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

Abstract

The present invention provides an ethylene-α-olefin copolymer which is excellent in moldability, and enables the production of a molded body (particularly a film) which is excellent in mechanical strength, and has a balance between transparency and blocking resistance. The copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms satisfies the following conditions (1) to (6). (1) The density is 890 to 925 kg / m 3 ; (2) The MFR (190°C, 2.16 kg load) is 0.1 g / 10 minutes or more and less than 3.0 g / 10 minutes; (3) The MT (melt tension) / η * (shear viscosity) is 1.20 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) ≤ 3.5 x 10 ‑13 x Mw 3.4 ; (5) -7.0 ≤ Mz / Mw - Mw / Mn ≤ 2.0; and (6) The melting curve of DSC has multiple peaks.

Description

Technical Field

[0001] The present invention relates to ethylene-α-olefin copolymers and thermoplastic resin compositions containing the ethylene-α-olefin copolymers, as well as films and multilayer films containing the same. Background Technology

[0002] Vinyl polymers are used in a wide variety of molding methods and applications, and various properties are required depending on the molding method and application. For example, during T-die molding, a necking phenomenon occurs where the film ends shrink towards the center. Once necking occurs, the film width becomes smaller, and the film ends are thicker than the center. Therefore, if the necking is large, the yield of the finished product will be poor, or the product cannot be made into the desired width. In blow molding, defects such as melt film sagging or breakage may occur, and in blow molding, defects such as unstable melt film or breakage may occur. To avoid these defects, it is necessary to select vinyl polymers with high melt tension relative to molecular weight.

[0003] While ethylene-based polymers without long branches, obtained using metallocene catalysts, exhibit excellent mechanical strength, they suffer from moldability issues. For example, shrinkage increases during T-die molding, sag occurs during blow molding, and wrinkles form due to molten film instability during blow molding. High-pressure low-density polyethylene, despite its high melt tension and excellent moldability, suffers from poor mechanical strength, such as tensile strength, tear strength, and impact resistance, due to its complex long branches.

[0004] To address these issues, various ethylene-based polymers with introduced long-chain branches have been developed. Patent Document 1 proposes a composition of an ethylene-based polymer obtained using a metallocene catalyst and high-pressure processed low-density polyethylene. However, with a high content of high-pressure processed low-density polyethylene, poor mechanical strength such as tensile strength, tear strength, or impact strength is expected; with a low content of high-pressure processed low-density polyethylene, poor moldability such as large shrinkage is expected due to insufficient increase in melt tension.

[0005] Furthermore, Patent Document 2 discloses an ethylene-based polymer obtained by solution polymerization in the presence of a catalyst composed of ethylene bis(indenyl) hafnium dichloride and methylaluminoxane; Patent Document 3 discloses an ethylene-based polymer obtained by gas-phase polymerization in the presence of a catalyst composed of ethylene bis(indenyl) zirconium dichloride supported on silica and methylaluminoxane; Patent Document 4 discloses an ethylene-based polymer obtained by solution polymerization in the presence of a geometry-restricting catalyst; and Patent Document 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. According to the records, these ethylene-based polymers, compared to linear ethylene-based polymers without long branches, exhibit increased melt tension and excellent formability, but their shrinkage remains relatively large. Therefore, it is expected that their improvement in formability is insufficient, and they are also insufficient in improving the anti-blocking properties of the film. When using vinyl polymers in membranes, anti-blocking agents are typically added to prevent adhesion. However, in some applications, from the perspectives of increased cost and hygiene of the contents, adding large amounts of anti-blocking agents is not preferable. Therefore, membranes with excellent anti-blocking properties even without the use of anti-blocking agents are desirable.

[0006] Patent documents 6, 7, and 8 disclose vinyl polymers with specific relationships between intrinsic viscosity and weight-average molecular weight, or between melt tension and shear viscosity, or between zero-shear viscosity and weight-average molecular weight. These vinyl polymers exhibit improved pull-out properties and, compared to existing vinyl polymers with long-chain branching introduced using metallocene catalysts, improved shrinkage and blow molding performance in T-die forming. However, further improvements in mechanical strength and transparency are still desired. While the high external haze due to the minute surface irregularities of the film results in excellent anti-blocking properties, a film with a superior balance between transparency and anti-blocking properties is still desirable from the viewpoint of identifying the contents and inspecting for defects in the film. Furthermore, improved transparency is also desirable when using vinyl polymers as bottles, etc.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 7-26079

[0010] Patent Document 2: Japanese Patent Application Publication No. 2-276807

[0011] Patent Document 3: Japanese Patent Application Publication No. 4-213309

[0012] Patent Document 4: International Publication No. 93 / 08221

[0013] Patent Document 5: Japanese Patent Application Publication No. 8-311260

[0014] Patent Document 6: Japanese Patent Application Publication No. 2006-233207

[0015] Patent Document 7: Japanese Patent Application Publication No. 2008-31380

[0016] Patent Document 8: Japanese Patent Application Publication No. 2009-197225 Summary of the Invention

[0017] The technical problem that the invention aims to solve

[0018] The object of the present invention is to provide an ethylene-α-olefin copolymer, a thermoplastic resin composition containing the polymer, and a film obtained from the polymer or the thermoplastic resin composition, which have superior formability and can produce molded articles (especially films) with excellent mechanical strength and a good balance of transparency and anti-blocking properties compared with existing known ethylene-based polymers.

[0019] Technical means for solving technical problems

[0020] The inventors of this invention conducted in-depth research and discovered an ethylene-α-olefin copolymer that exhibits excellent formability by imparting specific melting characteristics and molecular structure to the polymer. Furthermore, it is capable of manufacturing molded articles (especially films) with excellent mechanical strength and a good balance between transparency and anti-blocking properties, thus completing this invention.

[0021] This invention relates, for example, to the following [1] to [6].

[0022] [1] An ethylene-α-olefin copolymer, which is a copolymer of ethylene and α-olefins having 4 to 10 carbon atoms, wherein the ethylene-α-olefin copolymer satisfies the following conditions (1) to (6).

[0023] (1) Density is 890 kg / m³ 3 Above 925kg / m 3 Within the following range.

[0024] (2) The melt flow rate (MFR) at 190℃ and 2.16kg load is in the range of 0.1g / 10min or more and 3.0g / 10min or less.

