However, further improvement of mechanical strength or improvement of transparency is still desired. Although the external haze is high due to slight unevenness on the surface of the film, and thus the blocking resistance is excellent, a film having excellent transparency is still desired from the viewpoint of recognition of contents and inspection of defects in the film. Also, in the case where the ethylene-based polymer is used as a bottle or the like, transparency is also similarly required.

[0008] Prior Art Documents

[0009] Patent Literature

[0010] Patent Literature 1: Japanese Patent Application Laid-Open (JP-A) No. 7-26079

[0011] Patent Literature 2: Japanese Patent Application Laid-Open (JP-A) No. 2-276807

[0012] Patent Literature 3: Japanese Patent Application Laid-Open (JP-A) No. 4-213309

[0013] Patent Literature 4: International Publication No. 93 / 08221

[0014] Patent Literature 5: Japanese Patent Application Laid-Open (JP-A) No. 8-311260

[0015] Patent Document 6: Japanese Patent Application Publication No. 2006-233207

[0016] Patent Document 7: Japanese Patent Application Publication No. 2009-197225

[0017] Patent Document 8: International Publication No. 2013 / 099927

[0018] Patent Document 9: Japanese Patent Application Publication No. 2014-177506 Summary of the Invention

[0019] The technical problem that the invention aims to solve

[0020] The object of the present invention is to provide an ethylene-α-olefin copolymer with excellent formability and capable of forming films with particularly superior mechanical strength compared to known ethylene-based polymers, a thermoplastic resin composition containing the polymer, and films and laminates obtained from the polymer or the thermoplastic resin composition.

[0021] Another object of the present invention is to provide an ethylene resin composition capable of manufacturing molded articles (e.g., films and multilayer films having the films) with excellent transparency, and molded articles (e.g., films and multilayer films having the films) obtained from the ethylene resin composition.

[0022] Technical means for solving technical problems

[0023] The inventors of this invention conducted in-depth research and, by endowing the polymer with specific melting characteristics and molecular structure, discovered an ethylene-α-olefin copolymer that does not experience pulling fluctuations during T-die molding, has small shrinkage, and exhibits particularly excellent mechanical strength, thus completing this invention.

[0024] Furthermore, it was discovered that a composition containing two ethylene-based polymers with specific melting properties and molecular structures can produce molded articles (e.g., films and multilayer films having such films) with excellent melt film stability, excellent mechanical strength, and excellent transparency during blow molding, thereby completing the ethylene-based resin composition (Z) of the present invention.

[0025] The present invention relates, for example, to the following [1] to

[16] .

[0026] [1] An ethylene-α-olefin copolymer (A) is a copolymer of ethylene and α-olefins having 4 to 10 carbon atoms, wherein the ethylene-α-olefin copolymer (A) satisfies the following conditions (1) to (7).

[0027] (1) Density is 890 kg / m³ 3 Above 925kg / m 3 Within the following range.

[0028] (2) The melt flow rate (MFR) at 190°C under a load of 2.16 kg is in the range of 3.0 g / 10 min. or more and 15.0 g / 10 min. or less.

[0029] (3) The ratio (MT / η (g / P)) of the melt tension at 190°C (MT (g)) to the shear viscosity at 200°C and an angular velocity of 1.0 rad / sec (η (P)) is in the range of 1.40 x 10 * (P) or more and 2.90 x 10 * (P) or less. -4 -4

[0030] (4) The zero shear viscosity at 200°C (η0 (P)) and the weight average molecular weight (Mw) measured by the GPC-Viscosity Detector method (GPC-VISCO) satisfy the following relational expression (Eq-1).

[0031] 0.01 x 10 -13 x Mw 3.4 ≤ η0 ≤ 4.5 x 10 -13 x Mw 3.4 (Eq-1)

[0032] (5) The number average molecular weight (Mn), the weight average molecular weight (Mw) and the Z average molecular weight (Mz) measured by the GPC-Viscosity Detector method (GPC-VISCO) satisfy the following relational expression (Eq-2).

[0033] -2.0 ≤ Mz / Mw - Mw / Mn ≤ 15 (Eq-2)

[0034] (6) The total of the vinyl group, the vinylidene group, the 2-substituted internal olefin and the 3-substituted internal olefin per 1000 carbon atoms (number / 1000C) measured by 1 H-NMR is in the range of 0.1 or more and 1.0 or less.

[0035] (7) The melting curve obtained by differential scanning calorimetry (DSC) has a plurality of peaks.

[0036] [2] The ethylene-α-olefin copolymer (A) according to the above [1], which further satisfies the following condition (8).

[0037] (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.

[0038] [3] The ethylene-α-olefin copolymer (A) according to the above [1] or [2], which further satisfies the following condition (9).

[0039] ​​(9) the intrinsic viscosity ([η] (dl / g)) measured in decalin at 135°C and the weight average molecular weight (Mw) measured by the GPC-VISCO method (GPC-VISCO) satisfy the following relational expression (Eq-4).

[0040] 0.8 x 10 -4 0.776 ≤ [η] ≤ 1.65 x 10 -4 0.776 … (Eq-4)

[0041] [4] A thermoplastic resin composition (Y) containing the ethylene-α-olefin copolymer (A) described in any one of the above [1] to [3] and a thermoplastic resin (excluding the above ethylene-α-olefin copolymer (A)).

[0042] [5] The thermoplastic resin composition (Y) described in the above [4], wherein,

[0043] the above thermoplastic resin is an ethylene-α-olefin copolymer (B) satisfying the following conditions (a) to (d),

[0044] the above thermoplastic resin composition (Y) is an ethylene-based resin composition (Z) in which the mass fraction (W A ) of the above ethylene-α-olefin copolymer (A) is 5 mass% or more and 90 mass% or less, the mass fraction (W B ) of the above ethylene-α-olefin copolymer (B) is 10 mass% or more and 95 mass% or less (wherein the total of W A and W B is set to 100 mass%).

[0045] (a) the density is in the range of 890 kg / m 3 or more and 930 kg / m 3 or less.

[0046] (b) the melt flow rate (MFR) under a load of 2.16 kg at 190°C is in the range of 0.1 g / 10 minutes or more and 20 g / 10 minutes or less.

[0047] (c) the ratio (MT / η * (g / P)) of the melt tension at 190°C (MT (g)) to the shear viscosity at 200°C and an angular velocity of 1.0 rad / sec (η * (P)) is in the range of 1.0 x 10 -6 or more and 1.0 x 10 -4 or less.

[0048] ​​(d) the amount (%) of components having a Log molecular weight of 5.8 or more in the molecular weight distribution curve obtained by GPC is in the range of 0.01% or more and 5.0% or less.

[0049] [6] A film comprising the ethylene-α-olefin copolymer (A) according to any one of the above [1] to [3], or the thermoplastic resin composition (Y) according to the above [4] or [5].

[0050] [7] The film according to the above [6], comprising the ethylene-α-olefin copolymer (A) according to any one of the above [1] to [3].

[0051] [8] The film according to the above [6], comprising the thermoplastic resin composition (Y) according to the above [4].

[0052] [9] The film according to the above [6], comprising the thermoplastic resin composition (Y) according to the above [5].

[0053]

[10] A laminate having a layer comprising the ethylene-α-olefin copolymer (A) according to any one of the above [1] to [3], or the thermoplastic resin composition (Y) according to the above [4] or [5].

[0054]

[11] The laminate according to the above

[10] , further comprising a substrate layer.

[0055]

[12] The laminate according to the above

[11] , further comprising a barrier layer.

[0056]

[13] The laminate according to any one of the above

[10] to

[12] , having a layer comprising the ethylene-α-olefin copolymer (A) according to any one of the above [1] to [3].

[0057]

[14] The laminate according to any one of the above

[10] to

[12] , having a layer comprising the thermoplastic resin composition (Y) according to the above [4].

[0058]

[15] The laminate according to any one of the above

[10] to

[12] , having a layer comprising the thermoplastic resin composition (Y) according to the above [5].

[0059]

[16] A method for producing a laminate by extrusion lamination of the ethylene-α-olefin copolymer (A) according to any one of the above [1] to [3], or the thermoplastic resin composition (Y) according to the above [4] or [5] between a substrate layer and a barrier layer.

[0060] Effects of the Invention

[0061] The ethylene-α-olefin copolymer (A) and the thermoplastic resin composition (Y) containing the same according to the present application can be suitably used for producing a film, a laminate, and a container formed of the laminate, which are excellent in moldability (i.e., no draw fluctuation occurs at T-die molding, and the drawdown is small), and particularly excellent in mechanical strength. Further, the ethylene-α-olefin copolymer (A) and the thermoplastic resin composition (Y) containing the same according to the present application are excellent in adhesion strength when used for an adhesive layer of a laminate, and further excellent in heat sealability when used for a heat seal layer of a laminate.

[0062] Further, the ethylene-based resin composition (Z) according to the present application can be suitably used for producing a molded article (particularly a film) which is excellent in moldability, mechanical strength, and transparency. DETAILED DESCRIPTION

[0063] The ethylene-α-olefin copolymer (A) according to the present application will be described in detail below.

[0064] (Ethylene-α-olefin copolymer (A))

[0065] The ethylene-α-olefin copolymer (A) according to the present application is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 6 to 10 carbon atoms. As the α-olefin having 4 to 10 carbon atoms to be copolymerized with ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and the like can be exemplified.

[0066] The ethylene-α-olefin copolymer (A) according to the present application has the following characteristics (1) to (7).

[0067] (1) The density is 890 kg / m 3 925 kg / m 3 Preferably, 900 kg / m 3 920 kg / m 3 More preferably, 900 kg / m 3 915 kg / m 3 in the above range.

[0068] When the density is in the above lower limit or more, the tackiness of the surface of a film obtained by molding is less. When the density is in the above upper limit or less, the low-temperature sealability of a film obtained by molding is good.

[0069] The density depends on the α-olefin content of the ethylene-α-olefin copolymer (A), and the less the α-olefin content, the higher the density, and the more the α-olefin content, the lower the density. Since the α-olefin content of the ethylene-α-olefin copolymer (A) is determined by the composition ratio of the α-olefin to the ethylene (α-olefin / ethylene) in the polymerization system (for example, Walter Kaminsky, Makromol. Chem. 193, p. 606 (1992)), the ethylene-α-olefin copolymer (A) having the density in the above range can be produced by increasing or decreasing the α-olefin / ethylene.

[0070] The density was measured as described below.

[0071] In the MFR measurement, the obtained strand was heat-treated at 100°C for 30 minutes, and then left at room temperature for 1 hour, and then measured by the density gradient tube method.

[0072] (2) The melt flow rate (MFR) is in the range of 3.0 g / 10 minutes or more and 15.0 g / 10 minutes or less, preferably 4.0 g / 10 minutes or more and 10.0 g / 10 minutes or less, more preferably 5.0 g / 10 minutes or more and 8.0 g / 10 minutes or less.

[0073] When the melt flow rate (MFR) is above the lower limit, the shear viscosity of the ethylene-α-olefin copolymer (A) does not become too high, and the extrusion load is good. When the melt flow rate (MFR) is below the upper limit, the mechanical strength of the ethylene-α-olefin copolymer (A) is good.

[0074] The melt flow rate (MFR) depends greatly on the molecular weight, and the smaller the melt flow rate (MFR), the larger the molecular weight, and the larger the melt flow rate (MFR), the smaller the molecular weight. In addition, it is known that the molecular weight of an ethylene-based polymer is determined by the composition ratio of the hydrogen to the ethylene (hydrogen / ethylene) in the polymerization system (for example, Sadao Soni and others, eds., "Catalytic Olefin Polymerization", Shogakukan Scientific, 1990, p. 376). Therefore, by increasing or decreasing the hydrogen / ethylene, the melt flow rate (MFR) of the ethylene-based polymer can be increased or decreased. The melt flow rate (MFR) was measured in accordance with JIS K 7210 under the conditions of 190°C and a load of 2.16 kg.

[0075] (3) The ratio of the melt tension (MT (g)) to the shear viscosity (η * (P)) at 200°C and an angular velocity of 1.0 rad / sec (MT / η * (g / P)) is in the range of 1.40 x 10 -4 ~ 2.90 x 10 -4 , preferably 1.50 x 10 -4~ 2.70 x 10 -4 , more preferably 1.80 x 10 -4 ~ 2.45 x 10 -4 .

[0076] MT / η * When above the lower limit, the melt tension is high with respect to the molecular weight in the ethylene-α-olefin copolymer (A), and thus the moldability is excellent. MT / η * When below the upper limit, the mechanical strength of the ethylene-α-olefin copolymer (A) is excellent.

[0077] MT / η * Depending on the long-chain branch content of the ethylene-based polymer, the more the long-chain branch content, the greater the MT / η * The less the long-chain branch content, the smaller the MT / η * Long-chain branches are defined as branch structures having a length of a molecular weight (Me) or more between entanglements in the ethylene-based polymer, and it is known that by introducing long-chain branches, the melt properties and the mold processing properties of the ethylene-based polymer are significantly changed (for example, Kazuo Matsuura et al., "Polyethylene Technology Reader", Industrial Investigation Association, 2001, p. 32, 36).

[0078] MT / η * This can be adjusted by the kind of component (A) or the solid carrier (S) of the catalyst (X) for olefin polymerization described later. In addition, even in the case of using the same catalyst (X) for olefin polymerization, adjustment can be made by the polymerization conditions or the polymerization process, for example, by increasing the ethylene partial pressure, the MT / η * can be decreased. According to the production conditions of Example 12 described later, the MT / η * near the lower limit can be obtained; and according to the production conditions of Example 10 described later, the MT / η * near the upper limit can be obtained.

[0079] The melt tension (MT (g)) is determined by measuring the stress when stretched at a certain speed. The measurement uses a capillary rheometer (for example, a capillary rheometer CAPILOGRAPH ID manufactured by Orient Colloid Co., Ltd. used in the examples described later). The conditions are set to a resin temperature of 190°C, a melting time of 6 minutes, a tube diameter of 2 mm, an extrusion speed of 15 mm / minute, a take-up speed of 24 m / minute (in the case of a melt filament breakage, the take-up speed is decreased by 5 m / minute), a nozzle diameter of 2 mm, and a nozzle length of 8 mm.

[0080] Shear viscosity (η * ​​(P)〕 The measurement was performed as described below. Regarding the shear viscosity (η * ), the angular velocity [ω (rad / sec)] distribution of the shear viscosity (η * ) at a measurement temperature of 200°C was measured in the range of 0.01 ≤ ω ≤ 100. The measurement was performed using a viscoelasticity measuring device (for example, Physica MCR301 manufactured by Anton Paar in the examples described later), using a parallel plate as a sample holder, and the sample thickness was set to about 2.0 mm. Five points were set for each order of magnitude of ω. The strain amount was appropriately selected in the range of 3 to 10% so that the torque could be detected in the measurement range and the torque would not become too large.

[0081] The sample used for the shear viscosity measurement was produced as described below: using a molding machine (for example, a press molding machine manufactured by Joten Metal Industry in the examples described later), the measurement sample was press-molded to a thickness of 2 mm under the conditions of a preheating temperature of 190°C, a preheating time of 5 minutes, a heating temperature of 190°C, a heating time of 2 minutes, a heating pressure of 100 kgf / cm 2 , a cooling temperature of 20°C, a cooling time of 5 minutes, and a cooling pressure of 100 kgf / cm 2 .

[0082] (4) The zero shear viscosity at 200°C [η0(P)] satisfies the following relationship (Eq-1) with the weight average molecular weight (Mw) measured by the GPC-Viscosity Detector method (GPC-VISCO).

[0083] 0.01 x 10 -13 x Mw 3.4 ≤ η0≤ 4.5 x 10 -13 x Mw 3.4 … (Eq-1)

[0084] It is preferable to satisfy the following (Eq-1').

[0085] 0.1 x 10 -13 x Mw 3.4 ≤ η0≤ 3.0 x 10 -13 x Mw 3.4 … (Eq-1')

[0086] It is more preferable to satisfy the following (Eq-1").