[0025] (3) Melt tension at 190°C [MT(g)] and shear viscosity at 200°C and angular velocity of 1.0 rad / s [η] * The ratio of (P) to [MT / η] * (g / P)〕 at 1.20×10 -4 Above 2.90×10 -4Within the following range.

[0026] (4) The zero-shear viscosity [η0(P)] at 200℃ and the weight-average molecular weight (Mw) measured by the GPC-Viscosity Detector Method (GPC-VISCO) satisfy the following relationship (Eq-1).

[0027] 0.01×10 -13 ×Mw 3.4 ≤η0≤3.5×10 -13 ×Mw 3.4 …(Eq-1)

[0028] (5) The number-average molecular weight (Mn), weight-average molecular weight (Mw) and Z-average molecular weight (Mz) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relationship (Eq-2).

[0029] -7.0≤Mz / Mw-Mw / Mn≤2.0…(Eq-2)

[0030] (6) The melting curve obtained by differential scanning calorimetry (DSC) has multiple peaks.

[0031] [2] The ethylene-α-olefin copolymer described in [1] above also satisfies the following condition (7).

[0032] (7) The ratio of Z-average molecular weight (Mz) to weight-average molecular weight (Mw) measured by GPC-VISCO is in the range of 4.0 to 15.0.

[0033] [3] The ethylene-α-olefin copolymer described in [1] or [2] above also satisfies the following condition (8).

[0034] (8) The intrinsic viscosity [η] (dl / g) measured in decahydronaphthalene at 135℃ and the weight-average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relationship (Eq-3).

[0035] 0.7×10 -4 ×Mw 0.776 ≤[η]≤1.65×10 -4 ×Mw 0.776 …(Eq-3)

[0036] [4] A thermoplastic resin composition comprising the ethylene-α-olefin copolymer and thermoplastic resin (but excluding the ethylene-α-olefin copolymer) described in any one of [1] to [3] above.

[0037] [5] A membrane containing any one of the above [1] to [3] ethylene-α-olefin copolymer.

[0038] [6] A multilayer film having a layer containing any one of the ethylene-α-olefin copolymers described in any one of [1] to [3].

[0039] Invention Effects

[0040] The ethylene-α-olefin copolymer and the thermoplastic resin composition containing the polymer of the present invention are suitable for manufacturing molded articles (especially films) with excellent moldability and a good balance of transparency and anti-blocking properties. Detailed Implementation

[0041] The ethylene-α-olefin copolymer involved in this invention will be described in detail below.

[0042] [ethylene-α-olefin copolymer]

[0043] The ethylene-α-olefin copolymer involved in this invention is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 6 to 10 carbon atoms. Examples of α-olefins having 4 to 10 carbon atoms used for copolymerization with ethylene include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.

[0044] The ethylene-α-olefin copolymer of the present invention has the following properties (1) to (6).

[0045] (1) Density is 890 kg / m³ 3 Above 925kg / m 3 The following is preferred: 900 kg / m 3 Above 925kg / m 3 The following, more preferably 905 kg / m 3 The above 922kg / m 3 Within the following range.

[0046] When the density is above the lower limit, the surface of the formed film is less sticky; when the density is below the upper limit, the low-temperature sealing performance of the formed film is good.

[0047] Additionally, by making the density, for example, less than 915 kg / m³ 3 The value enables the manufacture of soft molded bodies that cannot be produced using high-pressure low-density polyethylene.

[0048] Density depends on the α-olefin content of the ethylene-α-olefin copolymer; the lower the α-olefin content, the higher the density, and vice versa. Since the α-olefin content of the ethylene-α-olefin copolymer is determined by the ratio of α-olefin to ethylene in the polymerization system (α-olefin / ethylene) (e.g., Walter Kaminsky, Makromol. Chem. 193, p. 606 (1992)), ethylene-α-olefin copolymers with densities within the above range can be produced by increasing or decreasing the α-olefin / ethylene ratio.

[0049] The density was measured as described below.

[0050] In the MFR determination, the obtained stock was heat-treated at 100°C for 30 minutes, then left at room temperature for 1 hour, and then the density gradient tube method was used for determination.

[0051] (2) The melt flow rate (MFR) is in the range of 0.1 g / 10 min or more and less than 3.0 g / 10 min, preferably 0.3 g / 10 min or more and 2.5 g / 10 min or less, and more preferably 0.4 g / 10 min or more and 2.0 g / 10 min or less.

[0052] When the melt flow rate (MFR) is above the lower limit, the shear viscosity of the ethylene-α-olefin copolymer does not become excessively 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 is good.

[0053] Melt flow rate (MFR) is largely dependent on molecular weight; a lower MFR generally indicates a higher molecular weight, and vice versa. Furthermore, it is known that the molecular weight of vinyl polymers is determined by the hydrogen-to-ethylene ratio (H / E) within the polymerization system (e.g., Soga Kazuo et al., eds., *Catalytic Olefin Polymerization*, Kodansha Scientific, 1990, p. 376). Therefore, by increasing or decreasing the hydrogen / ethylene ratio, the MFR of vinyl polymers can be increased or decreased. The MFR was determined according to JIS K 7210 at 190°C and a 2.16 kg load.

[0054] (3) Melt tension [MT(g)] and shear viscosity [η] at 200°C and angular velocity 1.0 rad / s * The ratio of (P) to [MT / η] * (g / P)〕 at 1.20×10 -4 ~2.90×10 -4 Preferred 1.30×10 -4 ~2.70×10-4 More preferably 1.30×10 -4 ~2.45×10 -4 Within the range.

[0055] MT / η * Above the lower limit, ethylene-α-olefin copolymers exhibit high melt tension relative to molecular weight, resulting in excellent moldability. MT / η * Below the upper limit, ethylene-α-olefin copolymers exhibit excellent mechanical strength.

[0056] MT / η * The MT / η ratio depends on the long-branch content of the ethylene polymer; the higher the long-branch content, the higher the MT / η ratio. * The larger the value, the lower the content of long-chain branches, and the lower the MT / η. * The smaller the length. Long branches are defined as branched structures with a length of more than 10 ...

[0057] MT / η * The composition (A) of the catalyst (X) for olefin polymerization, as described later, or the type of solid support (S) can be adjusted. Furthermore, even when using the same catalyst (X) for olefin polymerization, adjustments can be made through polymerization conditions or processes; for example, by increasing the partial pressure of ethylene, the MT / η ratio can be adjusted. * The decrease. Based on the manufacturing conditions of Example 3 described later, it is possible to obtain MT / η near the lower limit. * According to the manufacturing conditions of Example 5 described later, MT / η near the upper limit can be obtained. * .