[0087] 0.2 x 10 -13 x Mw 3.4 ≤ η0≤ 2.0 x 10 -13 x Mw 3.4 … (Eq-1")

[0088] ​It is known that, when a double logarithmic curve of zero shear viscosity [η0(P)] against weight average molecular weight (Mw) is plotted, a resin which does not show strain hardening like a linear ethylene-based polymer of which elongational viscosity does not show strain hardening follows a power law with a slope of 3.4, and, in contrast to this, a resin which shows strain rate hardening like a high-pressure low-density polyethylene shows a zero shear viscosity [η0(P)] lower than the power law (C Gabriel, H. Munstedt, J. Rheol., 47(3), 619 (2003)).

[0089] It can be considered that the relationship of zero shear viscosity [η0(P)] to weight average molecular weight (Mw) depends on the content and length of long chain branches in the ethylene-based polymer, and it can be considered that the more the content of long chain branches and the shorter the length of long chain branches, the smaller the value of zero shear viscosity [η0(P)] shows, and the less the content of long chain branches and the longer the length of long chain branches, the larger the value of zero shear viscosity [η0(P)] shows.

[0090] When the zero shear viscosity [η0(P)] at 200°C is below the upper limit, the elongational viscosity of the ethylene-based polymer shows strain rate hardening, so that draw resonance does not occur. Also, since the long chain branches are short and the entanglement between molecules is easily untangled, the molecules in the ethylene-based resin composition (Z) easily relax. The film composed of the ethylene-based resin composition (Z) has less surface unevenness and excellent transparency.

[0091] The zero shear viscosity [η0(P)] can be adjusted by the kind of component (A) or solid carrier (S) of the catalyst (X) for olefin polymerization described later. Also, even in the case of using the same catalyst (X) for olefin polymerization, adjustment can be made by the polymerization conditions or polymerization process, and, for example, by increasing the ethylene partial pressure, the zero shear viscosity [η0(P)] can be increased. According to the production conditions of Example 11 described later, a zero shear viscosity [η0(P)] near the lower limit can be obtained; and according to the production conditions of Example 9 described later, a zero shear viscosity [η0(P)] near the upper limit can be obtained.

[0092] The zero shear viscosity [η0(P)] at 200°C is measured as described below.

[0093] The angular velocity ω (rad / sec) distribution of shear viscosity (η * ) is measured at a measurement temperature of 200°C in the range of 0.01 ≤ ω ≤ 100. The measurement uses a viscoelasticity measuring device (for example, Physica MCR301 manufactured by Anton Paar GmbH used in Examples described later). The measurement is performed using a parallel-plate type shear measurement mode. A parallel plate was used as a sample holder, and the sample thickness was set to about 2.0 mm. Five points were set for each order of magnitude of ω. The strain amount was appropriately selected in the range of 3 to 10% so that the torque could be detected in the measurement range, and the torque did not become too large.

[0094] The sample used for the shear viscosity measurement was produced as described below: Using a molding machine (for example, a press molding machine manufactured by JISICO was used in the examples described later), the measurement sample was press-molded under conditions of a preheating temperature of 190°C, a preheating time of 5 minutes, a heating temperature of 190°C, a heating time of 2 minutes, a heating pressure of 100 kgf / cm 2 , a cooling temperature of 20°C, a cooling time of 5 minutes, and a cooling pressure of 100 kgf / cm 2 .

[0095] The zero shear viscosity (η0) was calculated by fitting the Carreau model of the following equation to the measured rheological curve (distribution of shear viscosity (η * ) with respect to angular velocity (ω)) using a nonlinear least squares method.

[0096] η * = η0[1 + (λω) a ] (n-1) / a

[0097] (λ represents a parameter having a time dimension, a represents a fitting parameter, and n represents the power law index of the material.)

[0098] Here, the fitting of d in the following equation was performed in such a manner that d becomes the smallest using a nonlinear least squares method.

[0099]

[0100] (ηexp(ω) represents the measured shear viscosity, and ηcalc(ω) represents the shear viscosity calculated by the Carreau model.)

[0101] The weight average molecular weight (Mw) and the like were measured using gel permeation chromatography (GPC) as described below.

[0102] The detector used a differential refractometer and a capillary viscometer, the column temperature was set to 145°C, o-dichlorobenzene was used as the mobile phase at a flow rate of 1.0 ml / min, the sample concentration was set to 0.1% by weight, and polystyrene was used as the standard polymer. In the examples described later, a GPC-VISCO PL-GPC220 manufactured by Agilent was used as the measuring device, two Agilent PLgel Olexis were used as the analysis column, and a product manufactured by Tosoh Corporation was used as the standard polystyrene. Regarding the molecular weight calculation, the measured viscosity was calculated from the viscometer and the refractometer, and the number average molecular weight (Mn), the weight average molecular weight (Mw), the Z average molecular weight (Mz), and the molecular weight distribution (Mw / Mn, Mz / Mw) were calculated using the measured universal calibration.

[0103] (5) The number average molecular weight (Mn), the weight average molecular weight (Mw), and the Z average molecular weight (Mz) measured by the GPC-VISCO method satisfy the following relationship (Eq-2).

[0104] -2.0 ≤ Mz / Mw - Mw / Mn ≤ 15... (Eq-2)

[0105] It is preferable to satisfy the following relationship (Eq-2').

[0106] -1.5 ≤ Mz / Mw - Mw / Mn ≤ 12... (Eq-2')

[0107] It is more preferable to satisfy the following relationship (Eq-2").

[0108] -1.0 ≤ Mz / Mw - Mw / Mn ≤ 10... (Eq-2")

[0109] When Mz / Mw - Mw / Mn is large, the molecular weight distribution extends to the high molecular weight side, and when Mz / Mw - Mw / Mn is above the lower limit, the shrinkage is excellent, and when Mz / Mw - Mw / Mn is below the upper limit, the film formability is excellent.

[0110] Mz / Mw - Mw / Mn can be adjusted by the kind of component (A) or solid carrier (S) of the catalyst (X) for olefin polymerization described later, and even when the same catalyst (X) for olefin polymerization is used, it can be adjusted by the polymerization conditions or polymerization process. According to the production conditions of Example 2 described later, Mz / Mw - Mw / Mn near the lower limit can be obtained, and according to the polymerization conditions of Example 11 described later, Mz / Mw - Mw / Mn near the upper limit can be obtained.

[0111] The number average molecular weight (Mn), the weight average molecular weight (Mw), and the Z average molecular weight (Mz) were measured according to the above method.

[0112] (6) The number average molecular weight (Mn), the weight average molecular weight (Mw), and the Z average molecular weight (Mz) were measured according to the above method. 1The number of vinyl groups, vinylidene groups, 2-substituted internal olefins (2-substituted vinylene), and 3-substituted internal olefins (3-substituted vinylene) measured by1H-NMR satisfies the following relationship (Eq-3).

[0113] 0.1 ≤ vinyl + vinylidene + 2-substituted internal olefin + 3-substituted internal olefin ≤ 1.0... (Eq-3)

[0114] It is preferable to satisfy the following relationship (Eq-3').

[0115] 0.3 ≤ vinyl + vinylidene + 2-substituted internal olefin + 3-substituted internal olefin ≤ 0.9... (Eq-3')

[0116] It is more preferable to satisfy the following relationship (Eq-3").

[0117] 0.5 ≤ vinyl + vinylidene + 2-substituted internal olefin + 3-substituted internal olefin ≤ 0.8... (Eq-3")

[0118] The number of vinyl groups, vinylidene groups, 2-substituted internal olefins (2-substituted vinylene), and 3-substituted internal olefins (3-substituted vinylene) in the polymer is measured by 1 The number per 1000 carbon atoms contained in the polymer measured by1H-NMR method. It is known that the generation amount ratio and the number of vinyl groups, vinylidene groups, 2-substituted internal olefins, and 3-substituted internal olefins increase or decrease depending on the transition metal compound used (H. SAIKI, S. MAKOTO, T. MASAO, S. MORIHIKO, Y. AKIHIRO, J. Polym. Sci., A: Polym. Chem., 38, 4641 (2000)). They can be adjusted by the kind of component (A) or solid carrier (S) of the olefin polymerization catalyst (X) described later. In addition, even in the case of using the same olefin polymerization catalyst (X), it can be adjusted by the polymerization conditions or polymerization process, for example, by increasing or decreasing the ethylene partial pressure, and it can be increased or decreased.

[0119] When the number of vinyl groups + vinylidene groups + 2-substituted internal olefins + 3-substituted internal olefins is above the lower limit, long chain branching is easily generated, and the moldability is excellent; when the number of vinyl groups + vinylidene groups + 2-substituted internal olefins + 3-substituted internal olefins is below the upper limit, the molten film of the extrusion laminate is not easily oxidized, the heat sealability is excellent, and the transparency and mechanical strength of the molded body are excellent.

[0120] The number of vinyl groups, vinylidene groups, 2-substituted internal olefins, and 3-substituted internal olefins measured by1H-NMR (500 MHz) is measured using a nuclear magnetic resonance device (for example, the AVANCE III (ultra-low temperature probe) type nuclear magnetic resonance device manufactured by Bruker used in the examples described later) as follows. 1 The number of vinyl groups, vinylidene groups, 2-substituted internal olefins, and 3-substituted internal olefins measured by1H-NMR (500 MHz) is measured using a nuclear magnetic resonance device (for example, the AVANCE III (ultra-low temperature probe) type nuclear magnetic resonance device manufactured by Bruker used in the examples described later).

[0121] Measurement mode was set to single pulse, pulse width 45°. Number of shots was set to 32k, observation range to 20ppm (-6 to 14ppm), repetition time to 7 seconds and number of accumulations to 64. After dissolving the sample 20 mg in ortho-dichlorobenzene-d 40.6 ml, measurement was performed at 120°C.

[0122] In 1 In the H-NMR spectrum, the relative values of the number of double bonds calculated from the integral values of the signals from various double bonds (vinyl group, vinylidene group, internal olefin) and the total number of carbon atoms calculated from the total integral value of the H signals in the range of 4.5 ppm to 5.8 ppm were obtained, and the number of various double bonds per 1000 carbons in the polymer was calculated. 1 In the H-NMR spectrum, the relative values of the number of double bonds calculated from the integral values of the signals from various double bonds (vinyl group, vinylidene group, internal olefin) and the total number of carbon atoms calculated from the total integral value of the H signals in the range of 4.5 ppm to 5.8 ppm were obtained, and the number of various double bonds per 1000 carbons in the polymer was calculated.

[0123] (7) The melting curve obtained by differential scanning calorimetry (DSC) has multiple peaks.

[0124] In the case where the melting curve has multiple peaks, the low-melting-point component is large, and the heat sealability at low temperature is excellent.

[0125] With respect to differential scanning calorimetry (DSC), a differential scanning calorimeter (for example, Diamond DSC manufactured by PerkinElmer, Inc. used in the Examples described later) was used and measurement was performed as described below.

[0126] About 5 mg of the sample was charged into an aluminum pan, and the temperature was raised to 200°C at 10°C / minute, held at 200°C for 10 minutes, then lowered to -30°C at 10°C / minute, and then raised to 200°C at 10°C / minute to obtain the endothermic curve at that time. The fact that the endothermic curve has two or more peaks means that the melting curve obtained by differential scanning calorimetry (DSC) has multiple peaks.

[0127] The ethylene-α-olefin copolymer (A) of the present application preferably has the characteristics shown in (8) below.

[0128] (8) The ratio (Mz / Mw) of the Z-average molecular weight (Mz) to the weight-average molecular weight (Mw) measured by the GPC-VISCO method (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 the high-molecular-weight component, and the shrinkage is excellent when the Mz / Mw is above the lower limit, and the film formability is excellent when the Mz / Mw is below the upper limit.

[0129] Mz / Mw can be adjusted by the kind of component (A) or solid carrier (S) of the olefin polymerization catalyst (X) described later, and even in the case of using the same olefin polymerization catalyst (X), it can be adjusted by the polymerization conditions or polymerization process. According to the production conditions of Example 2 described later, Mz / Mw near the lower limit can be obtained; according to the polymerization conditions of Example 11 described later, Mz / Mw near the upper limit can be obtained.

[0130] The ethylene-a-olefin copolymer (A) of the present application preferably has the property shown in the following (9).

[0131] (9) 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-4).

[0132] 0.8 x 10 -4 x Mw 0.776 ≤ [η] ≤ 1.65 x 10 -4 x Mw 0.776 … (Eq-4)

[0133] It is preferable to satisfy the following (Eq-4').

[0134] 0.9 x 10 -4 x Mw 0.776 ≤ [η] ≤ 1.45 x 10 -4 x Mw 0.776 … (Eq-4')

[0135] It is more preferable to satisfy the following (Eq-4").

[0136] 1.0 x 10 -4 x Mw 0.776 ≤ [η] ≤ 1.30 x 10 -4 x Mw 0.776 … (Eq-4")

[0137] It is known that when long-chain branches are introduced in an ethylene-based polymer, the intrinsic viscosity [[η] (dl / g)] decreases with respect to the molecular weight compared to a linear ethylene-based polymer without long-chain branches (for example, Walther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched Polymer II, p. 137 (1999)). Therefore, in the case where the intrinsic viscosity [[η] (dl / g)] is 1.65 x 10 -4 x Mw 0.776 , the ethylene-based polymer has a plurality of long-chain branches, and the moldability and flowability are excellent.

[0138] The intrinsic viscosity [[η] (dl / g)] can be adjusted by the kind of the component (A) or the solid carrier (S) of the olefin polymerization catalyst (X) described later. Also, even in the case of using the same olefin polymerization catalyst (X), it can be adjusted by the polymerization conditions or polymerization process, for example, by increasing the ethylene partial pressure, the intrinsic viscosity [[η] (dl / g)] can be increased. In the production conditions of Example 8 described later, the intrinsic viscosity [[η] (dl / g)] near the lower limit can be obtained; according to the production conditions of Example 9 described later, the intrinsic viscosity [[η] (dl / g)] near the upper limit can be obtained.

[0139] The intrinsic viscosity [[η] (dl / g)] is measured as described below using decalin solvent. About 20 mg of the sample is dissolved in 15 ml of decalin, and the relative viscosity ηsp is measured in an oil bath at 135°C. After dilution by adding 5 ml of decalin solvent to this decalin solution, the relative viscosity ηsp is measured in the same manner. This dilution operation is repeated twice, and the value of ηsp / C at the time when the concentration (C) is extrapolated to 0 is calculated as the intrinsic viscosity [η] (unit: dl / g) as shown in the following equation.

[0140] [η] = lim (ηsp / C) (C→0)

[0141] The weight average molecular weight (Mw) is measured by the above method.

[0142] (Production method of ethylene-α-olefin copolymer (A))

[0143] Next, the production method of the ethylene-α-olefin copolymer (A) of the present application will be described.

[0144] The ethylene-α-olefin copolymer (A) of the present application 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) containing the following component (A) and solid carrier (S).

[0145] (Catalyst (X) for olefin polymerization)

[0146] The olefin polymerization catalyst (X) contains the following component (A) and solid carrier (S).

[0147] < Component (A) >

[0148] The 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 kind of transition metal compound (1). That is, as the component (A), one kind of transition metal compound (1) can be used, or a plurality of kinds of transition metal compounds (1) can be used.

[0149]

[0150] In the above formula (1), M is a zirconium atom or a hafnium atom, preferably a zirconium atom.

[0151] In the above formula (1), n is an integer of 1 to 4 selected in such a manner that the transition metal compound (1) is electrically neutral, preferably 2.

[0152] In the above formula (1), 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, preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0153] As the above halogen atom, fluorine, chlorine, bromine, iodine can be exemplified, and chlorine is particularly preferred.

[0154] As the above hydrocarbon group having 1 to 20 carbon atoms, for example, the following can be exemplified:

[0155] methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl (butane-2-yl), tert-butyl (2-methylpropane-2-yl), isobutyl (2-methylpropyl), pentane-2-yl, 2-methylbutyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), diisopentyl (1,2-dimethylpropyl), iso-hexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, texyl (2,3-dimethylbutane-2-yl), 4,4-dimethylpentyl, and the like, straight-chain or branched-chain alkyl groups;

[0156] vinyl, allyl, propenyl (prop-1-en-1-yl), isopropenyl (prop-1-en-2-yl), allenyl (prop-1,2-dien-1-yl), but-3-en-1-yl, crotyl (but-2-en-1-yl), but-3-en-2-yl, methallyl (2-methylallyl), buta-1,3-dienyl, pent-4-en-1-yl, pent-3-en-1-yl, pent-2-en-1-yl, isopentenyl (3-methylbut-3-en-1-yl), 2-methylbut-3-en-1-yl, pent-4-en-2-yl, isoprene (3-methylbut-2-en-1-yl), and the like, straight-chain or branched-chain alkenyl groups or groups containing unsaturated double bonds;

[0157] ethynyl, prop-2-yn-1-yl, propargyl (prop-1-yn-1-yl), and the like, straight-chain or branched-chain alkynyl groups or groups containing unsaturated triple bonds;

[0158] linear or branched alkyl groups containing aromatic groups such as benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl (4-isopropylbenzyl), 2,4,6-triisopropylbenzyl, 4-tert-butylbenzyl, 3,5-di-tert-butylbenzyl, 1-phenylethyl, benzhydryl (diphenylmethyl), and groups containing unsaturated double bonds;

[0159] cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, 1-adamantyl, 2-adamantyl, and the like;

[0160] cycloheptatrienyl, norbornenyl;

[0161] aromatic substituents such as phenyl, tolyl (methylphenyl), xylyl (dimethylphenyl), mesityl (2,4,6-trimethylphenyl), cuminyl (isopropylphenyl), mesityl (2,3,5,6-tetramethylphenyl), 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, naphthyl, biphenyl, terphenyl, binaphthyl, acenaphthyl, phenanthryl, anthryl, pyrenyl, ferrocenyl, and the like, preferably methyl, isobutyl, neopentyl, diisopentyl (Siamyl), benzyl, phenyl, tolyl, xylyl, mesityl, cuminyl.

[0162] The above hydrocarbon group having 1 to 20 carbon atoms can be a halogenated hydrocarbon group in which part or all of the hydrogen atoms of the above hydrocarbon group having 1 to 20 carbon atoms are substituted with halogen atoms, and as examples thereof, fluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, pentafluorophenylmethyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, tri-fluoromethylphenyl, bis-trifluoromethylphenyl, and the like can be listed, preferably pentafluorophenyl.

[0163] As the above silicon-containing group, for example, trimethylsilyl, triethylsilyl, triisopropylsilyl, diphenylmethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, triphenylsilyl, tris(trimethylsilyl)silyl, trimethylsilylmethyl, and the like can be listed, preferably trimethylsilylmethyl.

[0164] As the above-mentioned oxygen-containing group, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, allyloxy group, n-butoxy group, sec-butoxy group, isobutoxy group, t-butoxy group, benzyloxy group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-di-t- butylphenoxy group, 2,4,6-trimethylphenoxy group, 2,4,6-triisopropylphenoxy group, acetyloxy group, t-amyloyl group, benzoyloxy group, trifluoroacetyloxy group, perchloric acid anion, periodate anion, preferably methoxy group, ethoxy group, isopropoxy group, t-butoxy group.

[0165] As the above-mentioned nitrogen-containing group, for example, amino group, cyano group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, allylamino group, diallylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholinyl group, pyrrolyl group, bistriflylimide group, and the like.

[0166] As the above-mentioned conjugated diene derivative group, for example, 1,3-butadienyl group, isoprenyl group (2-methyl-l,3-butadienyl group), metaprenyl group (1,3-pentadienyl group), 2,4-hexadienyl group, 1,4-diphenyl-l,3-pentadienyl group, cyclopentadienyl group, and the like, preferably 1,3-butadienyl group, 1,3-pentadienyl group.

[0167] In the above-mentioned formula (1), Q is a carbon atom or a silicon atom, preferably a silicon atom.

[0168] In the above-mentioned 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, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms.

[0169] As the hydrocarbon group having 1 to 20 carbon atoms of R 1 ~R 14 , linear or branched alkyl groups such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, isopropyl group, sec-butyl group (butane-2-yl group), t-butyl group (2-methylpropane-2-yl group), isobutyl group (2-methylpropyl group), pentane-2-yl group, 2-methylbutyl group, isopentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), diisopentyl group (1,2-dimethylpropyl group), isohexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, Thexyl group (2,3-dimethylbutane-2-yl group), 4,4-dimethylpentyl group, and the like;

[0170] linear or branched alkenyl group such as vinyl, allyl, propenyl (prop-1-en-1-yl), isopropenyl (prop-1-en-2-yl), propadienyl (prop-1,2-dien-1-yl), but-3-en-1-yl, crotyl (but-2-en-1-yl), but-3-en-2-yl, methallyl (2-methylallyl), buta-1,3-dienyl, pent-4-en-1-yl, pent-3-en-1-yl, pent-2-en-1-yl, isopentenyl (3-methylbut-3-en-1-yl), 2-methylbut-3-en-1-yl, pent-4-en-2-yl, isoprene (3-methylbut-2-en-1-yl), and the like, or an unsaturated double bond-containing group;

[0171] linear or branched alkynyl group such as ethynyl, prop-2-yn-1-yl, propargyl (prop-1-yn-1-yl), and the like, or an unsaturated triple bond-containing group;

[0172] linear or branched alkyl group containing an aromatic group such as benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl (4-isopropylbenzyl), 2,4,6-triisopropylbenzyl, 4-tert-butylbenzyl, 3,5-di-tert-butylbenzyl, 1-phenylethyl, benzhydryl (diphenylmethyl), pentafluorophenylmethyl, and the like, and an unsaturated double bond-containing group;

[0173] cyclic saturated hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, 1-adamantyl, 2-adamantyl, and the like;

[0174] cycloheptatrienyl, norbornenyl;

[0175] aromatic substituent such as phenyl, tolyl (methylphenyl), xylyl (dimethylphenyl), mesityl (2,4,6-trimethylphenyl), cumyl (isopropylphenyl), mesityl (2,3,5,6-tetramethylphenyl), 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, naphthyl, biphenyl, terphenyl, binaphthyl, acenaphthyl, phenanthryl, anthryl, pyrenyl, ferrocenyl, and the like;

[0176] halogenated hydrocarbon group in which the above hydrocarbon group having 1 to 20 carbon atoms or all of the hydrogen atoms thereof are substituted with halogen atoms such as fluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluorophenylmethyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, trifluoromethylphenyl, bistrifluoromethylphenyl, and the like,

[0177] Preferably, the following compounds are used: methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, neopentyl, tert-pentyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclooctenyl, norbornyl, bicyclo[2.2.2]octane-1-yl, 1-adamantyl, 2-adamantyl, benzyl, diphenylmethyl , cumyl, 1,1-diphenylethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, cinnamyl, phenyl, tolyl, xylyl, mesitylelel, cumenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 4-adamantylphenyl, naphthyl, biphenyl, terphenyl, binatyl, phenanthryl, anthracene, ferrocene, pentafluorophenyl.

[0178] As R 1 ~R 14 The silicon-containing group having 1 to 20 carbon atoms is preferably trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, triphenylsilyl, cyclopentadienyldimethylsilyl, cyclopentadienyldiphenylsilyl, indenedimethylsilyl, fluorenyldimethylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-triisopropylsilylphenyl, 3,5-bis(trimethylsilyl)phenyl, etc. Examples include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-triisopropylsilylphenyl, and 3,5-bis(trimethylsilyl)phenyl.

[0179] As R 1 ~R 14Oxide groups with 1 to 20 carbon atoms include, for example, methoxy, ethoxy, isopropoxy, allyloxy, n-butoxy, tert-butoxy, pentadienoxy, benzyloxy, phenoxy, naphthoxy, tolyloxy, isopropylphenoxy, allylphenoxy, tert-butylphenoxy, methoxyphenoxy, biphenoxy, binaphthoxy, allyloxymethyl, benzyloxymethyl, phenoxymethyl, methoxyethyl, methoxyallyl, benzyloxyallyl, phenoxyallyl, dimethoxymethyl, dioxopentyl, tetramethyldioxopentyl, dioxohexyl, dimethyldioxohexyl, methoxyphenyl, isopropoxyphenyl, and allyloxy The compounds include methylphenyl, phenoxyphenyl, methylenedioxyphenyl, 3,5-dimethyl-4-methoxyphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, furanyl, methylfuranyl, tetrahydropyranyl, furfuryl, benzofuranyl, dibenzofuranyl, etc., preferably methoxy, isopropoxy, tert-butoxy, allyloxy, phenoxy, dimethoxymethyl, dioxolanecycloyl, methoxyphenyl, isopropoxyphenyl, allyloxyphenyl, phenoxyphenyl, 3,5-dimethyl-4-methoxyphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, furanyl, methylfuranyl, benzofuranyl, dibenzofuranyl, etc.

[0180] As R 1 ~R 14 Nitrogen-containing groups with 1 to 20 carbon atoms include, for example, amino, dimethylamino, diethylamino, allylamino, benzylamino, dibenzylamino, pyrrolyl, piperidinyl, morpholinyl, dimethylaminomethyl, benzylaminomethyl, pyrrolylmethyl, dimethylaminoethyl, pyrrolylethyl, dimethylaminopropyl, pyrrolylpropyl, dimethylaminoallyl, pyrrolylallyl, aminophenyl, dimethylaminophenyl, 3,5-dimethyl-4-dimethylaminophenyl, 3,5-diisopropyl-4-dimethylaminophenyl, julolidinyl, tetramethyljulolidinyl, pyrrolylphenyl, and pyrrolylphenyl. Carbazolylphenyl, di-tert-butylcarbazolylphenyl, pyrrole, pyridinyl, quinolinyl, tetrahydroquinolinyl, isoquinolinyl, tetrahydroisoquinolinyl, indolyl, dihydroindolyl, carbazolyl, di-tert-butylcarbazolyl, imidazolyl, dimethylimidazolyl, benzimidazolyl, oxazolyl, oxazolyl, benzoxazolyl, etc., preferably amino, dimethylamino, diethylamino, pyrroleyl, dimethylaminophenyl, 3,5-dimethyl-4-dimethylaminophenyl, 3,5-diisopropyl-4-dimethylaminophenyl, juloridinyl, tetramethyljuloridinyl, pyrroleylphenyl, pyrrole, pyridinyl, carbazolyl, imidazolyl.

[0181] In equation (1) above, R 1 ~R 6 Adjacent substituents in the middle (e.g., R) 1 With R 2 R2 R 3 R 3 R 4 R 4 R 5 R 5 R 6 ) can be combined with each other to form a ring which can have a substituent. As the ring formed at this time, a 5- to 8-membered ring which can have a substituent, formed of a saturated hydrocarbon (hydrocarbon other than the indenyl ring portion described above) or an unsaturated hydrocarbon, which forms a fused ring with the indenyl ring portion, is preferred. Of these, in the case where a plurality of rings are present, they can be the same as or different from each other. The above-mentioned ring is more preferably a 5-membered ring or a 6-membered ring, without particular limitation as long as the effects of the present application can be achieved, and at this time, as the structure in which the above-mentioned ring is combined with the indenyl ring portion of the parent nucleus, for example, a benzindenyl ring, a tetrahydrobenzoindenyl ring, a cyclopentanotetrahydronaphthalene ring can be exemplified, with a benzindenyl ring, a tetrahydrobenzoindenyl ring being preferred. These rings can have a substituent.

[0182] In the above formula (1), R 7 to R 12 adjacent to each other (for example, 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 ) can be combined with each other to form a ring which can have a substituent. As the ring formed at this time, a 5- to 8-membered ring which can have a substituent, formed of a saturated hydrocarbon (hydrocarbon other than the indenyl ring portion described above) or an unsaturated hydrocarbon, which forms a fused ring with the indenyl ring portion, is preferred. Of these, in the case where a plurality of rings are present, they can be the same as or different from each other. The above-mentioned ring is more preferably a 5-membered ring or a 6-membered ring, without particular limitation as long as the effects of the present application can be achieved, and at this time, as the structure in which the above-mentioned ring is combined with the indenyl ring portion of the parent nucleus, for example, a benzindenyl ring, a tetrahydrobenzoindenyl ring, a cyclopentanotetrahydronaphthalene ring, a tetrahydrofluorene ring, a fluorene ring can be exemplified, with a benzindenyl ring, a tetrahydrobenzoindenyl ring being preferred. These rings can have a substituent.

[0183] In the above formula (1), R 13 and R 14These rings can also have substituents. The rings formed at this time are preferably 3 to 8-membered saturated or unsaturated rings which can have substituents. There is no particular limitation as long as the effects of the present application can be achieved, and a 4 to 6-membered ring is preferred, and in this case, as the structure combined with Q, for example, a cyclobutane ring, a cyclopentane ring, a fluorene ring, a silyl-cyclobutane (silyl-cyclobutane) ring, a silyl-cyclopentane (silyl-cyclopentane) ring, a silyl-cyclohexane (silyl-cyclohexane) ring, a silyl-fluorene ring are exemplified, and a cyclopentane ring, a silyl-cyclobutane ring, a silyl-cyclopentane ring are preferred. These rings can have substituents.

[0184] The following shows specific examples of the transition metal compound (1), but the scope of the present application is not particularly limited to these specific examples.

[0185] For convenience, the structure of the ligand other than the portion indicated by the removal of MXn (metal portion) of the above-mentioned transition metal compound (1) is divided into 2-indenyl ring portion, 1-indenyl ring portion, indenyl ring portion R 1 , R 6 , and R 8 substituent, indenyl ring portion R 2 , R 5 , R 9 , and R 12 substituent, indenyl ring portion R 3 , R 4 , R 10 , and R 11 substituent, 1-indenyl ring portion R 7 substituent, and structure of bridging portion. The abbreviation of the 2-indenyl ring portion is α, the abbreviation of the 1-indenyl ring portion is β, the abbreviation of the indenyl ring portion R 1 , R 6 , and R 8 substituent is γ, the abbreviation of the indenyl ring portion R 2 , R 5 , R 9 , and R 12 substituent is δ, the abbreviation of the indenyl ring portion R 3 , R 4 , R 10 , and R 11 substituent is ε, the abbreviation of the 1-indenyl ring portion R 7 substituent is ζ, and the abbreviation of the structure of bridging portion is η, and the abbreviations of each substituent are shown in [Table 1] to [Table 7].

[0186] [Table 1]

[0187] [Table 1]

[0188] 2-indenyl ring portion

[0189]

[0190] [Table 2]

[0191] [Table 2]

[0192] 1-indenyl ring moiety

[0193]

[0194] wherein the above [Table 1] to [Table 2] wave line indicates the binding site with the bridging moiety.

[0195] [Table 3]

[0196] [Table 3]

[0197] Indenyl ring R1, R6, R8 substituents

[0198] γ-1 hydrogen γ-2 methyl γ-3 ethyl γ-4 n-propyl γ-5 allyl γ-6 n-butyl γ-7 but-3-en-1-yl γ-8 benzyl γ-9 pentafluorophenylmethyl γ-10 phenyl γ-11 tolyl γ-12 naphthyl γ-13 4-t-butylphenyl γ-14 5-methyl-2-furyl γ-15 5-methyl-2-thienyl

[0199] R in the above [Table 3] 1 , R 6 and R 8 substituents can be the same or different from each other in their combinations.

[0200] [Table 4]

[0201] [Table 4]

[0202] Indenyl ring R2, R5, R9, R12 substituents

[0203]

[0204] R in the above [Table 4] 2 , R 5 , R 9 and R 12 substituents can be the same or different from each other in their combinations.

[0205] [Table 5]

[0206] [Table 5]

[0207] Indenyl ring R3, R4, R10, R11 substituents

[0208] ε-1 hydrogen ε-2 methyl ε-3 methoxy ε-4 ethyl ε-5 ethoxy ε-6 n-propyl ε-7 isopropyl ε-8 isopropoxy ε-9 n-butyl ε-10 isobutyl ε-11 sec-butyl ε-12 t-butyl ε-13 neopentyl ε-14 cyclopentyl ε-15 cyclohexyl ε-16 Thexyl ε-17 t-octyl ε-18 phenoxy

[0209] R in the above [Table 5] 3 , R 4 , R 10 and R 11 substituents can be the same or different from each other in their combinations.