[0058] Melt tension (MT(g)) was measured as described below. Melt tension (MT) (unit: g) is determined by measuring the stress when stretched at a certain speed. The measurement was performed using a capillary rheometer (for example, in the embodiments described later, a Capilograph 1D capillary rheometer manufactured by Toyo Seiki Co., Ltd. was used). 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 (decrease winding speed by 5 m / min when molten wire breaks), nozzle diameter Nozzle length 8mm.

[0059] Shear viscosity at 200℃ and angular velocity of 1.0 rad / s [η] * (P)] was measured as described below. Regarding shear viscosity (η)* The shear viscosity (η) at a measurement temperature of 200℃ was determined within the range of 0.01 ≤ ω ≤ 100. * The angular velocity distribution [ω (rad / s)] of the viscoelasticity was determined using a viscoelasticity measuring apparatus (e.g., the Anton Paar Physica MCR301 viscoelasticity measuring apparatus used in the embodiments described later). A parallel plate was used as the sample holder, and the sample thickness was set to approximately 2.0 mm. Five measurement points were set for each order of magnitude of ω. The strain was appropriately selected within the range of 3% to 10% to ensure that torque could be detected within the measurement range without becoming excessively large.

[0060] The samples used for shear viscosity determination were prepared as follows: using a molding machine (e.g., a pressure molding machine manufactured by Shinto Metal Industries in the examples described later), at a preheating temperature of 190°C, a preheating time of 5 minutes, a heating temperature of 190°C, a heating time of 2 minutes, and a heating pressure of 100 kgf / cm². 2 Cooling temperature 20℃, cooling time 5 minutes, cooling pressure 100 kgf / cm² 2 Under these conditions, the sample was pressurized and molded to a thickness of 2 mm.

[0061] (4) The zero-shear viscosity [η0(P)] at 200℃ and the weight-average molecular weight (Mw) measured by GPC-VISCO satisfy the following relationship (Eq-1).

[0062] 0.01×10 -13 ×Mw 3.4 ≤η0≤3.5×10 -13 ×Mw 3.4 …(Eq-1)

[0063] Preferably, the following (Eq-1') is satisfied.

[0064] 0.05×10 -13 ×Mw 3.4 ≤η0≤3.0×10 -13 ×Mw 3.4 …(Eq-1')

[0065] More preferably, it satisfies the following (Eq-1).

[0066] 0.1×10 -13 ×Mw 3.4 ≤η0≤2.5×10 -13 ×Mw 3.4 …(Eq-1)

[0067] It is known that when plotting a double logarithmic curve of zero-shear viscosity [η0(P)] versus weight-average molecular weight (Mw), resins such as linear vinyl polymers without long branches, whose elongation viscosity does not indicate strain curing, follow a power law with a slope of 3.4. In contrast, resins such as high-pressure low-density polyethylene, whose elongation viscosity indicates strain-rate curing, exhibit a zero-shear viscosity [η0(P)] below the power law (C Gabriel, H. Munstedt, J. Rheol., 47(3), 619(2003)). When the zero-shear viscosity [η0(P)] at 200°C is below the upper limit, the elongation viscosity of vinyl polymers indicates strain-rate curing and therefore does not exhibit tensile fluctuations.

[0068] Furthermore, tensile stress is generated due to the stretching flow as molten resin flows into the mold. Once this tensile stress exceeds a critical value, brittle fracture occurs, resulting in unstable flow at the mold exit known as melt fracture, which forms minute irregularities on the surface of the molded body (FNCogswell, Polymer Melt Rheology, Wiley, 1981). When the zero-shear viscosity [η0(P)] is within the aforementioned range, the tensile stress increases at the strain rate during normal molding processes, leading to moderate melt fracture. Due to this melt fracture, minute irregularities are moderately formed on the film surface, resulting in a film with an excellent balance between transparency and anti-blocking properties.

[0069] The relationship between zero-shear viscosity [η0(P)] and weight-average molecular weight (Mw) can be considered to depend on the content and length of long branches in the vinyl polymer. It can be assumed that the more long branches there are and the shorter the length of the long branches, the smaller the value of zero-shear viscosity [η0(P)] will be; the less long branches there are and the longer the length of the long branches, the larger the value of zero-shear viscosity [η0(P)] will be.

[0070] The zero-shear viscosity [η0(P)] can be adjusted by changing the composition (A) of the catalyst (X) for olefin polymerization (described later) or the type of solid support (S). Furthermore, even when using the same catalyst (X) for olefin polymerization, the zero-shear viscosity [η0(P)] can be increased by adjusting the polymerization conditions or polymerization process; for example, by increasing the partial pressure of ethylene. According to the manufacturing conditions of Example 4 described later, a zero-shear viscosity [η0(P)] near the lower limit can be obtained; according to the manufacturing conditions of Example 3 described later, a zero-shear viscosity [η0(P)] near the upper limit can be obtained.

[0071] The zero-shear viscosity [η0(P)] at 200℃ was measured as follows.

[0072] The shear viscosity (η) was measured at a temperature of 200℃ within the range of 0.01 ≤ ω ≤ 100. *The angular velocity ω (rad / s) distribution of [the data] was determined using a viscoelasticity measuring apparatus (e.g., the Anton Paar Physica MCR301 viscoelasticity measuring apparatus used in the embodiments described later). A parallel plate was used as the sample holder, and the sample thickness was set to approximately 2.0 mm. Five measurement points were set for each order of magnitude of ω. The strain was appropriately selected within the range of 3% to 10% to ensure that torque could be detected within the measurement range without becoming excessively large.

[0073] The samples used for shear viscosity determination were prepared as follows: using a molding machine (e.g., a pressure molding machine manufactured by Shinto Metal Industries in the examples described later), at a preheating temperature of 190°C, a preheating time of 5 minutes, a heating temperature of 190°C, a heating time of 2 minutes, and a heating pressure of 100 kgf / cm². 2 Cooling temperature 20℃, cooling time 5 minutes, cooling pressure 100 kgf / cm² 2 Under these conditions, the sample was pressurized and molded to a thickness of 2 mm.

[0074] Zero shear viscosity (η0) is obtained by fitting the Carreau model of the following equation to the measured rheological curve using the nonlinear least squares method: [Shear viscosity (η0)] * The angular velocity (ω) distribution is calculated from the distribution of ω.

[0075] η * =η0〔1+(λω) a ] (n-1) / a

[0076] [λ represents the parameter with a time dimension, a represents the fitting parameter, and n represents the power law index of the material.]

[0077] Among them, the fitting using the nonlinear least squares method is performed in a way that minimizes d in the following formula.

[0078]

[0079] [ηexp(ω) represents the measured shear viscosity, and ηcalc(ω) represents the shear viscosity calculated using the Carreau model.]

[0080] Weight-average molecular weight (Mw) and other parameters were determined using gel permeation chromatography (GPC) as described below.

[0081] The detectors used were a differential refractometer and a capillary viscometer. The column temperature was set to 145°C. o-Dichlorobenzene was used as the mobile phase, the flow rate was set to 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, an Agilent GPC-VISCO PL-GPC220 viscometer was used as the measuring apparatus, two Agilent PLgel Olexis columns were used, and the standard polystyrene was a product of Tosoh Corporation. For molecular weight calculation, the measured viscosity was calculated using the viscometer and refractometer, and the number-average molecular weight (Mn), weight-average molecular weight (Mw), Z-average molecular weight (Mz), and molecular weight distribution (Mw / Mn, Mz / Mw) were determined using a universal calibration.

[0082] (5) The number-average molecular weight (Mn), weight-average molecular weight (Mw) and Z-average molecular weight (Mz) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relationship (Eq-2).

[0083] -7.0≤Mz / Mw-Mw / Mn≤2.0…(Eq-2)

[0084] Preferably, the following relation (Eq-2') is satisfied.

[0085] -6.0≤Mz / Mw-Mw / Mn≤1.0…(Eq-2')

[0086] More preferably, it satisfies the following relation (Eq-2").

[0087] -5.0≤Mz / Mw-Mw / Mn≤0.0…(Eq-2")

[0088] When Mz / Mw-Mw / Mn is large, the molecular weight distribution expands towards the high molecular weight side. When Mz / Mw-Mw / Mn is above the lower limit, the melt film has excellent stability, and when it is below the upper limit, the film has excellent formability.

[0089] Mz / Mw-Mw / Mn can be adjusted by the composition (A) of the catalyst (X) for olefin polymerization described later or by the type of solid support (S). Furthermore, even when using the same catalyst (X) for olefin polymerization, it can be adjusted by the polymerization conditions or the polymerization process. According to the manufacturing conditions of Example 2 described later, Mz / Mw-Mw / Mn near the lower limit can be obtained; according to the polymerization conditions of Example 1 described later, Mz / Mw-Mw / Mn near the upper limit can be obtained.

[0090] Number-average molecular weight (Mn), weight-average molecular weight (Mw), and Z-average molecular weight (Mz) were determined according to the methods described above.

[0091] (6) The melting curve obtained by differential scanning calorimetry (DSC) has multiple peaks.

[0092] When it has multiple peaks, it has more low-melting-point components and excellent heat-sealing properties at low temperatures.

[0093] Differential scanning calorimetry (DSC) is performed using a differential scanning calorimeter (e.g., the Diamond DSC manufactured by PerkinElmer, as described in the examples below).

[0094] Approximately 5 mg of sample was placed in an aluminum dish, and the temperature was increased to 200°C at a rate of 10°C / min. After holding at 200°C for 10 minutes, the temperature was decreased to -30°C at a rate of 10°C / min, and then increased to 200°C at a rate of 10°C / min. The endothermic curve at this point was obtained. The presence of more than two peaks in this endothermic curve indicates that the melt curve obtained by differential scanning calorimetry (DSC) contains multiple peaks.

[0095] The ethylene-α-olefin copolymer of the present invention preferably has the following properties (7).

[0096] (7) The ratio of Z-average molecular weight (Mz) to weight-average molecular weight (Mw) (Mz / Mw), measured by GPC-VISCO method, is in the range of 4.0 to 15.0, preferably 5.0 to 12.0, and more preferably 6.0 to 10.0. The larger the Mz / Mw, the more high molecular weight components there are. When Mz / Mw is above the lower limit, the anti-blocking property is excellent, and when Mz / Mw is below the upper limit, the transparency is excellent.

[0097] Mz / Mw can be adjusted by the composition (A) of the catalyst (X) for olefin polymerization described later or by the type of solid support (S), and even when using the same catalyst (X) for olefin polymerization, it can be adjusted by the polymerization conditions or polymerization process. According to the manufacturing conditions of Example 3 described later, an Mz / Mw close to the lower limit can be obtained; according to the polymerization conditions of Example 4 described later, an Mz / Mw close to the upper limit can be obtained.

[0098] The ethylene-α-olefin copolymer of the present invention preferably has the following properties (8).

[0099] (8) The intrinsic viscosity [η] (dl / g) measured in decahydronaphthalene at 135℃ and the weight-average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relationship (Eq-3).

[0100] 0.7×10 -4 ×Mw 0.776 ≤[η]≤1.65×10 -4 ×Mw 0.776…(Eq-3)

[0101] Preferably, the following (Eq-3') is satisfied.

[0102] 0.7×10 -4 ×Mw 0.776 ≤[η]≤1.40×10 -4 ×Mw 0.776 …(Eq-3')

[0103] More preferably, it satisfies the following (Eq-3).

[0104] 0.8×10 -4 ×Mw 0.776 ≤[η]≤1.20×10 -4 ×Mw 0.776 …(Eq-3)

[0105] It is known that when long branches are introduced into vinyl polymers, the intrinsic viscosity [η](dl / g) relative to molecular weight decreases compared to linear vinyl polymers without long branches (e.g., Walther Burchard, ADVANCES INPOLYMER SCIENCE, 143, Branched Polymer II, p. 137 (1999)). Therefore, when the intrinsic viscosity [η](dl / g) is 1.65 × 10⁻⁶, the intrinsic viscosity [η](dl / g) decreases. -4 ×Mw 0.776 In the following cases, ethylene-based polymers have multiple long branches, resulting in excellent moldability and flowability.