[0210] [Table 6]

[0211] [Table 6]

[0212] 1-indenyl ring R7substituent

[0213]

[0214] [Table 7]

[0215] [Table 7]

[0216] bridging moiety

[0217] η-1 methylene η-2 1,1-ethylene η-3 benzyl (phenylmethylene) η-4 dimethylmethylene (isopropylidene) η-5 methylethylmethylene (sec-butylidene) η-6 diethylmethylene (3-pentylidene) η-7 dipropylmethylene (4-heptylidene) η-8 dibutylmethylene (5-nonylidene) η-9 dibenzylmethylene η-10 (methyl)(phenyl)methylene (1-phenylethylidene) η-11 (methyl)(4-methylphenyl)methylene η-12 (methyl)(4-methoxyphenyl)methylene η-13 diphenylmethylene η-14 di(4-methylphenyl)methylene η-15 di(4-methoxyphenyl)methylene η-16 di(4-dimethylaminophenyl)methylene η-17 1,1-cyclobutylidene η-18 1,1-cyclopentylidene η-19 1,1-cyclohexylidene η-20 dimethylsilyl η-21 diethylsilyl η-22 divinylsilyl η-23 dipropylsilyl η-24 diisopropylsilyl η-25 diallylsilyl η-26 din-butylsilyl η-27 dit-butylsilyl η-28 din-hexylsilyl η-29 diphenylsilyl η-30 di(4-methylphenyl)silyl η-31 1,1-silylcyclobutyl (trimethylsilyl) η-32 1,1-silylcyclopentyl (tetramethylsilyl) η-33 1,1-silylcyclohexyl (pentamethylsilyl) η-34 (methyl)(ethyl)silyl η-35 (methyl)(vinyl)silyl η-36 (methyl)(allyl)silyl η-37 (methyl)(n-hexyl)silyl η-38 (methyl)(n-octyl)silyl η-39 (methyl)(n-decyl)silyl η-40 (methyl)(cyclohexyl)silyl η-41 (methyl)(phenyl)silyl

[0218] As specific examples of the metal moiety MXn, the following can be cited:

[0219] ZrF2, ZrCl2, ZrBr2, ZrI2, Zr(Me)2, Zr(Bn)2, Zr(allyl)2, Zr(CH2-tBu)2, Zr(1,3-pentadienyl), 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(OiPr)2, Zr(NMe2)2, Zr(OMs)2, Zr(OTs)2, Zr(OTf)2,

[0220] HfF2, HfCl2, HfBr2, HfI2, Hf(Me)2, Hf(Bn)2, Hf(allyl)2, Hf(CH2-tBu)2, Hf(1,3-pentadienyl), Hf(1,3-pentadienyl), Hf(2,4-hexadienyl), Hf(1,4-diphenyl-1,3-pentadienyl), Hf(CH2-Si(Me)3)2, Hf(OMe)2, Hf(OiPr)2, Hf(NMe2)2, Hf(OMs)2, Hf(OTs)2, Hf(OTf)2, and the like.

[0221] Me is methyl, Bn is benzyl, tBu is tert-butyl, Si(Me)3 is trimethylsilyl, OMe is methoxy, OiPr is isopropoxy, NMe2 is dimethylamino, OMs is methanesulfonate, OTs is p-toluenesulfonate, OTf is triflate.

[0222] According to the above, in the case of the 2-indenyl ring moiety being α-1 in [Table 1], the 1-indenyl ring moiety being β-5 in [Table 2], the indenyl ring moiety R 1 , R 6 and R 8 substituents are all γ-1 in [Table 3], the 2-indenyl ring moiety R 2 and R5 Substituents are each δ-1, 2-indenyl ring portion R in [Table 4] 3 and R 4 Substituents are each ε-1, 1-indenyl ring portion R in [Table 5] 7 Substituents are ζ-30, 1-indenyl ring portion R in [Table 6] 9 Substituents are δ-38, 1-indenyl ring portion R in [Table 4] 12 Substituents are a combination of δ-3, bridging portion is η-20 in [Table 7], and MXn of the metal portion is ZrCl2in [Table 4], and a compound represented by the following formula [6] is exemplified.

[0223]

[0224] Further, in a case where the 2-indenyl ring portion is α-1 in [Table 1], the 1-indenyl ring portion is β-2 in [Table 2], substituents are each γ-1, indenyl ring portion R in [Table 3] 1 , R 6 and R 8 Substituents are each γ-1, 2-indenyl ring portion R in [Table 3] 2 and R 5 Substituents are each δ-2, 2-indenyl ring portion R in [Table 4] 3 and R 4 Substituents are each ε-1, 1-indenyl ring portion R in [Table 5] 7 Substituents are a combination of ζ-1, bridging portion is η-4 in [Table 7], and MXn of the metal portion is Zr(NMe2)2in [Table 6], and a compound represented by the following formula [7] is exemplified.

[0225]

[0226] Further, in a case where the 2-indenyl ring portion is α-3 in [Table 1], the 1-indenyl ring portion is β-1 in [Table 2], substituents are each γ-2, indenyl ring portion R in [Table 3] 1 and R 6 Substituents are each γ-2, indenyl ring portion R in [Table 3] 2 , R 5 and R 12 Substituents are each δ-1, 1-indenyl ring portion R in [Table 4] 7 Substituents are ζ-12, 1-indenyl ring portion R in [Table 6] 8 Substituents are γ-1, 1-indenyl ring portion R in [Table 3] 9 Substituents are δ-42, 1-indenyl ring portion R in [Table 4] 10 Substituents are ε-3, 1-indenyl ring portion R in [Table 5] 11The following compound is an example of a compound represented by formula [8] when the substituent is ε-12 in [Table 5], the bridging part is η-31 in [Table 7], and the metal part MXn is HfMe2.

[0227]

[0228] Additionally, in the 2-indenyl ring portion, the α-1 and 1-indenyl ring portions in [Table 1] are represented, and the β-1 and 2-indenyl ring portions in [Table 2] are represented. 1 and R 6 All substituents are γ-1,2-indenyl ring moieties 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 All substituents are ε-1, 2-indenyl ring moieties R in [Table 5] 5 The substituent is the δ-2,1-indenyl ring moiety R in [Table 4]. 7 The substituents are the ζ-1, 1-indenyl ring moiety R in [Table 6]. 8 The substituents are the γ-9, 1-indenyl ring moiety R in [Table 3]. 9 and R 12 The following compound is an example of a compound represented by formula [9], wherein all substituents are δ-1 in [Table 4], the bridging part is η-29 in [Table 7], and the metal part MXn is Zr(1,3-pentadienyl).

[0229]

[0230] The aforementioned transition metal compound (1) can be manufactured using existing known methods, and the manufacturing method is not particularly limited.

[0231] The substituted indene compound as a starting material can be produced using a publicly known method, and the production method is not particularly limited. As the publicly known production method, for example, the production methods disclosed in “Organometallics 1994, 13, 954.”, “Organometallics 2006, 25, 1217.”, Japanese Patent Application Laid-Open No. 2006-509059, “Bioorg. Med. Chem. 2008, 16, 7399.”, WO 2009 / 080216, “Organometallics 2011, 30, 5744.”, Japanese Patent Application Laid-Open No. 2011-500800, “Organometallics 2012, 31, 4962.”, “Chem. Eur. J. 2012, 18, 4174.”, Japanese Patent Application Laid-Open No. 2012-012307, Japanese Patent Application Laid-Open No. 2012-121882, Japanese Patent Application Laid-Open No. 2014-196319, Japanese Patent Application Laid-Open No. 2014-513735, Japanese Patent Application Laid-Open No. 2015-063495, Japanese Patent Application Laid-Open No. 2016-501952, Japanese Patent Application Laid-Open No. 2019-059933, and the like can be exemplified.

[0232] As the publicly known production method of the transition metal compound (1) and the precursor compound (ligand), for example, “Macromolecules 2001, 34, 2072.”, “Macromolecules 2003, 36, 9325.”, “Organometallics 2004, 23, 5332.”, “Eur. J. Inorg. Chem. 2005, 1003.”, “Eur. J. Inorg. Chem. 2009, 1759.”, and the like can be exemplified.

[0233] Further, in the above-described transition metal compound (1), there are two directions (front face and back face) of the face of the indenyl ring portion sandwiching the bridging portion and binding to the central metal. Therefore, in the case where the 2-indenyl ring portion does not have a symmetrical face, for example, there are two structural isomers represented by the following general formulae [10a] or [10b].

[0234]

[0235] Similarly, in the case where the substituent R 13 is different from R 14 , for example, there are also two structural isomers represented by the following general formulae [11a] or [11b].

[0236]

[0237] The purification, fractionation or selective production of the structural isomer mixture can be performed using a known method, and the production method is not particularly limited. As the known production method, in addition to the methods listed as the production method of the above-mentioned transition metal compound (1), the production methods disclosed in Japanese Patent Application Laid-Open No. 10-109996, "Organometallics 1999, 18, 5347.", "Organometallics 2012, 31, 4340.", Japanese Patent Application Laid-Open No. 2011-502192, and the like can be listed.

[0238] Among the above-mentioned transition metal compounds (1), the transition metal compound can be used alone as one kind, or two or more kinds can be used in combination, a structural isomer mixture can be used, one kind of structural isomer can be used alone, or two or more kinds of structural isomer mixtures can be used. As described above, according to the present application, as the transition metal compound constituting the catalyst for olefin polymerization, the above-mentioned transition metal compound (1) can be used alone to produce an ethylene-based polymer into which a large amount of long chain branching is introduced with high catalytic activity, and within a range not impairing this effect, one or more kinds of transition metal compounds other than the above-mentioned transition metal compound (1) can be used as the above-mentioned transition metal compound. At this time, the transition metal compound (1) can be in any of the above-mentioned modes.

[0239] < Solid carrier (S) >

[0240] The solid carrier (S) contained in the catalyst (X) for olefin polymerization is an inorganic compound or an organic compound, and is a solid in a particulate or fine particulate form.

[0241] As the inorganic compound used as the above-mentioned solid carrier (S), a porous oxide, a solid aluminoxane compound, an inorganic chloride, clay, a clay mineral, or an ion-exchangeable layered compound can be listed.

[0242] As the above-mentioned porous oxide, SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, and ThO2, or the like, or a composite or mixture containing them can be used, and specifically, natural or synthetic zeolite, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, and SiO2-TiO2-MgO, and the like can be used. Among these, a substance in which SiO2 is the main component is preferred.

[0243] The above porous oxide can contain a small amount of carbonates, sulfates, nitrates, oxide components of Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, Li2O, and the like.

[0244] The properties of such porous oxides vary depending on the kind and the manufacturing method thereof, and the particle diameter of the solid carrier (S) is usually 0.2 to 300 μm, preferably 1 to 200 μm, the specific surface area is usually 50 to 1200 m 2 / g, preferably 100 to 1000 m 2 / g, and the pore volume is usually 0.3 to 30 cm 3 / g. Such a carrier can be used after being fired at, for example, 100 to 1000°C, preferably 150 to 700°C, as needed.

[0245] As the above solid aluminoxane compound, there can be mentioned an aluminoxane having a structure represented by the following general formula (S-a), an aluminoxane having a structure represented by the following general formula (S-b), and an aluminoxane having a structure in which a repeating unit represented by the following general formula (S-c) and a repeating unit represented by the following general formula (S-d) are present, and the like.

[0246]

[0247] In the above formulas (S-a) to (S-d), 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 methyl, ethyl, propyl, isopropyl, isopropenyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclohexyl, cyclooctyl, phenyl, tolyl, ethylphenyl, and the like, and are preferably methyl, ethyl, isobutyl, and particularly preferably methyl. Also, a part of R e may be substituted with a halogen atom such as chlorine or bromine, and the halogen content can be 40% by weight or less based on R e . The straight line in the above formulas (S-c) and (S-d) not connected to an atom represents a bond to another atom not shown.

[0248] In the above formulas (S-a) and (S-b), r represents an integer of 2 to 500, preferably 6 to 300, and particularly preferably 10 to 100. In the above formulas (S-c) and (S-d), s and t each represent an integer of 1 or more. r, s, and t are selected so that the above aluminoxane can substantially maintain a solid state under the reaction environment employed.

[0249] The solid aluminoxane compound described above is different from the known carriers for olefin polymerization catalysts in that it does not contain inorganic solid components such as silica and alumina, and organic polymer components such as polyethylene and polystyrene, and is a solidified substance in which an aluminum alkyl compound is the main component. The "solid" means that the aluminoxane component substantially maintains a solid state under the reaction environment employed. More specifically, it means that the aluminoxane component substantially maintains a solid state when the above component (A) is brought into contact with the aluminoxane component to produce a catalyst for the polymerization of an olefin (e.g., a catalyst for the polymerization of ethylene), and when the polymerization of an olefin (e.g., ethylene) is carried out using the catalyst for the polymerization of an olefin thus produced (e.g., suspension polymerization).

[0250] Whether the aluminoxane component described above is in a solid state can be most easily confirmed by visual observation, but in many cases it is difficult to confirm by visual observation, for example, during polymerization. In this case, it can be judged, for example, from the properties of the polymer powder obtained after polymerization or the state of adhesion on the reactor, and the like. Conversely, if the properties of the polymer powder are good and the adhesion on the reactor is small, even if a small amount of the aluminoxane component described above dissolves out under the polymerization environment, it does not depart from the gist of the present application. As an index for judging the properties of the polymer powder, the bulk density, the particle shape, the surface shape, the degree of presence of amorphous polymer, and the like can be listed, and from a quantitative viewpoint, the bulk density of the polymer is preferred. The bulk density described above is usually in the range of 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

[0251] The solubility ratio of the solid aluminoxane compound described above in n-hexane maintained at a temperature of 25°C is usually in the range of 0 to 40 mol%, preferably 0 to 20 mol%, and particularly preferably 0 to 10 mol%.

[0252] The solubility ratio described above is determined by adding 2 g of the solid aluminoxane compound carrier to 50 ml of n-hexane maintained at 25°C, stirring for 2 hours, then separating the solution fraction using a G-4 glass filter, and measuring the aluminum concentration in the filtrate. Thus, the solubility ratio is determined as the ratio of the aluminum atoms present in the above filtrate to the amount of aluminum atoms corresponding to 2 g of the aluminoxane used.

[0253] As the solid aluminoxane compound described above, a publicly known solid aluminoxane can be used without any limitation, and a solid polyaluminoxane composition described in International Publication No. 2014 / 123212, for example, can also be used. As publicly known production methods, for example, production methods described in Japanese Patent No. 7-42301, Japanese Patent Laid-Open No. 6-220126, Japanese Patent Laid-Open No. 6-220128, Japanese Patent Laid-Open No. 11-140113, Japanese Patent Laid-Open No. 11-310607, Japanese Patent Laid-Open No. 2000-38410, Japanese Patent Laid-Open No. 2000-95810, International Publication No. 2010 / 55652, and the like can be exemplified.

[0254] The average particle diameter of the solid aluminoxane compound described above is usually 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 can be obtained by observing the particles with a scanning electron microscope, measuring the particle diameters of 100 or more particles, and performing weight averaging. First, with respect to the particle diameter d of each particle, the length is measured with two parallel lines sandwiching the particle image in the horizontal direction and the vertical direction, and is obtained using the following formula.

[0255] Particle diameter d = ((horizontal direction length) 2 + (vertical direction length) 2 ) 0.5

[0256] Next, with respect to the weight average particle diameter of the solid aluminoxane compound, the particle diameter d obtained above and the number of particles n are used to obtain the following formula.

[0257] Average particle diameter = ∑nd 4 / ∑nd 3

[0258] The specific surface area of the solid aluminoxane compound described above is preferably 50 to 1,000 m 2 / g, and more preferably 100 to 800 m 2 / g. The pore volume is preferably 0.1 to 2.5 cm 3 / g.

[0259] As the inorganic halide described above, for example, MgCl2, MgBr2, MnCl2, MnBr2, and the like can be exemplified. The inorganic halide can be used directly, or can be pulverized using a ball mill or a vibration mill and then used. Also, a substance in which the inorganic halide is dissolved in a solvent such as alcohol and then precipitated in a fine particle form using a precipitant can also be used.

[0260] Clay is typically composed primarily of clay minerals. Additionally, ion-exchangeable layered compounds are crystalline compounds with a parallel, stacked structure formed by ionic bonds and other weak bonding forces, in which ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. Furthermore, these clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products; synthetic compounds can also be used.