[0106] The intrinsic viscosity [η](dl / g) can be adjusted by the composition (A) of the catalyst (X) for olefin polymerization described later or by the type of solid support (S). Furthermore, even when using the same catalyst (X) for olefin polymerization, the intrinsic viscosity [η](dl / g) can be adjusted by the polymerization conditions or polymerization process; for example, by increasing the partial pressure of ethylene, the intrinsic viscosity [η](dl / g) can be increased. Under the manufacturing conditions of Example 4 described later, an intrinsic viscosity [η](dl / g) near the lower limit can be obtained; according to the manufacturing conditions of Example 2 described later, an intrinsic viscosity [η](dl / g) near the upper limit can be obtained.

[0107] The intrinsic viscosity [η] (dl / g) was determined using decahydronaphthalene solvent as described below. Approximately 20 mg of the sample was dissolved in 15 ml of decahydronaphthalene, and the relative viscosity ηsp was measured in an oil bath at 135°C. After diluting the decahydronaphthalene solution with an additional 5 ml of decahydronaphthalene solvent, the same procedure was repeated to measure the relative viscosity ηsp. This dilution procedure was repeated twice, and the value of ηsp / C, extrapolated to 0 from the concentration (C), was calculated as shown in the following formula, and this value was taken as the intrinsic viscosity [η] (unit: dl / g).

[0108] [η]=lim(ηsp / C)(C→0)

[0109] The weight-average molecular weight (Mw) was determined according to the method described above.

[0110] [process for producing ethylene-α-olefin copolymer]

[0111] The method for manufacturing the ethylene-α-olefin copolymer of the present invention will now be described.

[0112] The ethylene-α-olefin copolymer of the present invention can be efficiently manufactured by polymerizing ethylene with α-olefins having 4 to 10 carbon atoms in the presence of an olefin polymerization catalyst (X) containing the following components.

[0113] [catalyst (x) for olefin polymerization]

[0114] The catalyst (X) for olefin polymerization comprises the following components (A) and a solid support (S).

[0115] <Ingredients (A)>

[0116] Component (A) is a transition metal compound represented by formula (1) below (hereinafter also referred to as "transition metal compound (1)"). The catalyst (X) for olefin polymerization contains at least one transition metal compound (1). That is, as component (A), one transition metal compound (1) or multiple transition metal compounds (1) may be used.

[0117]

[0118] In the above formula (1), M is a zirconium atom or a hafnium atom, preferably a zirconium atom.

[0119] In the above formula (1), n ​​is an integer from 1 to 4 selected in a way that makes the transition metal compound (1) electrically neutral, preferably 2.

[0120] In the above formula (1), X is independently a hydrogen atom, a halogen atom, a hydrocarbon group with 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 with 1 to 20 carbon atoms.

[0121] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with chlorine being particularly preferred.

[0122] Examples of hydrocarbon groups with 1 to 20 carbon atoms mentioned above include:

[0123] Alkyl groups of the following: methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl (butan-2-yl), tert-butyl (2-methylpropane-2-yl), isobutyl (2-methylpropyl), pentane-2-yl, 2-methylbutyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), diisopentyl (Siamyl)(1,2-dimethylpropyl), isohexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, Thexyl (2,3-dimethylbutan-2-yl), 4,4-dimethylpentyl, etc., in straight-chain or branched form;

[0124] The following are straight-chain or branched alkenyl groups or groups containing unsaturated double bonds: 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, crotonyl (but-2-en-1-yl), but-3-en-2-yl, methpropenyl (2-methylallyl), but-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, isopentenyl (3-methylbut-2-en-1-yl), etc.

[0125] Alkyne groups, whether straight-chain or branched, or containing unsaturated triple bonds, such as ethynyl, prop-2-yn-1-yl, propyne (prop-1-yn-1-yl).

[0126] Benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cumyl (4-isopropylbenzyl), 2,4,6-triisopropylbenzyl, 4-tert-butylbenzyl, 3,5-di-tert-butylbenzyl, 1-phenylethyl, diphenylmethyl (diphenylmethyl) and other aromatic straight-chain or branched alkyl groups and groups containing unsaturated double bonds;

[0127] Cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, 1-adamantyl, and 2-adamantyl;

[0128] Cycloheptatrienyl, norbornyl;

[0129] Aromatic substituents such as phenyl, tolyl (methylphenyl), xylyl (dimethylphenyl), mesitylelel (2,4,6-trimethylphenyl), cumenyl (isopropylphenyl), tetramethylyl (2,3,5,6-tetramethylphenyl), 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-tert-butylphenyl, 3,5-ditert-butylphenyl, naphthyl, biphenyl, terphenyl, binatyl, acenaphthyl, phenanthryl, anthraceneyl, pyrene, ferrocene, etc., preferably methyl, isobutyl, neopentyl, diisopentyl (Siamyl), benzyl, phenyl, tolyl, xylyl, mesitylelel, or cumenyl.

[0130] The aforementioned hydrocarbon group with 1 to 20 carbon atoms can be a haloalkyl group in which some or all of the hydrogen atoms of the aforementioned hydrocarbon group with 1 to 20 carbon atoms are replaced by halogen atoms. Examples of such haloalkyl groups include fluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluorophenylmethyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, trifluoromethylphenyl, and bis(trifluoromethylphenyl), with pentafluorophenyl being the most preferred.

[0131] Examples of silicon-containing compounds include trimethylsilyl, triethylsilyl, triisopropylsilyl, diphenylmethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, triphenylsilyl, tri(trimethylsilyl)silyl, trimethylsilylmethyl, etc., with trimethylsilylmethyl being the most preferred.

[0132] Examples of the aforementioned oxygen-containing compounds include methoxy, ethoxy, n-propoxy, isopropoxy, allyloxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, benzyloxy, methoxymethoxy, phenoxy, 2,6-dimethylphenoxy, 2,6-diisopropylphenoxy, 2,6-di-tert-butylphenoxy, 2,4,6-trimethylphenoxy, 2,4,6-triisopropylphenoxy, acetoxy, tert-valerate, benzoyloxy, trifluoroacetoxy, perchlorate anion, and periodate anion, with methoxy, ethoxy, isopropoxy, and tert-butoxy being preferred.

[0133] Examples of nitrogen-containing groups mentioned above include amino, cyano, methylamino, dimethylamino, ethylamino, diethylamino, allylamino, diallylamino, benzylamino, dibenzylamino, pyrrolyl, piperidinyl, morpholino, pyrroleyl, and bis(trifuranyl)imide.

[0134] Examples of the conjugated diene derivative groups mentioned above include 1,3-butadienyl, isoprene (2-methyl-1,3-butadienyl), isoprene (1,3-pentadienyl), 2,4-hexadienyl, 1,4-diphenyl-1,3-pentadienyl, cyclopentadienyl, etc., with 1,3-butadienyl and 1,3-pentadienyl being preferred.

[0135] In the above formula (1), Q is a carbon atom or a silicon atom, preferably a silicon atom.

[0136] In equation (1) above, R 1 ~R 14 Each of the following is 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, or an oxygen-containing group having 1 to 20 carbon atoms.

[0137] As R 1 ~R 14 Hydrocarbon groups with 1 to 20 carbon atoms can be listed as straight-chain or branched alkyl groups, such as 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), isohexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, Thexyl (2,3-dimethylbutyl-2-yl), 4,4-dimethylpentyl, etc.

[0138] The straight-chain or branched alkenyl groups or groups containing unsaturated double bonds of 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, crotonyl (but-2-en-1-yl), but-3-en-2-yl, methpropenyl (2-methylallyl), but-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, isopentenyl (3-methylbut-2-en-1-yl), etc.

[0139] Alkyne groups, whether straight-chain or branched, or containing unsaturated triple bonds, such as ethynyl, prop-2-yn-1-yl, propyne (prop-1-yn-1-yl).

[0140] Benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cumyl(4-isopropylbenzyl), 2,4,6-triisopropylbenzyl, 4-tert-butylbenzyl, 3,5-di-tert-butylbenzyl, 1-phenylethyl, diphenylmethyl (diphenylmethyl), pentafluorophenylmethyl, etc., containing aromatic straight-chain or branched alkyl groups and groups containing unsaturated double bonds;

[0141] Cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, 1-adamantyl, and 2-adamantyl;

[0142] Cycloheptatrienyl, norbornyl;

[0143] Aromatic substituents of phenyl, tolyl (methylphenyl), xylyl (dimethylphenyl), mesitylelyl (2,4,6-trimethylphenyl), cumenyl (isopropylphenyl), tetramethylyl (2,3,5,6-tetramethylphenyl), 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, naphthyl, biphenyl, tert-phenyl, binatyl, acenaphthyl, phenanthryl, anthracene, pyrene, ferrocene, etc.

[0144] Halogenated hydrocarbon groups, such as fluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluorophenylmethyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, trifluoromethylphenyl, and bis(trifluoromethylphenyl), wherein the hydrogen atoms of the hydrocarbon group having 1 to 20 carbon atoms are partially or completely replaced by halogen atoms.

[0145] 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.

[0146] As R 1 ~R 14The 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.

[0147] As R 1 ~R 14 Oxide 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.

[0148] As R 1 ~R 14Nitrogen-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.

[0149] In equation (1) above, R 1 ~R 6 Adjacent substituents in the middle (e.g., R) 1 With R 2 R 2 With R 3 R 3 With R 4 R 4 With R 5 and R 5 With R 6 These rings can combine to form substituent rings. Preferably, the rings formed are 5- to 8-membered rings that form a fused ring with the indene ring portion, can have substituents, and are formed from saturated hydrocarbons (excluding the indene ring portion) or unsaturated hydrocarbons. In the case of multiple rings, they can be the same or different from each other. There are no particular limitations as long as the effects of the present invention are achieved. More preferably, the rings are 5- or 6-membered rings. In this case, the structure formed by combining the above-mentioned rings with the indene ring portion of the parent core can include, for example, benzo[a]indene rings, tetrahydrobenzodiindene rings, and cyclopentadiene rings, with benzo[a]indene rings and tetrahydrobenzodiindene rings being preferred. These rings can have substituents.

[0150] In equation (1) above, R 7 ~R 12 Adjacent substituents in the middle (e.g., R) 7 With R 8 R 8 With R9 R 9 With R 10 R 10 With R 11 and R 11 With R 12 These rings can combine to form substituent rings. Preferably, the rings formed are 5- to 8-membered rings that form a fused ring with the indene ring portion, can have substituents, and are formed from saturated hydrocarbons (excluding the indene ring portion) or unsaturated hydrocarbons. In the case of multiple rings, they can be the same or different from each other. There are no particular limitations as long as the effects of the present invention are achieved. More preferably, the rings are 5- or 6-membered rings. Examples of structures formed by combining the above-mentioned rings with the indene ring portion of the parent core include benzo[a]indene rings, tetrahydrobenzodiindene rings, cyclopentadiene rings, tetrahydrofluorene rings, and fluorene rings, with benzo[a]indene rings and tetrahydrobenzodiindene rings being preferred. These rings can have substituents.

[0151] In equation (1) above, R 13 With R 14 These rings can combine with each other to form rings containing Q, and these rings may also have substituents. The resulting rings are preferably saturated or unsaturated rings of 3 to 8 members that can have substituents. There are no particular limitations as long as the effects of the present invention are achieved; 4 to 6-membered rings are preferred. Examples of structures that can be combined with Q include cyclobutane rings, cyclopentane rings, fluorene rings, silylcyclobutane (silylhexane) rings, silylcyclopentane (silylhexane) rings, silylcyclohexane (silylhexane) rings, and silylfluorene rings, with cyclopentane rings, silylcyclobutane rings, and silylcyclopentane rings being preferred. These rings may have substituents.

[0152] The following are specific examples of transition metal compounds (1), but the scope of the invention is not particularly limited to these specific examples.

[0153] For convenience, the ligand structure of the above transition metal compound (1), excluding the portion shown as MXn (metal part), is divided into a 2-indenyl ring portion, a 1-indenyl ring portion, and an indenyl ring portion R. 1 R 6 and R 8 Substituents, indene ring moiety R 2 R 5 R 9 and R 12 Substituents, indene ring moiety R 3 R 4 R 10 and R 11 Substituents, 1-indenyl ring moiety R 7There are seven types of structures, including those with substituents and bridging components. The 2-indenyl ring portion is abbreviated as α, the 1-indenyl ring portion as β, and the indenyl ring portion as R... 1 R 6 and R 8 The abbreviation for substituent is γ, and the indenyl ring portion R 2 R 5 R 9 and R 12 The abbreviation for substituent is δ, and the indenyl ring part is R. 3 R 4 R 10 and R 11 The abbreviation for substituent is ε, and the 1-indenyl ring portion R 7 The abbreviation of the substituent is denoted as ζ, and the abbreviation of the bridging part is denoted as η. The abbreviations of each substituent are shown in [Table 1] to [Table 7].