[0261] In addition, examples of clay, clay minerals, or ion-exchangeable layered compounds include clay, clay minerals, and ionic crystalline compounds with layered crystalline structures such as hexagonal close-packed type, antimony type, CdCl2 type, and CdI2 type.

[0262] Examples of such clays and clay minerals include kaolin, bentonite, wood-knot clay, frog-eye clay, diaspore, ferrosilicon, pyrophyllite, mica, montmorillonite, vermiculite, chlorite, palygorskite, kaolinite, perlite, dickite, halloysite, etc. Examples of ion-exchangeable layered compounds include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O.

[0263] Such clays, clay minerals, or ion-exchangeable layered compounds preferably have their radius measured using the mercury infiltration method. The above-mentioned materials have a pore volume of 0.1 cc / g or higher, with materials having a pore volume of 0.3 to 5 cc / g being particularly preferred. Here, regarding the pore volume, the mercury injection method using a mercury porosimeter is used to determine the pore radius. The range was measured. The radius was used for measurement. When using substances with a pore volume of less than 0.1 cc / g as carriers, there is a tendency to find it difficult to obtain high polymerization activity.

[0264] It is also preferable to perform chemical treatment on the clay and clay mineral. As the chemical treatment, surface treatment for removing impurities adhering to the surface, treatment for imparting an effect on the crystal structure of the clay, and the like can be used. As the chemical treatment, acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like can be specifically mentioned. In the acid treatment, in addition to being able to remove impurities from the surface, it is also possible to increase the surface area by dissolving cations such as Al, Fe, and Mg in the crystal structure. In the alkali treatment, the crystal structure of the clay is destroyed, and a change in the clay structure is imparted. In addition, in the salt treatment and the organic matter treatment, it is possible to form ion complexes, molecular complexes, organic derivatives, and the like, and change the surface area or the interlayer distance.

[0265] The ion-exchangeable layered compound can be a layered compound in a state in which the interlayer exchangeable ions are exchanged with other large ions by ion exchangeability, so that the interlayer is enlarged. Such a large ion assumes the role of a pillar supporting the layered structure, and is generally referred to as a pillar. In addition, the case in which such other substances are introduced into the interlayer of the layered compound is referred to as intercalation. As the guest compound for performing intercalation, cationic inorganic compounds such as TiCI4and ZrCI4, metal alkoxides (R is a hydrocarbon group or the like) such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3, [Al 13 O4(OH) 24 ] 7+ , [Zr4(OH) 14 ] 2+ , [Fe3O(OCOCH3)6] + and the like. These compounds can be used alone, or two or more thereof can be used in combination. In addition, when these compounds are intercalated, a polymer obtained by hydrolysis of metal alkoxides (R is a hydrocarbon group or the like) such as Si(OR)4, Al(OR)3, and Ge(OR)4, a colloidal inorganic compound such as SiO2, and the like can also be present. In addition, as the pillar, oxides and the like obtained by heating and dehydrating the layered compound after intercalation of the above metal hydroxide ions can be mentioned.

[0266] The clay, the clay mineral, and the ion-exchangeable layered compound can be used as they are, or can be used after being subjected to processes such as ball milling and sieving. In addition, they can also be used after being rehydrated and adsorbed, or after being subjected to a heating and dehydration process. Furthermore, one kind can be used alone, or two or more thereof can be used in combination.

[0267] As organic compounds used as the aforementioned solid support (S), examples include particulate or microparticle solids with a particle size in the range of 10 to 300 μm. Specific examples of the aforementioned organic compounds include polymers mainly composed of olefins with 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or polymers or reactants mainly composed of vinylcyclohexane, styrene, and divinylbenzene, as well as particulate or microparticle solids of their modified forms.

[0268] From the viewpoint of preventing foreign matter during molding, porous oxides are preferred as the aforementioned solid carrier (S).

[0269] <Ingredient (C)>

[0270] The catalyst (X) for olefin polymerization preferably further contains component (C), which is at least one compound selected from organometallic compounds (c-1), organoaluminum oxide compounds (c-2), and compounds (c-3) that react with component (A) to form ion pairs, as shown in the following general formulas (3) to (5).

[0271] R a m Al(OR b ) n H p X q …(3)

[0272] In equation (3), R a and R b Each of the following groups independently represents a hydrocarbon group with 1 to 15 carbon atoms, X represents a halogen atom, m is a number of 0 < m ≤ 3, n is a number of 0 ≤ n < 3, p is a number of 0 ≤ p < 3, q ​​is a number of 0 ≤ q < 3, and m + n + p + q = 3.

[0273] M a AlR a 4…(4)

[0274] In equation (4), M a Represents Li, Na, or K, R a This indicates a hydrocarbon group with 1 to 15 carbon atoms.

[0275] R a r M b R b s X t …(5)

[0276] In equation (5), R a and R brespectively independently represent a hydrocarbon group having 1 or more and 15 or less carbon atoms, M b is selected from Mg, Zn and Cd, X represents a halogen atom, r is 0 < r < 2, s is 0 < s < 1, t is 0 < t < 1, and r + s + t = 2.

[0277] In the above organic metal compound (c-1), a compound represented by the above formula (3) is preferable, and specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, and the like can be exemplified.

[0278] dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, and the like;

[0279] alkylaluminum sesquihalide such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, and the like;

[0280] alkylaluminum dihalide such as methyldichloroaluminum, ethyldichloroaluminum, isopropylaluminum dichloride, ethyldibromoaluminum, and the like;

[0281] hydrogenated alkylaluminum such as dihydrogenated methylaluminum, dihydrogenated ethylaluminum, dihydrogenated isopropylaluminum, dihydrogenated n-butylaluminum, dihydrogenated isobutylaluminum, dihydrogenated isohexylaluminum, dihydrogenated phenylaluminum, dihydrogenated cyclohexylaluminum, dihydrogenated sec-heptylaluminum, dihydrogenated sec-nonylaluminum, and the like;

[0282] alkoxydialkylaluminum such as ethoxydimethylaluminum, ethoxydiethylaluminum, methoxydiisopropylaluminum, ethoxydiisobutylaluminum, and the like.

[0283] As examples of the above formula (4), lithium aluminum hydride and the like can be exemplified. As examples of the above formula (5), dialkylzinc compounds described in Japanese Patent Application Publication No. 2003-171412 and the like can be exemplified, and the use in combination with a phenol compound and the like is also possible.

[0284] As the above organoaluminum oxy compound (c-2), an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and aluminoxane prepared from trimethylaluminum or triisobutylaluminum, for example, methylaluminoxane is particularly preferable. Such an organoaluminum oxy compound can be used alone as one kind or in combination of two or more kinds.

[0285] As the compound (c-3) which forms an ion pair with the above-mentioned component (A), a Lewis acid, an ionic compound, a borane compound, a carborane compound, a heteropoly compound, and a homopoly compound, and the like described in Japanese Patent Laid-Open No. 501950 / 1995, Japanese Patent Laid-Open No. 502036 / 1995, Japanese Patent Laid-Open No. 3-179005, Japanese Patent Laid-Open No. 3-179006, Japanese Patent Laid-Open No. 3-207703, Japanese Patent Laid-Open No. 3-207704, and US 5321106, and the like can be used.

[0286] The catalyst (X) for the polymerization of an olefin compound is not only very high in polymerization activity for an olefin compound when an organoaluminum compound such as methylaluminoxane is used as a cocatalyst component, but also reacts with active hydrogen in a solid carrier to easily produce a solid carrier component containing the cocatalyst component, and therefore it is preferred that the component (C) contains at least the organoaluminum compound (c-2).

[0287] <Method of using each component and order of addition>

[0288] The catalyst (X) for the polymerization of an olefin compound can be produced by mixing and contacting the component (A) and the component (S), and optionally the component (C) in an unreactive hydrocarbon.

[0289] As the method of contacting each component, in view of the order of contacting, for example, the following can be listed:

[0290] (i) a method of contacting the component (S) with the component (A);

[0291] (ii) a method of contacting the component (S) with the component (C), and then contacting the component (A);

[0292] (iii) a method of contacting the component (A) with the component (C), and then contacting the component (S);

[0293] (iv) a method of contacting the component (S) with the component (C), and then contacting a mixture of the component (A) and the component (C);

[0294] (v) a method of contacting the component (S) with the component (C), and then contacting a mixture of the component (A) and the component (C), and the like.

[0295] In the case where a plurality of components (C) are used, the components (C) can be the same as or different from each other. Among the above-mentioned methods, (i), (ii), and (iii) are preferred.

[0296] In each of the above methods showing the contact sequence, in the process including the contact of the component (S) with the component (C) and the process including the contact of the component (S) with the component (A), by allowing the component (G) to coexist, the fouling in the polymerization reaction is suppressed or the particle properties of the resulting polymer are improved. As the component (G), a compound having a polar functional group can be used, preferably a non-ion surfactant, more preferably a polyoxyalkylene block, a higher aliphatic amide, a polyoxyalkylene, a polyoxyalkylene alkyl ether, an alkyl diethanol amine, a polyoxyalkylene alkyl amine, a glycerin fatty acid ester, an N-acyl amino acid. One kind thereof can be used, or two or more kinds thereof can be used in combination.

[0297] As the solvent used in the preparation of the catalyst (X) for the polymerization of an olefin, an inert hydrocarbon solvent can be exemplified, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as chloroethylene, chlorobenzene, dichloromethane, or a mixture thereof, or the like.

[0298] When the component (C) is contacted with the component (S), chemical bonding occurs by the reaction of the reaction site in the component (C) with the reaction site in the component (S), and a contact of the component (C) with the component (S) is formed. The contact time of the component (C) with the component (S) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is usually -50 to 200°C, preferably -20 to 120°C. In the case where the initial contact of the component (C) with the component (S) is performed drastically, in most cases, the component (S) is disintegrated due to the reaction heat or the reaction energy, and the form of the resulting solid catalyst component is deteriorated, which makes it difficult to continue the operation due to the poor form of the polymer when it is used for the polymerization. Therefore, at the initial contact of the component (C) with the component (S), in order to suppress the reaction heat, it is preferable to contact at a lower temperature, or to control the reaction heat so that the reaction can be performed at a rate at which the initial contact temperature can be maintained. The same applies to the case where the component (C) is contacted with the component (S) and then the component (C) is re-contacted. The contact weight ratio of the component (C) to the component (S) [weight of the component (C) / weight of the component (S)] can be arbitrarily selected, and in the case where the contact weight ratio is high, more component (A) can be contacted, and the catalytic activity per unit weight of the solid catalyst component can be improved.

[0299] The contact weight ratio of the component (C) to the component (S) [weight of the component (C) / weight of the component (S)] is preferably 0.05 to 3.0, particularly preferably 0.1 to 2.0.

[0300] The contact time when the contact of component (C) and component (S) with component (A) is usually 1 minute to 20 hours, preferably 1 minute to 10 hours, and the contact temperature is usually in the range of -50 to 200°C, preferably -50 to 100°C.

[0301] Component (C-1) is usually used in an amount such that the molar ratio [(C-1) / M] of component (C-1) to the total transition metal atoms (M) in component (A) becomes 0.01 to 100,000, preferably 0.05 to 50,000.

[0302] Component (C-2) is usually used in an amount such that the molar ratio [(C-2) / M] of component (C-2) (aluminum atom conversion) to the total transition metal atoms (M) in component (A) becomes 10 to 500,000, preferably 20 to 100,000.

[0303] Component (C-3) is usually used in an amount such that the molar ratio [(C-3) / M] of component (C-3) to the total transition metal atoms (M) in component (A) becomes 1 to 10, preferably 1 to 5.

[0304] The ratio of component (C) to the total transition metal atoms (M) in component (A) can be found by inductively coupled plasma emission spectrometry (ICP analysis). In the polymerization of ethylene, the olefin polymerization catalyst (X) can be used directly, or the olefin polymerization catalyst can be used after being pre-polymerized with an olefin to form a pre-polymerized catalyst (XP).

[0305] The pre-polymerized catalyst (XP) can be produced by pre-polymerizing ethylene or the like in the presence of the olefin polymerization catalyst (X) in an inert hydrocarbon solvent, and can be performed in any method of batch, semi-continuous, or continuous, and can be performed under reduced pressure, normal pressure, or elevated pressure. Also, it is desirable to produce the pre-polymerized catalyst (XP) in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g, per 1 g of the solid catalyst component.

[0306] After the pre-polymerized catalyst (XP) produced in the inert hydrocarbon solvent is separated from the suspension, it is again suspended in the inert hydrocarbon, ethylene can be introduced into the resulting suspension, and ethylene can also be introduced after drying.

[0307] The pre-polymerization temperature is -20 to 80°C, preferably 0 to 60°C, and the pre-polymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours. The pre-polymerization preferably uses an olefin in which ethylene is the main component.

[0308] As the form of the solid catalyst component used as the prepolymerization, the forms described above can be used without any limitation. Also, component (C) is used as needed, 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 of aluminum atoms (Al) in component (C) to transition metal atoms (M) in component (A) (Al / M) is 0.1 to 10,000, preferably 0.5 to 5,000.

[0309] The concentration of the catalyst (X) for olefin polymerization in the prepolymerization system is usually 1 to 1,000 g / L, more desirably 10 to 500 g / L, in terms of the catalyst for olefin polymerization / polymerization volume ratio. In the prepolymerization, the above component (G) can be allowed to coexist in order to suppress fouling or improve the particle properties.

[0310] In addition, in order to improve the fluidity of the prepolymerization catalyst (XP), suppress the generation of hot spots, lumps or polymer blocks during polymerization, component (G) can be brought into contact with the prepolymerization catalyst (XP) temporarily generated by the prepolymerization.

[0311] The temperature at the time of contact with the above 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.

[0312] At the time of contact of the catalyst (X) for olefin polymerization with component (G), component (G) is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, more desirably 0.4 to 5 parts by weight, relative to 100 parts by weight of the catalyst (X) for olefin polymerization.

[0313] The mixing contact of the catalyst (X) for olefin polymerization with component (G) can be carried out in an inert hydrocarbon solvent, and the same solvents as described above can be used as the inert hydrocarbon solvent.

[0314] In the method for producing an ethylene-based polymer according to the present application, as the catalyst (X) for olefin polymerization, a catalyst obtained by drying the prepolymerization catalyst (XP) (hereinafter also referred to as "dried prepolymerization catalyst") can be used. The drying of the prepolymerization catalyst (XP) is usually carried out after removing the hydrocarbon as the dispersion medium from the obtained suspension of the prepolymerization catalyst by filtration or the like.

[0315] The drying of the prepolymerization catalyst (XP) is carried out by keeping the prepolymerization catalyst (XP) at a temperature of 70°C or lower, preferably in the range of 20 to 50°C, under the flow of an inert gas. The volatile component content of the resulting dried prepolymerization catalyst is desirably 2.0% by weight or less, preferably 1.0% by weight or less. The less the volatile component content of the dried prepolymerization catalyst, the better, and there is no particular lower limit, but in practice, it is 0.001% by weight. The drying time also depends on the drying temperature, and is usually 1 to 48 hours.

[0316] The dried prepolymerization catalyst described above has excellent fluidity, and thus can be stably supplied to a polymerization reactor. Also, when the dried prepolymerization catalyst described above is used, since a solvent for suspension can not be involved in the gas phase polymerization system, the polymerization can be stably carried out.

[0317] [Method for producing ethylene-based polymer]

[0318] Next, a method for producing an ethylene-based polymer according to the present application will be described. An ethylene-based polymer is obtained by polymerizing (homopolymerizing or copolymerizing) ethylene in the presence of the above-described catalyst for olefin polymerization (X). By using the catalyst for olefin polymerization (X), an ethylene-based copolymer having high polymerization activity, excellent molding processability and mechanical strength, and a large amount of long-chain branches at a low density can be efficiently produced. The ethylene-based polymer of the present application refers to a polymer having an ethylene content of 10 mol% or more in the polymer.

[0319] In the present application, the 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 it is preferable to use the above-described prepolymerization catalyst (XP) in the suspension polymerization method and the gas phase polymerization method.