[0154] [Table 1]

[0155] [Table 1]

[0156] 2-Indene ring portion

[0157]

[0158] [Table 2]

[0159] [Table 2]

[0160] 1-Indene ring portion

[0161]

[0162] In Tables 1 to 2 above, the wavy lines represent the joints with the bridging sections.

[0163] [Table 3]

[0164] [Table 3]

[0165] Indene ring R1, R6, R8 substituents

[0166] gamma-1 hydrogen gamma-2 methyl gamma-3 ethyl gamma-4 n-propyl gamma-5 allyl gamma-6 n-butyl gamma-7 but-3-en-1-yl gamma-8 benzyl gamma-9 pentafluorophenylmethyl gamma-10 phenyl gamma-11 tolyl gamma-12 naphthyl gamma-13 4-t-butylphenyl gamma-14 5-methyl-2-furyl gamma-15 5-methyl-2-thienyl

[0167] R in [Table 3] above 1 R 6 and R 8 Substituents can be the same or different from each other in their combination.

[0168] [Table 4]

[0169] [Table 4]

[0170] Indene ring R2, R5, R9, R12 substituents

[0171]

[0172] R in [Table 4] above 2 R 5 R 9 and R 12 Substituents can be the same or different from each other in their combination.

[0173] [Table 5]

[0174] [Table 5]

[0175] Indene ring R3, R4, R10, R11 substituents

[0176] epsilon-1 hydrogen epsilon-2 methyl epsilon-3 methoxy epsilon-4 ethyl epsilon-5 ethoxy epsilon-6 n-propyl epsilon-7 isopropyl epsilon-8 isopropoxy epsilon-9 n-butyl epsilon-10 i-butyl epsilon-11 sec-butyl epsilon-12 t-butyl epsilon-13 neopentyl epsilon-14 cyclopentyl epsilon-15 cyclohexyl epsilon-16 thexyl epsilon-17 t-octyl epsilon-18 phenoxy

[0177] R in [Table 5] above 3 R 4 R 10 and R 11 Substituents can be the same or different from each other in their combination.

[0178] [Table 6]

[0179] [Table 6]

[0180] 1-Indene ring R7 substituent

[0181]

[0182] [Table 7]

[0183] [Table 7]

[0184] Bridge connection section

[0185] eta-1 methylene eta-2 1,1-ethylene eta-3 benzyl (phenylmethylene) eta-4 dimethylmethylene (isopropylidene) eta-5 methylethylmethylene (sec-butylidene) eta-6 diethylmethylene (3-pentylidene) eta-7 dipropylmethylene (4-heptylidene) eta-8 dibutylmethylene (5-nonylidene) eta-9 dibenzylmethylene eta-10 (methyl)(phenyl)methylene (1-phenylethylidene) eta-11 (methyl)(4-methylphenyl)methylene eta-12 (methyl)(4-methoxyphenyl)methylene eta-13 diphenylmethylene eta-14 di(4-methylphenyl)methylene eta-15 di(4-methoxyphenyl)methylene eta-16 di(4-dimethylaminophenyl)methylene eta-17 1,1-cyclobutylidene eta-18 1,1-cyclopentylidene eta-19 1,1-cyclohexylidene eta-20 dimethylsilyl eta-21 diethylsilyl eta-22 divinylsilyl eta-23 dipropylsilyl eta-24 diisopropylsilyl eta-25 diallylsilyl eta-26 dibutylsilyl eta-27 dit-butylsilyl eta-28 dihexylsilyl eta-29 diphenylsilyl eta-30 di(4-methylphenyl)silyl eta-31 1,1-silylcyclobutyl (trimethylsilyl) eta-32 1,1-silylcyclopentyl (tetramethylsilyl) eta-33 1,1-silylcyclohexyl (pentamethylsilyl) eta-34 (methyl)(ethyl)silyl eta-35 (methyl)(vinyl)silyl eta-36 (methyl)(allyl)silyl eta-37 (methyl)(n-hexyl)silyl eta-38 (methyl)(n-octyl)silyl eta-39 (methyl)(n-decyl)silyl eta-40 (methyl)(cyclohexyl)silyl eta-41 (methyl)(phenyl)silyl

[0186] As specific examples of the metal portion MXn, the following can be listed:

[0187] ZrF2, ZrCl2, ZrBr2, ZrI2, Zr(Me)2, Zr(Bn)2, Zr(allyl)2, Zr(CH2-tBu)2, Zr(1,3-butadienyl), Zr(1,3-pentadienyl), Zr(2,4-hexadienyl), Zr(1,4-diphenyl-1,3-pentadienyl), Zr(CH2-Si(Me)3)2, Zr(OMe)2, Zr(OiPr)2, Zr(NMe2)2, Zr(OMs)2, Zr(OTs)2, Zr(OTf)2

[0188] HfF2, HfCl2, HfBr2, HfI2, Hf(Me)2, Hf(Bn)2, Hf(allyl)2, Hf(CH2-tBu)2, Hf(1,3-butadienyl), 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, etc.

[0189] Me represents methyl, Bn represents benzyl, tBu represents tert-butyl, Si(Me)3 represents trimethylsilyl, OMe represents methoxy, OiPr represents isopropoxy, NMe2 represents dimethylamino, OMs represents methanesulfonate, OTs represents p-toluenesulfonate, and OTf represents trifluoromethanesulfonate.

[0190] According to the above records, the 2-indenyl ring portion is α-1 in [Table 1], the 1-indenyl ring portion is β-5 in [Table 2], and the indenyl ring portion R... 1 R 6 and R 8 All substituents are γ-1,2-indenyl ring moieties R in [Table 3]. 2 and R 5 All substituents are δ-1, 2-indenyl ring moieties R in [Table 4] 3 and R 4 All substituents are from the ε-1 and 1-indenyl ring moiety R in [Table 5]. 7 The substituents are ζ-30 and 1-indenyl ring moiety R in [Table 6]. 9 The substituents are δ-38 and 1-indenyl ring moiety R in [Table 4]. 12 In the case where the substituent is δ-3 in [Table 4], the bridging part is η-20 in [Table 7], and the metal part MXn is ZrCl2, the following compound is shown in formula [6].