[0320] As specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chlorinated ethylene and chlorobenzene; dichloromethane; and mixtures thereof can be given. In addition, in the liquid phase polymerization method, the olefin itself can be used as a solvent.

[0321] When the polymerization of ethylene is carried out using the above-described catalyst for olefin polymerization, it is generally used in an amount such that the component (A) becomes 1 x 10 -12 to 1 x 10 -1 mole per 1 liter of the reaction volume, preferably 1 x 10 -8 to 1 x 10 -2 mole. Also, it is preferable to use the component (C), particularly the organoaluminum compound represented by formula (3) in (c-1).

[0322] Further, the polymerization temperature of ethylene using the above-described 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 reaction can be carried out in any method of batch, semi-continuous, or continuous under the conditions of a polymerization pressure of usually normal pressure to 100 kgf / cm 2 , preferably normal pressure to 50 kgf / cm 2 . Further, the polymerization can be carried out in two or more stages under different reaction conditions.

[0323] The molecular weight of the obtained polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Generally, the more the low molecular weight component, the more the adhesion to the wall of the polymerization reactor and the stirring blade, and the more the burden on the cleaning process, and sometimes the production rate is reduced. In the polymerization, in order to suppress fouling or improve the particle properties, the component (G) can be co-presented.

[0324] Further, in the present application, the monomer to be 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. As specific examples of the α-olefins having 4 to 10 carbon atoms, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene can be mentioned. Further, within the range not impairing the effects of the present application, monomers other than ethylene and the α-olefins having 4 to 10 carbon atoms can be supplied, or can not be supplied.

[0325] (Thermoplastic resin composition (Y) and the like)

[0326] By blending the ethylene-α-olefin copolymer (A) according to the present application with a thermoplastic resin other than the ethylene-α-olefin copolymer (A) according to the present application (hereinafter referred to as "other thermoplastic resin (RY)"), a thermoplastic resin composition (Y) excellent in moldability and excellent in mechanical strength can be obtained. The blending ratio of the ethylene-α-olefin copolymer (A) according to the present application to the other thermoplastic resin (RY) (mass of the ethylene-α-olefin copolymer (A) / mass of the other thermoplastic resin (RY)) is usually in the range of 99.9 / 0.1 to 0.1 / 99.9.

[0327] As the other thermoplastic resin (RY), crystalline thermoplastic resins such as polyolefins, polyamides, polyesters, and polyacetals; non-crystalline thermoplastic resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate, polyphenylene ether, and polyacrylate can be used. It is also preferable to use polyvinyl chloride.

[0328] As the above polyolefin, specifically, ethylene-based polymers, propylene-based polymers, butene-based polymers, 4-methyl-l-pentene-based polymers, 3-methyl-l-butene-based polymers, hexene-based polymers, and the like can be exemplified. Among them, ethylene-based polymers, propylene-based polymers, and 4-methyl-l-pentene-based polymers are preferable, and in the case of ethylene-based polymers, conventional ethylene-based polymers can be used, or ethylene-vinyl copolymers containing a polar group can be used, and more preferably, conventional ethylene-based polymers are used. The ethylene-based polymers and propylene-based polymers can be those containing monomers derived from biomass.

[0329] In the ethylene-a-olefin copolymer (A) of the present application, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifog agent, a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an anti-aging agent, a hydrochloric acid absorber, an antioxidant, and the like can be added as needed without impairing the object of the present application.

[0330] (Ethylene-based resin composition (Z))

[0331] As one mode of the thermoplastic resin composition (Y) of the present application, an ethylene-based resin composition (Z) in which the above other thermoplastic resin (RY) is an ethylene-a-olefin copolymer (B) described below, and the ratio of the above ethylene-a-olefin copolymer (A) to the above ethylene-a-olefin copolymer (B) is within a prescribed range can be exemplified.

[0332] (Ethylene-α-olefin copolymer (B))

[0333] The above ethylene-a-olefin copolymer (B) is a copolymer of ethylene and an a-olefin having 4 to 10 carbon atoms, preferably an a-olefin having 6 to 10 carbon atoms. As the a-olefin having 4 to 10 carbon atoms to be copolymerized with ethylene, 1-butene, 1-hexene, 4-methyl-l-pentene, 1-octene, 1-decene, and the like can be exemplified.

[0334] The ethylene-a-olefin copolymer (B) has the following (a) to (d) properties.

[0335] (a) The density is in the range of 890 kg / m 3 930 kg / m 3 900 kg / m 3 925 kg / m 3 905 kg / m 3 920 kg / m 3 the range of below.

[0336] When the density is above the lower limit, the film surface formed by molding the ethylene-based resin composition (Z) has less stickiness; when the density is below the upper limit, the film formed by molding the ethylene-based resin composition (Z) has good impact strength, heat sealing strength, and good mechanical strength such as the tear strength of the bag made from the film.

[0337] (b) The melt flow rate (MFR) is in the range of 0.1 g / 10 min to 20 g / 10 min, preferably 0.5 g / 10 min to 10 g / 10 min, and more preferably 0.8 g / 10 min to 8.0 g / 10 min.

[0338] When the melt flow rate (MFR) is above the lower limit, the film formed from the vinyl resin composition (Z) has fewer fisheyes and a better appearance. When the melt flow rate (MFR) is below the upper limit, the vinyl resin composition (Z) has high melt tension and good formability, including melt film stability.

[0339] (c) Melt tension at 190°C [MT(g)] and shear viscosity at 200°C and angular velocity of 1.0 rad / s [η] * (P)〕(P is Poise) ratio〔MT / η * (g / P)〕 at 1.0×10 -6 Above 1.0×10 -4 The following is preferred: 5.0×10 -6 Above 8.0×10 -5 Below, more preferably 1.0×10 -5 Above 6.0×10 -5 Within the following range.

[0340] MT / η * Above the lower limit, the resulting ethylene-α-olefin copolymer (B) exhibits high melt tension relative to its molecular weight, resulting in excellent moldability of the ethylene-based resin composition (Z). MT / η * Below the upper limit, the ethylene-based resin composition (Z) exhibits excellent mechanical strength. MT / η * The MT / η ratio depends on the long-branch content of the vinyl polymer; the higher the long-branch content, the higher the MT / η ratio. * The larger the value, the lower the content of long-branched chains, and the higher the MT / η ratio. * The smaller.

[0341] Melt tension at 190°C [MT(g)] and shear viscosity at 200°C and angular velocity of 1.0 rad / s [η] * (P)〕 is measured in the same way as (3) above.

[0342] (d) the amount of components having a Log molecular weight of 5.8 or more in the molecular weight distribution curve obtained by GPC is in the range of 0.01% or more and 5.0% or less, preferably 0.01% or more and 4.0% or less, more preferably 0.01% or more and 3.0% or less.

[0343] When the amount of components having a Log molecular weight of 5.8 or more in the molecular weight distribution curve obtained by GPC is below the upper limit, the entanglement between molecules due to high molecular weight molecular chains in the ethylene-a-olefin copolymer (B) is easily resolved, so the molecules in the ethylene-based resin composition (Z) are easily relaxed. Therefore, the surface of a film containing the ethylene-based resin composition (Z) has less surface irregularities and has excellent transparency. In addition, when it is above the lower limit, the moldability of the ethylene-based resin composition (Z) is excellent.

[0344] The amount of components having a Log molecular weight of 5.8 or more in the molecular weight distribution curve obtained by GPC was calculated by measuring using gel permeation chromatography under the following conditions. In the examples described later, the following device or the like was used.

[0345] [Device or the like used]

[0346] Measurement device: HLC-8321 GPC / HT type (manufactured by Tosoh Corporation)

[0347] Data processing software: Empower 3 (manufactured by Waters Corporation)

[0348] Column: 2 x TSKgel GMH6-HT + 2 x TSKgel GMH6-HTL

[0349] (All are 7.5 mm I.D. x 30 cm, manufactured by Tosoh Corporation)

[0350] Polystyrene: monodisperse polystyrene (manufactured by Tosoh Corporation); #3 std set

[0351] [Measurement conditions]

[0352] Column temperature: 140°C

[0353] Mobile phase: o-dichlorobenzene (containing 0.025% BHT)

[0354] Detector: differential refractometer

[0355] Flow rate: 1.0 ml / minute

[0356] Sample concentration: 0.1% (w / v)

[0357] Injection amount: 400 μL

[0358] Sampling time interval: 0.5 seconds

[0359] Column calibration: Polystyrene

[0360] Molecular weight conversion: PE conversion / universal calibration method

[0361] The percentage of components with a Log molecular weight of 5.8 or higher is calculated based on the obtained molecular weight distribution curve.

[0362] <Method for manufacturing ethylene-α-olefin copolymer (B)>

[0363] The ethylene-α-olefin copolymer (B) described above can be obtained by polymerizing ethylene with an α-olefin having 4 to 10 carbon atoms. Any copolymer that satisfies the above conditions is acceptable, and the polymerization catalyst and polymerization conditions used are not particularly limited. For example, commercially available products such as linear low-density polyethylene, ethylene-α-olefin copolymers, or high-density polyethylene can be used as the ethylene-α-olefin copolymer (B). Specifically, products that meet conditions (a) to (d) can be selected from products such as LLDPE Evolue (registered trademark) and ULTZEX (registered trademark) manufactured by Priman Polymers Co., Ltd.

[0364] <Ethylene-based resin composition (Z)>

[0365] The ethylene-based resin composition (Z) of the present invention contains the above-mentioned ethylene-α-olefin copolymer (A) and the above-mentioned ethylene-α-olefin copolymer (B), wherein the mass fraction (W) of the above-mentioned ethylene-α-olefin copolymer (A) is... A The mass fraction (W) of the above-mentioned ethylene-α-olefin copolymer (B) and the above-mentioned ethylene-α-olefin copolymer (B) B The total is set at 100% by mass, W A 5-90% by weight, W B It is 10–95% by weight. Here, W A Preferably, it is 10 to 80% by weight, more preferably 20 to 70% by weight. Within this range, the vinyl resin composition (Z) exhibits excellent moldability and mechanical strength, and the film formed from the vinyl resin composition (Z) has excellent transparency.

[0366] In addition, the ethylene-based resin composition (Z) according to the present application can be composed substantially only of the above-described ethylene-α-olefin copolymer (A) and the above-described ethylene-α-olefin copolymer (B), but is not limited thereto, and can contain a thermoplastic resin other than the above-described ethylene-α-olefin copolymer (A) and the above-described ethylene-α-olefin copolymer (B) (hereinafter referred to as "another thermoplastic resin (RZ)") in addition to the above-described ethylene-α-olefin copolymer (A) and the above-described ethylene-α-olefin copolymer (B). By blending the "another thermoplastic resin (RZ)" in the above-described ethylene-α-olefin copolymer (A) and the above-described ethylene-α-olefin copolymer (B), the ethylene-based resin composition (Z) obtained as the thermoplastic resin composition (Y) is excellent in moldability and mechanical strength.

[0367] The blending ratio of the total of the above-described ethylene-α-olefin copolymer (A) and the above-described ethylene-α-olefin copolymer (B) to the "another thermoplastic resin (RZ)" (total mass of ethylene-α-olefin copolymer (A) and ethylene-α-olefin copolymer (B) / mass of another thermoplastic resin (RZ)) 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.

[0368] (Other thermoplastic resin (RZ))

[0369] As the above-described "another thermoplastic resin (RZ)", the resins exemplified as the above-described "another thermoplastic resin (RY)" can be used.

[0370] In the ethylene-based resin composition (Z) according to the present application, the above-described "another thermoplastic resin (RZ)" can be blended as needed within a range not impairing the object of the present application.

[0371] The total blending amount of the additives is usually 10 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the total of the components other than the additives in the ethylene-based resin composition (Z).

[0372] <Manufacturing method of ethylene-based resin composition (Z)>

[0373] The ethylene-based resin composition (Z) can be manufactured by melt-blending the aforementioned ethylene-α-olefin copolymer (A) and the aforementioned ethylene-α-olefin copolymer (B), or by dry-blending the granules obtained from granulating the ethylene-α-olefin copolymer (A) with the granules of the ethylene-α-olefin copolymer (B). When manufacturing by melt blending, a continuous extruder or a closed mixer can be used. Examples include single-screw extruders, twin-screw extruders, mixing rollers, Banbury mixers, kneaders, etc. Among these, single-screw extruders and / or twin-screw extruders are preferred from the viewpoints of economy and processing efficiency.

[0374] Here, in the above-mentioned melt mixing and dry blending, in addition to the above-mentioned ethylene-α-olefin copolymer (A) and ethylene-α-olefin copolymer (B), the above-mentioned "other thermoplastic resins" may also be blended. Furthermore, in addition to the "other thermoplastic resins", the above-mentioned additives may be further added, or the above-mentioned additives may be further added to replace the "other thermoplastic resins".

[0375] There is no particular limitation on the order in which the above-mentioned "other thermoplastic resins (RZ)" and the above-mentioned additives are added. For example, the above-mentioned "other thermoplastic resins (RZ)" and the above-mentioned additives may be blended simultaneously with one or both of the above-mentioned ethylene-α-olefin copolymer (A) and the above-mentioned ethylene-α-olefin copolymer (B), or they may be added after the above-mentioned ethylene-α-olefin copolymer (A) and the above-mentioned ethylene-α-olefin copolymer (B) have been compounded.

[0376] The aforementioned ethylene-α-olefin copolymer (A) and ethylene-α-olefin copolymer (B) may each contain at least one type of structural unit derived from biomass, specifically ethylene or α-olefin. The same type of monomer constituting the polymer may be derived solely from biomass, solely from fossil fuels, or may contain both. Monomers derived from biomass are monomers formed from all renewable natural raw materials and their residues, including fungi, yeast, algae, and bacteria, whether plant-based or animal-based, and have a carbon content of 1 × 10⁻⁶. -12 The proportion of the biomass contains 14C isotope, and the biomass carbon concentration (pMC) measured according to ASTM D6866 is approximately 100 (pMC). Ethylene and α-olefins derived from biomass can be obtained, for example, by currently known methods. From the viewpoint of reducing environmental impact, it is preferable that the above-mentioned ethylene-α-olefin copolymer (A) and / or the above-mentioned ethylene-α-olefin copolymer (B) contain structural units derived from monomers derived from biomass.

[0377] (Molded body, film, laminate)

[0378] By processing the ethylene-α-olefin copolymer (A) of the present application or the thermoplastic resin composition (Y) containing the same (e.g., the ethylene-based resin composition (Z)), a molded body, preferably a film, more preferably a laminate containing the same, having excellent mechanical strength can be obtained with excellent moldability.

[0379] The ethylene-α-olefin copolymer (A) of the present application or the thermoplastic resin composition (Y) containing the same can be processed by general film molding or sheet molding, blow molding, injection molding, and extrusion molding, etc. In film molding, extrusion lamination molding, T-film molding, inflation molding (air cooling, water cooling, multi-stage cooling, high-speed processing), etc. can be exemplified. The obtained film can also be used as a single layer, but by making it into a multi-layer, various functions can be further imparted. As the molding method employed at this time, co-extrusion methods can be exemplified. On the other hand, by a lamination molding method such as extrusion lamination molding or dry lamination, it is possible to laminate with paper or barrier films (aluminum foil, vapor deposition film, coated film, etc.) which are difficult to co-extrude. For the production of high-function products by multi-layerization by co-extrusion methods in blow molding or injection molding, extrusion molding, it is possible to do the same as in film molding.

[0380] As the molded body obtained by processing the ethylene-α-olefin copolymer (A) of the present application or the thermoplastic resin composition (Y) containing the same, films, sheets, blow-molded infusion bags, blow-molded bottles, gasoline tanks, tubes obtained by extrusion molding, pipes, wire sheaths, tear-off type caps, injection-molded articles of daily sundries, etc., fibers, large molded articles obtained by rotational molding, etc. can be exemplified.

[0381] Further, the film obtained by processing the ethylene-α-olefin copolymer (A) of the present application or the thermoplastic resin composition (Y) containing the same is suitable for various packaging films, protective films, infusion bags, agricultural materials, etc. for water-containing product packaging bags, liquid soup packaging bags, liquid paper containers, lamination base films, special shape liquid packaging bags (stand-up pouches, etc.), standard bags, heavy packaging bags, envelope films, sand sugar bags, oil-containing product packaging bags, food packaging, etc. Further, the above-mentioned film can also be used as a multi-layer film by being attached to a substrate of nylon, polyester, polyolefin film, etc.

[0382] The laminate having at least one layer containing the ethylene-α-olefin copolymer (A) of the present application or the thermoplastic resin composition (Y) containing the same is described in more detail below.

[0383] As an example of a layer other than the above-mentioned layers constituting the laminate, a base material layer and a barrier layer can be given.

[0384] As a base material used as the base material layer, a film of polyamide, polyester, polypropylene, polyethylene, ethylene-vinyl alcohol copolymer, or the like can be given. The above-mentioned film is preferably a stretched film. Paper or a paper base material obtained by applying polyethylene to paper can also be given. These base materials can be subjected to printing or various coating as needed. Various pretreatments such as corona treatment, flame treatment, plasma treatment, ultraviolet treatment, adhesion coating treatment, or the like can also be performed as needed.

[0385] As the base material, high-quality paper, kraft paper, thin paper, drawing paper, and the like, glassine paper, woven fabric, nonwoven fabric, stretched nylon, unstretched nylon, special nylon (MXD6 or the like), K-nylon (polyvinylidene fluoride coating), stretched PET (polyethylene terephthalate), unstretched PET (polyethylene terephthalate), K-PET (polyethylene terephthalate), stretched polypropylene (OPP), unstretched polypropylene (CPP), K-PP, co-extruded film PP, and the like can be given.

[0386] As a barrier base material used as the barrier layer, a metal foil or a thermoplastic resin film vapor-deposited with a metal or an inorganic substance can be given, and a thermoplastic resin film subjected to barrier coating can also be given. As the thermoplastic resin film, stretched nylon, stretched PET (polyethylene terephthalate), stretched polypropylene (OPP), unstretched polypropylene (CPP), and the like can be given.

[0387] The raw material of a part of the laminate of the base material, the barrier base material, and the like can contain an ethylene-based polymer or a propylene-based polymer containing a monomer derived from biomass.

[0388] In the present application, a metal foil refers to a metal foil of aluminum, gold, silver, iron, copper, nickel, an alloy in which these are the main components, or the like. A thermoplastic resin film vapor-deposited with a metal refers to a film in which a metal such as aluminum or silicon is vapor-deposited on the surface of a film of polyester, polyamide, or the like. A thermoplastic resin film vapor-deposited with an inorganic substance refers to a thermoplastic resin film vapor-deposited with silicon dioxide or aluminum oxide. Barrier coating refers to coating a barrier resin such as polyvinyl alcohol or polyvinylidene chloride on the surface of a film.

[0389] The base material layer can be used as a printing base material, for example. On the other hand, the barrier base material is not generally used as a printing base material.

[0390] The following illustrates the structure of a specific laminate in the present application, but is not limited thereto.

[0391] The PE laminate in the following structures means that the ethylene-based resin is laminated by extrusion lamination molding. The ethylene-based resin used in at least one layer of the PE laminate in each structure is the ethylene-α-olefin copolymer (A) of the present application or the composition (W) containing the same.

[0392] When the PE laminate using the ethylene-α-olefin copolymer (A) of the present application or the composition (W) containing the same is used as an adhesive layer adjacent to an aluminum evaporation layer or an aluminum foil of an aluminum evaporation film, the adhesion strength of the PE laminate to the aluminum evaporation layer or the aluminum foil is excellent.

[0393] The co-extrusion laminate (acid copolymer / PE laminate) means that the acid copolymer and the ethylene-based resin are two-layered by co-extrusion lamination, and the acid copolymer is adjacent to the aluminum foil. As examples of the acid copolymer, ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylate copolymer (EEA, EMA, EMMA, etc.) can be listed. The film used in the innermost layer (the side opposite to the stretched base film) is a thermoplastic resin film, and an ethylene-based resin film or a propylene-based resin film is preferably used.

[0394] Stretched nylon / adhesive / PE laminate (1) / PE laminate (2),

[0395] Paper / PE laminate,

[0396] Stretched polypropylene / adhesive / PE laminate (1) / aluminum foil / adhesive / film or PE laminate (2),

[0397] Stretched polypropylene / adhesive / PE laminate (1) / aluminum evaporation film (aluminum evaporation layer adjacent to the layer of PE laminate (1)),

[0398] Stretched polypropylene / adhesive / PE laminate (1) / aluminum evaporation film / adhesive / film or PE laminate (2) (aluminum evaporation layer adjacent to the layer of PE laminate (1)),

[0399] Stretched polypropylene / adhesive / extrusion laminate (1) / inorganic evaporation film,

[0400] Stretched polypropylene / adhesive / PE laminate (1) / inorganic evaporation film / adhesive / film or PE laminate (2),

[0401] Stretched polyethylene terephthalate / adhesive / extrusion laminate (1) / aluminum foil / adhesive / film or PE laminate (2),

[0402] Stretched polyethylene terephthalate / adhesive / extrusion laminate (1) / aluminum evaporation film / adhesive / film or PE laminate (2) (aluminum evaporation layer adjacent to the layer of PE laminate (1)),

[0403] Stretched polyethylene terephthalate / adhesive / PE laminate (1) / inorganic vapor deposition film,

[0404] Stretched polyethylene terephthalate / adhesive / PE laminate (1) / inorganic vapor deposition film / adhesive / film or PE laminate (2),

[0405] PE laminate (1) / paper / PE laminate (2) / aluminum foil / co-extrusion laminate (acid copolymer / PE laminate (3)),

[0406] PE laminate (1) / paper / PE laminate (2) / aluminum foil / adhesive / polyethylene terephthalate / adhesive / film or PE laminate (3),

[0407] PE laminate (1) / paper / PE laminate (2) / aluminum vapor deposition film / adhesive / film or PE laminate (3),

[0408] PE laminate (1) / paper / PE laminate (2) / inorganic vapor deposition film / adhesive / film or PE laminate (3)

[0409] Example

[0410] The present application will be described more specifically below by way of examples. However, the present application is not limited to the description of the following examples.

[0411] [Measurement and evaluation method]

[0412] In the following examples, etc., various physical properties of the ethylene-α-olefin copolymer, etc. were measured according to the method described in the [Specific Embodiments] section, as the evaluation method not described in the [Specific Embodiments] section, the following method was used.

[0413] Extrusion lamination evaluation :

[0414] [Shrinkage]

[0415] An extruder having a T-die with a die width of 500 mm was used, and an ethylene-α-olefin copolymer (hereinafter also referred to as "ethylene-based polymer") was extrusion laminated on a 50 g / m 2 kraft paper as a base material under the following conditions.

[0416] • Air gap: 130 mm

[0417] • Resin temperature under die: 320°C

[0418] • Draw speed: 80 m / min

[0419] • Film thickness: 20 μm

[0420] The width of the T-die was set to L0, and the width of the film laminated on the kraft paper at each take-up speed was set to L, and the draw down was calculated by L0- L.

[0421] [Membrane breakage speed, draw fluctuation]

[0422] An extruder having a T-die with a die width of 500 mm was used, and an ethylene-based polymer was extrusion laminated on a 50 g / m 2 kraft paper as a base material under conditions of a gas gap of 130 mm, a resin temperature at the die of 320°C. The extrusion amount was set so that the film thickness reached 20 μm at a take-up speed of 80 m / min. The take-up speed at the time of breakage of the molten film was measured by gradually increasing the take-up speed. In addition, the draw down at a take-up speed of 200 m / min was measured 5 times, and in the case where the average value of the draw down reached a value of ±1.5 mm or more for 2 or more times, it was evaluated that draw fluctuation had occurred.

[0423] [Aluminum adhesion strength ratio]

[0424] An extruder having a T-die with a die width of 500 mm was used, and an ethylene-based polymer was extrusion laminated on a 50 g / m 2 kraft paper as a base material under conditions of a gas gap of 130 mm, a resin temperature at the die of 320°C. The extrusion amount was set so that the film thickness reached 20 μm at a take-up speed of 80 m / min. The take-up speed at the time of breakage of the molten film was measured by gradually increasing the take-up speed. In addition, the draw down at a take-up speed of 200 m / min was measured 5 times, and in the case where the average value of the draw down reached a value of ±1.5 mm or more for 2 or more times, it was evaluated that draw fluctuation had occurred.

[0425] AL adhesion strength ratio = peel strength / peel strength (LDPE)

[0426] [Trunk tear strength]

[0427] An extruder having The extruder and laminator manufactured by Sumitomo Heavy Industries, Ltd., with a 500mm T-die width, used a 50g / m² substrate. 2 On kraft paper, a laminated vinyl polymer was extruded to achieve a film thickness of 20 μm under conditions of an air gap of 130 mm, a resin temperature of 320 °C under the die, and a drawing speed of 80 m / min. Following JIS K7128-1, the resulting laminate was cut into pieces 50 mm wide and 150 mm long, with a 75 mm slit cut in the center of the width. Tear strength was measured at a speed of 200 mm / min.

[0428] Cast molding evaluation :

[0429] Use with An extruder and a casting film forming machine manufactured by TANABE PLASTICS MACHINERY CO.,LTD. with a die width of 500 mm were used to produce a 40 μm thick film from ethylene-based polymers at a die temperature of 40 °C and a cooling roller temperature of 40 °C. During film formation, 2 wt% of anti-blocking agent masterbatch (20 wt% concentration, EAZ-20 manufactured by Priman Polymers Co., Ltd.) and 1 wt% of slip agent masterbatch (4 wt% concentration, ESQ-4 manufactured by Priman Polymers Co., Ltd.) were dry-blended into the ethylene-based polymer. The resulting film was then subjected to the following measurements.

[0430] Blow molding evaluation:

[0431] use An extruder and a blow molding machine manufactured by Sumitomo Heavy Industries, Ltd., with a die diameter of 100 mm, were used to produce a 40 μm thick film from an ethylene-based polymer under conditions of die temperature 190 °C, extrusion rate 29 kg / hr, and tube width 320 mm. The following parameters were measured on the obtained film.

[0432] [Haze]

[0433] The total haze of the obtained membrane was measured in accordance with JIS 7136.

[0434] [Internal Haze]

[0435] The obtained membrane was placed in a sample cell filled with cyclohexanol and measured according to JIS 7136.

[0436] [Gloss level 20°]

[0437] The gloss of the obtained film was measured at an incident angle of 20° in accordance with JIS Z8741.

[0438] Tensile failure stress

[0439] The MD and TD directions of the obtained membrane were measured according to JIS K6781 at a test speed of 500 mm / min.

[0440] [Tensive Modulus of Elasticity]

[0441] The MD and TD directions of the obtained membrane were measured according to JIS K6781 at a test speed of 200 mm / min.

[0442] [Dart Impact]

[0443] According to ASTM D1709 A, the obtained membrane is clamped using a pneumatic clamp, and a hemispherical dart is dropped from a certain height. The load at which the membrane breaks by 50% is read from the chart.

[0444] [Melt tension of the composition]

[0445] The film obtained by blow molding was measured using a capillary rheometer (CAPILOGRAPH 1D) manufactured by Toyo Seiki Co., Ltd. The conditions were set as follows: resin temperature 190°C, melting time 6 minutes, and tube diameter... Extrusion speed 15 mm / min, winding speed 24 m / min (with the molten wire breaking, the winding speed is gradually reduced in increments of 5 m / min), nozzle diameter Nozzle length 8mm.

[0446] [Melted film stability]

[0447] Visually confirm the stability of the molten film (bubble) during blow molding. The symbols (evaluation results) in Table 13 have the following meanings.

[0448] 〇: Stability of molten film (bubble)

[0449] ×: The molten film (bubble) has poor stability and shakes violently.

[0450] [Ingredients Used]

[0451] The transition metal compounds and components (G) used in the examples are as follows.

[0452] Transition metal compound (A-1): dimethylmethylenesilyl(2-indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-7-methoxy-1-indenyl)zirconium dichloride [synthesized according to the method described in Japanese Patent Application Publication No. 2019-059933.]

[0453] Transition metal compound (B-1): dimethylmethylenesilyl(3-n-propylcyclopentadienyl)(cyclopentadienyl)zirconium dichloride [synthesized according to the method described in Japanese Patent No. 5455354.]

[0454] Transition metal compound (B-2): Isopropylidene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride [synthesized according to the method described in Japanese Patent Application Publication No. 4-69394.]

[0455] Ingredient (G-1): Lauryl diethanolamine (manufactured by Kao Corporation)

[0456] Ingredient (G-2): EMULGEN (registered trademark) 108 (manufactured by Kao Corporation)

[0457] <Synthesis of Prepolymer Catalyst (XP-1)>

[0458] In a 270L reactor equipped with a stirrer, under a nitrogen atmosphere, silica (average particle size 70μm, specific surface area 340m²) manufactured by FUJI SILYSIA Corporation was used as a solid carrier (S). 2 / g, pore volume 1.3cm 3 10 kg of methylaluminoxane (calcined at 250℃) was suspended in 77 L of toluene and then cooled to 0–5℃. Over 30 minutes, 20.4 L of a toluene solution of methylaluminoxane (component C) (calculated as 3.5 mol / L Al) was added dropwise to the suspension. The temperature was maintained at 0–5℃. After reacting at 0–5℃ for another 30 minutes, the temperature was raised to 95–100℃ over approximately 1.5 hours, and the reaction was continued at 95–100℃ for 4 hours. The mixture was then cooled to room temperature, the supernatant was removed by decantation, and the mixture was washed twice with toluene to prepare a toluene slurry of 58.0 L. A portion of the obtained slurry was taken to investigate its concentration; the slurry concentration was 248.0 g / L, and the Al concentration was 1.21 mol / L.

[0459] Next, 6.1 L of the toluene slurry and 21.9 L of toluene obtained above were loaded into a 114 L reactor equipped with a stirrer after complete nitrogen replacement. 5.4 L of an 8 mM toluene solution of the transition metal compound (A-1) was added. After contacting at a system temperature of 20–25 °C for 1 hour, the supernatant was removed by decantation, and the mixture was washed twice with hexane to prepare a total slurry of 30.9 L. While adjusting the obtained slurry to 10–15 °C, 3.1 L of a 0.92 M hexane solution of diisobutylaluminum hydride was added. Ethylene gas was initially supplied at a flow rate of 0.74 kg / hr. After adding 34.3 mL of 1-hexene, the temperature was raised. While adjusting the system temperature to 32–38 °C, 34.3 mL of 1-hexene was added every hour for a total of 5 times. After 6 hours of ethylene supply, the ethylene supply was stopped when the ethylene supply reached 4.5 kg. Subsequently, the system was thoroughly nitrogen-replaced, the supernatant was removed by decantation, and the mixture was washed four times with hexane to prepare a slurry of 21.9 L. While maintaining the obtained slurry at 35–40 °C, 6.1 L of a 10 g / L hexane solution of component (G-1) was added, and the mixture was contacted for 2 hours. The entire amount of the obtained slurry was added to a 43 L evaporative dryer equipped with a stirrer under a nitrogen atmosphere. The pressure inside the dryer was reduced to -68 kPaG over approximately 60 minutes. After reaching -68 kPaG, the dryer was vacuum dried for approximately 4.3 hours to remove hexane and volatile components from the prepolymer catalyst. The pressure was then reduced to -100 kPaG, and vacuum dried for 8 hours to obtain 6.2 kg of prepolymer catalyst (XP-1). A portion of the obtained prepolymer catalyst (XP-1) was taken for analysis of its composition. Each 1 g of prepolymer catalyst contained 0.56 mg of Zr atoms.

[0460] <Synthesis of Prepolymer Catalyst (XP-2)>

[0461] In a 270L reactor equipped with a stirrer, under a nitrogen atmosphere, silica (average particle size 70μm, specific surface area 340m²) manufactured by FUJI SILYSIA Corporation was used as a solid carrier (S). 2 / g, pore volume 1.3cm 310 kg of methylaluminoxane (calcined at 250℃) was suspended in 77 L of toluene and then cooled to 0–5℃. Over 30 minutes, 20.4 L of a toluene solution of methylaluminoxane (component C) (calculated as 3.5 mol / L Al) was added dropwise to the suspension. The temperature was maintained at 0–5℃. After reacting at 0–5℃ for another 30 minutes, the temperature was raised to 95–100℃ over approximately 1.5 hours, and the reaction was continued at 95–100℃ for 4 hours. The mixture was then cooled to room temperature, the supernatant was removed by decantation, and the mixture was washed twice with toluene to prepare a toluene slurry of 58.0 L. A portion of the obtained slurry was taken to investigate its concentration; the slurry concentration was 248.0 g / L, and the Al concentration was 1.21 mol / L.

[0462] Next, 6.1 L of the toluene slurry and 22.7 L of toluene obtained above were added to a 114 L stirred reactor after thorough nitrogen replacement. 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. After contacting at a system temperature of 70–75 °C for 1 hour, the supernatant was removed by decantation, and the mixture was washed twice with hexane to prepare a total slurry volume of 29.8 L. While adjusting the obtained slurry temperature to 35–40 °C, 4.0 L of a 0.92 M hexane solution of diisobutylaluminum hydride was added, and ethylene gas was initially supplied at a flow rate of 795.4 L / hr. After 5 hours of ethylene supply, when the ethylene supply reached 3,980 L, the ethylene supply was stopped. Subsequently, the system was thoroughly nitrogen-replaced, the supernatant was removed by decantation, and the mixture was washed four times with hexane to prepare a total slurry volume of 21.7 L. While maintaining the obtained slurry at 35–40°C, 3.8 L of a 10 mg / mL hexane solution of component (G-2) was added, and the mixture was contacted for 2 hours. The entire volume of the obtained slurry was then added to a 43 L evaporative dryer equipped with a stirrer under a nitrogen atmosphere. The pressure inside the dryer was reduced to -68 kPaG over approximately 60 minutes. After reaching -68 kPaG, vacuum drying was performed for approximately 4.3 hours to remove hexane and volatile components from the prepolymer catalyst. The pressure was then further reduced to -100 kPaG, and vacuum drying was performed for 8 hours to obtain 6.1 kg of prepolymer catalyst (XP-2). A portion of the obtained prepolymer catalyst (XP-2) was examined for its composition; each 1 g of prepolymer catalyst component contained 0.52 mg of Zr atoms.

[0463] <Manufacturing of Ethylene-α-olefin Copolymers>

[0464] [Example 1]

[0465] Ethylene-based polymers were manufactured using a gas-phase polymerization process employing a fluidized bed gas-phase polymerization reactor. 24 kg of spherical ethylene polymer particles with an average particle size of 900 μm were pre-introduced into the reactor, and nitrogen was supplied. After forming a fluidized bed, ethylene, hydrogen, 1-hexene, a prepolymer catalyst, and Electrostripper EA (manufactured by Kao Corporation) were continuously supplied under the polymerization conditions shown in Table 8 to achieve a stable state. The polymerization product was continuously removed from the reactor and dried using a drying device to obtain ethylene-α-olefin copolymer (A-1) powder.

[0466] Using a twin-screw co-rotating screw manufactured by Ikegai Co., Ltd. The obtained ethylene-based polymer powder was melt-blended in an extruder at a set temperature of 200℃ and a screw speed of 300 rpm, then extruded into strands and cut into granules. The obtained granules were used as samples for physical property testing. The test results are shown in Table 9.

[0467] Next, the obtained granules were used for the extrusion lamination evaluation described above. The results are shown in Table 11. Furthermore, the obtained granules were used for the casting molding evaluation described above. The results are shown in Table 12.

[0468] [Examples 3, 4, 8-12]

[0469] Except for the changes in polymerization conditions described in Table 8, the same procedure as in Example 1 was followed to obtain powders of ethylene-α-olefin copolymers (A-3, 4, 8 to 12), and various measurements and evaluations were performed. The results are shown in Tables 9, 11, and 12. In Table 8, CHEMISTAT 2500 (manufactured by Sanyo Chemical Industry Co., Ltd.) was listed as a component not used in Example 1.

[0470] [Example 2]

[0471] Using the fluidized bed gas-phase polymerization reactor from Example 1 as the foreground reactor, with an internal volume of 0.6 m³... 3In a two-stage polymerization process using a fluidized bed gas-phase polymerization reactor as the downstream reactor, ethylene-based polymers are manufactured. Two-stage polymerization refers to the continuous transfer of the polymer reactants obtained from the upstream polymerization reactor to the downstream polymerization reactor, where the polymerization reaction continues. 24 kg of spherical ethylene polymer particles with an average particle size of 900 μm are pre-introduced into the upstream polymerization reactor. Nitrogen gas is supplied to form a fluidized bed. Ethylene, hydrogen, 1-hexene, prepolymerization catalyst, and Electrostripper EA are continuously supplied to both the upstream and downstream polymerization reactors under the polymerization conditions shown in Table 8 to achieve a stable state. The prepolymerization catalyst and Electrostripper EA are only supplied to the upstream polymerization reactor. The polymer reactants obtained from the two-stage polymerization process in the downstream polymerization reactor are continuously extracted from the downstream polymerization reactor and dried using a drying device to obtain ethylene-α-olefin copolymer (A-2) powder.

[0472] The obtained ethylene-α-olefin copolymer (A-2) powder was subjected to various measurements and evaluations in the same manner as in Example 1. The results are shown in Tables 9, 11, and 12.

[0473] [Examples 5-7]

[0474] Except for the changes in polymerization conditions as described in Table 8, the same procedure as in Example 2 was followed to obtain ethylene-α-olefin copolymer (A-5 to 7) powders, and various measurements and evaluations were performed. The results are shown in Tables 9, 11, and 12.

[0475] [Comparative Example 1]

[0476] Except for the changes in polymerization conditions as described in Table 8, the same procedure as in Example 1 was followed to obtain an ethylene-α-olefin copolymer (a-1) powder, and various measurements and evaluations were performed. The results are shown in Tables 9, 11, and 12. In Table 8, CHEMISTAT (registered trademark) 2500 (manufactured by Sanyo Chemical Industry Co., Ltd.) was listed as a component not used in Example 1.

[0477] [Comparative Example 2]

[0478] For Asahi Kasei Corporation's high-pressure low-density polyethylene SUNTEC-LD "L1850A" (density: 918 kg / m³) 3 (MFR: 6.5g / 10 minutes), and performed the same extrusion lamination evaluation and casting molding evaluation as in Example 1. The results are shown in Tables 11 and 12.

[0479] [Comparative Example 3]

[0480] Following the same procedure as described in Manufacturing Example 1 of Japanese Patent No. 5943941, an ethylene-α-olefin copolymer (a-3) powder was obtained. Various measurement results are shown in Table 9.

[0481] [Examples 13 and 14]

[0482] Except for the changes in polymerization conditions as described in Table 8, the same procedure as in Manufacturing Example 1 was followed to obtain ethylene-α-olefin copolymer (A-13, 14) powder and perform various measurements on the granules. The results are shown in Table 9.

[0483] <Ethylene-α-olefin copolymer (B)>

[0484] [Ethylene-α-olefin copolymer (B-1)]

[0485] The physical properties of Evolue GD1588 manufactured by Priman Polymers Co., Ltd. were determined.

[0486] The measurement results are shown in Table 10.

[0487] [Ethylene-α-olefin copolymer (b-2)]

[0488] The physical properties of NEO-ZEX 2006H manufactured by Praman Polymer Co., Ltd. were determined.

[0489] The measurement results are shown in Table 10.

[0490] [Ethylene-α-olefin copolymer (B-3)]

[0491] The physical properties of Evolue SP1510 manufactured by Priman Polymers Co., Ltd. were determined.

[0492] The measurement results are shown in Table 10.

[0493] <Preparation of Vinyl Resin Compositions>

[0494] [Example 15]

[0495] The obtained ethylene-α-olefin copolymer (A-13) pellets (5% by weight) and ethylene-α-olefin copolymer (B-1) pellets (95% by weight) were dry-blended and evaluated for blow molding. The evaluation results are shown in Table 13.

[0496] [Example 16]

[0497] The obtained ethylene-α-olefin copolymer (A-13) pellets (10 wt%) and ethylene-α-olefin copolymer (B-1) pellets (90 wt%) were dry-blended and evaluated for blow molding. The evaluation results are shown in Table 13.

[0498] [Example 17]

[0499] The obtained ethylene-α-olefin copolymer (A-13) pellets (15 wt%) and ethylene-α-olefin copolymer (B-1) pellets (85 wt%) were dry-blended and evaluated for blow molding. The evaluation results are shown in Table 13.

[0500] [Example 18]

[0501] The obtained ethylene-α-olefin copolymer (A-14) pellets (60 wt%) and ethylene-α-olefin copolymer (B-3) pellets were dry-blended and evaluated for blow molding. The evaluation results are shown in Table 13.

[0502] [Example 19]

[0503] The obtained ethylene-α-olefin copolymer (A-14) pellets (80 wt%) and ethylene-α-olefin copolymer (B-3) pellets were dry-blended and evaluated for blow molding. The evaluation results are shown in Table 13.

[0504] [Example 20]

[0505] The obtained ethylene-α-olefin copolymer (A-6) pellets (20 wt%) and ethylene-α-olefin copolymer (B-1) pellets were dry-blended and evaluated for blow molding. The evaluation results are shown in Table 13.

[0506] [Example 21]

[0507] The obtained ethylene-α-olefin copolymer (A-6) pellets (30 wt%) and ethylene-α-olefin copolymer (B-1) pellets were dry-blended and evaluated for blow molding. The evaluation results are shown in Table 13.

[0508] [Comparative Example 4]

[0509] The obtained ethylene-α-olefin copolymer (a-3) pellets (80 wt%) and ethylene-α-olefin copolymer (B-3) pellets were dry-blended and evaluated by blow molding. The evaluation results are shown in Table 13.

[0510] [Comparative Example 5]

[0511] The blow molding evaluation was performed using an ethylene-α-olefin copolymer (B-1). The evaluation results are shown in Table 13.

[0512] [Reference Example 1]

[0513] The obtained ethylene-α-olefin copolymer (A-13) pellets (15 wt%) and ethylene-α-olefin copolymer (b-2) pellets were dry-blended and evaluated for blow molding. The evaluation results are shown in Table 13.

[0514] [Table 8-1]

[0515]

[0516] [Table 8-2]

[0517]

[0518] [Table 9-1]

[0519]

[0520] [Table 9-2]

[0521]

[0522] [Table 10]

[0523] Table 10

[0524]

[0525] [Table 11]

[0526]

[0527] [Table 12]

[0528]

[0529] [Table 13]

[0530]

Claims

1. An ethylene-α-olefin copolymer (A) which is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, the ethylene-α-olefin copolymer (A) being characterized in that: (1) the melt flow rate (MFR) at 190°C under a load of 2.16 kg is in the range of 3.0 g / 10 minutes or more and 15.0 g / 10 minutes or less; (2) the melt flow rate (MFR) at 190°C under a load of 2.16 kg is in the range of 3.0 g / 10 minutes or more and 15.0 g / 10 minutes or less; (3) the melt flow rate (MFR) at 190°C under a load of 21.6 kg is in the range of 0.1 g / 10 minutes or more and 20.0 g / 10 minutes or less; (4) the melt flow rate (MFR) at 190°C under a load of 21.6 kg is in the range of 0.1 g / 10 minutes or more and 20.0 g / 10 minutes or less; (5) the number average molecular weight (Mn), the weight average molecular weight (Mw) and the 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) the number average molecular weight (Mn), the weight average molecular weight (Mw) and the 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); and (7) the melting curve obtained by differential scanning calorimetry (DSC) has a plurality of peaks.

2. The ethylene-α-olefin copolymer (A) according to claim 1, characterized in that: (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 or more and 25.0 or less. (1) density in the range of 890 kg / m 3 above 925 kg / m 3 below the range of 925 kg / m 3. The ethylene-α-olefin copolymer (A) according to claim 1 or 2, characterized in that: (9) the intrinsic viscosity [η] (dl / g) measured in decahydronaphthalene 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-4), 0.5 < [η] x Mw < 10 (Eq-4). (3) the ratio of the melt tension at 190°C (MT (g)) to the shear viscosity at 200°C, angular velocity 1.0 rad / sec (η (P)) (MT / η (g / P)) is in the range of 1.40 x 10 * -4 -4 above 2.90 x 10 -13 below;​​ (4) the zero shear viscosity at 200°C (η0(P)) and the weight average molecular weight (Mw) measured by the GPC-VISCO method (GPC-VISCO) satisfy the following relationship (Eq-1), 0.01 x 10 -13 × Mw 3.4 ≤ η0≤ 4.5 x 10 -13 × Mw 3.4 (Eq-1); 4. A thermoplastic resin composition (Y) characterized by: containing the ethylene-α-olefin copolymer (A) according to any one of claims 1 to 3 and a thermoplastic resin, wherein the thermoplastic resin does not include the ethylene-α-olefin copolymer (A) described above.

5. The thermoplastic resin composition (Y) according to claim 4, characterized in that: the thermoplastic resin is an ethylene-α-olefin copolymer (B) satisfying the following conditions (a) to (d), (a) the melt flow rate (MFR) at 190°C under a load of 2.16 kg is in the range of 0.1 g / 10 minutes or more and 20.0 g / 10 minutes or less; (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 minutes or more and 20.0 g / 10 minutes or less; (c) the melt flow rate (MFR) at 190°C under a load of 21.6 kg is in the range of 0.1 g / 10 minutes or more and 20.0 g / 10 minutes or less; and (d) the amount (%) of a component having a Log molecular weight of 5.8 or more in the molecular weight distribution curve measured by GPC is in the range of 0.01% or more and 5.0% or less. (6) by 1 the total of the vinyl group, vinylidene group, 2-substituted internal olefin, 3-substituted internal olefin per 1000 carbon atoms measured by1H-NMR is in the range of 0.1 or more and 1.0 or less in terms of the ratio relative to 1000 carbon atoms; 6. A film characterized by: containing the ethylene-α-olefin copolymer (A) according to any one of claims 1 to 3 or the thermoplastic resin composition (Y) according to claim 4 or 5.

7. The film according to claim 6, characterized by: containing the ethylene-α-olefin copolymer (A) according to any one of claims 1 to 3.

8. The film according to claim 6, characterized by: containing the thermoplastic resin composition (Y) according to claim 4.

9. The film according to claim 6, characterized by: containing the thermoplastic resin composition (Y) according to claim 5.

10. A laminate characterized by: ​ ​ 0.8 x 10 -4 x Mw 0.776 ≤ [η] ≤ 1.65 x 10 -4 x Mw 0.776 (Eq-4). ​ ​ ​ ​ The thermoplastic resin composition (Y) is an ethylene-α-olefin copolymer (A) having a mass fraction (W A ) of 5 mass% or more and 90 mass% or less, an ethylene-α-olefin copolymer (B) having a mass fraction (W B ) of 10 mass% or more and 95 mass% or less, and a thermoplastic resin (C) having a mass fraction (W A ) of 0 mass% or more and 90 mass% or less, wherein the sum of W B is 100 mass%. (a) a density of 890 kg / m 3 above 930 kg / m 3 in the following ranges; ​ (c) the ratio of the melt tension at 190°C (MT (g)) to the shear viscosity at 200°C, angular velocity 1.0 rad / sec (η (P)) (MT / η (g / P)) is in the range of 1.0 x 10 * * -6 -4 -2.0.​​​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ having a layer containing the ethylene-α-olefin copolymer (A) according to any one of claims 1 to 3, or the thermoplastic resin composition (Y) according to claim 4 or 5.

11. The laminate according to claim 10, wherein: further has a base material layer.

12. The laminate according to claim 11, wherein: further has a barrier layer.

13. The laminate according to any one of claims 10 to 12, wherein: has a layer containing the ethylene-α-olefin copolymer (A) according to any one of claims 1 to 3.

14. The laminate according to any one of claims 10 to 12, wherein: has a layer containing the thermoplastic resin composition (Y) according to claim 4.

15. The laminate according to any one of claims 10 to 12, wherein: has a layer containing the thermoplastic resin composition (Y) according to claim 5.

16. A method for producing a laminate, wherein: the ethylene-α-olefin copolymer (A) according to any one of claims 1 to 3, or the thermoplastic resin composition (Y) according to claim 4 or 5 is extrusion laminated between a base material layer and a barrier layer.

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