[0191]

[0192] Additionally, in the case where the 2-indenyl ring portion is α-1 in [Table 1], the 1-indenyl ring portion is β-2 in [Table 2], and the indenyl ring portion R... 1 R 6 and R 8 All substituents are γ-1,2-indenyl ring moieties R in [Table 3]. 2 and R 5 The substituents are all from the δ-2, 2-indenyl ring moiety R in [Table 4]. 3 and R 4 All substituents are from the ε-1 and 1-indenyl ring moiety R in [Table 5].7 The following compound is an example of a compound with the substituent being ζ-1 in [Table 6], the bridging part being η-4 in [Table 7], and the metal part being Zr(NMe2)2.

[0193]

[0194] Additionally, in the 2-indenyl ring portion, the α-3 and 1-indenyl ring portions are shown in [Table 1], and the β-1 and 2-indenyl ring portions are shown in [Table 2], R. 1 and R 6 All substituents are γ-2 and indenyl ring moiety R from [Table 3]. 2 R 5 and R 12 The substituents are all from the δ-1 and 1-indenyl ring moiety R in [Table 4]. 7 The substituents are the ζ-12, 1-indenyl ring moiety R in [Table 6]. 8 The substituents are the γ-1, 1-indenyl ring moiety R in [Table 3]. 9 The substituents are δ-42 and 1-indenyl ring moiety R in [Table 4]. 10 The substituent is the ε-3,1-indenyl ring moiety R in [Table 5]. 11 The 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.

[0195]

[0196] 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 12The 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).

[0197]

[0198] The aforementioned transition metal compound (1) can be manufactured using existing known methods, and the manufacturing method is not particularly limited.

[0199] Substituted indene compounds, which serve as starting materials, can be manufactured using known methods, and the manufacturing method is not particularly limited. Examples of known manufacturing methods include: "Organometallics 1994, 13, 954," "Organometallics 2006, 25, 1217," Japanese Patent Publication No. 2006-509059, "Bioorg.Med.Chem.2008, 16, 7399," WO2009 / 080216, "Organometallics 2011, 30, 5744," and Japanese Patent Publication No. 2011-500800. Manufacturing methods disclosed in publications such as "2012, 31, 4962," "Chem.Eur.J. 2012, 18, 4174," Japanese Patent Application Publication No. 2012-012307, Japanese Patent Application Publication No. 2012-121882, Japanese Patent Application Publication No. 2014-196319, Japanese Patent Publication No. 2014-513735, Japanese Patent Application Publication No. 2015-063495, Japanese Patent Publication No. 2016-501952, and Japanese Patent Application Publication No. 2019-059933.

[0200] Well-known methods for the preparation of transition metal compounds (1) and precursor compounds (ligands) can be cited, 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.”, etc.

[0201] Furthermore, in the aforementioned transition metal compound (1), the indenyl ring portion, which is bonded to the central metal by the bridging portion, has two orientations (front and back). Therefore, in the case where the 2-indenyl ring portion does not have a symmetry plane, as an example, there are two structural isomers represented by the following general formula [10a] or [10b].

[0202]

[0203] Similarly, the substituent R in the bridging part 13 With R 14 In different cases, as an example, there are also two structural isomers as shown in the following general formula [11a] or [11b].

[0204]

[0205] The purification, grading, or selective production of these structural isomer mixtures can be carried out using known methods, and the manufacturing method is not particularly limited. In addition to the methods listed above for the production of the transition metal compound (1), known manufacturing methods include those disclosed in Japanese Patent Application Publication No. 10-109996, "Organometallics 1999, 18, 5347," "Organometallics 2012, 31, 4340," and Japanese Patent Publication No. 2011-502192.

[0206] Within the range of the aforementioned transition metal compound (1), one type of transition metal compound may be used alone, or two or more may be used in combination. A mixture of structural isomers may be used, or one structural isomer may be used alone, or a mixture of two or more structural isomers may be used. As described above, according to the present invention, as a transition metal compound constituting a catalyst for olefin polymerization, only the aforementioned transition metal compound (1) may be used to produce ethylene polymers with a large number of long-branched chains with high catalytic activity. Without impairing this effect, one or more transition metal compounds different from the aforementioned transition metal compound (1) may also be used in combination. In this case, the transition metal compound (1) may be any of the above-described methods.

[0207] <Solid carrier (S)>

[0208] The solid support (S) contained in the catalyst (X) for olefin polymerization is an inorganic or organic compound, and is a particulate or microparticle solid.

[0209] Examples of inorganic compounds that can be used as the solid support (S) mentioned above include porous oxides, solid aluminoxane compounds, inorganic chlorides, clays, clay minerals, or ion-exchangeable layered compounds.

[0210] As the aforementioned porous oxides, SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, and ThO2, or complexes or mixtures containing them, can be used. Specifically, natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, and SiO2-TiO2-MgO can be used. Among these, substances with SiO2 as the main component are preferred.

[0211] Among them, the above-mentioned porous oxides may contain small amounts of carbonates, sulfates, nitrates and oxides of Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, Li2O, etc.

[0212] The properties of such porous oxides vary depending on their type and preparation method. As a solid carrier (S), the particle size is typically 0.2–300 μm, preferably 1–200 μm, and the specific surface area is typically 50–1200 m². 2 / g, preferably 100-1000m 2 Within the range of / g, the micropore volume is typically between 0.3 and 30 cm³. 3 Within the range of / g. Such a carrier can be used after firing at, for example, 100 to 1000°C, preferably 150 to 700°C, as needed.

[0213] Examples of solid aluminum oxane compounds include aluminum oxanes with structures shown in the following general formula (S-a), aluminum oxanes with structures shown in the following general formula (S-b), and aluminum oxanes having repeating units shown in the following general formula (S-c) and the following general formula (S-d).

[0214]

[0215] In the above equations (S-a)~(S-d), R e Each group is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4. Examples of such groups include methyl, ethyl, propyl, isopropyl, isopropenyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclohexyl, cyclooctyl, phenyl, tolyl, and ethylphenyl, with methyl, ethyl, and isobutyl being preferred, and methyl being particularly preferred. Furthermore, R e A portion of it can be replaced by halogen atoms such as chlorine or bromine, and the halogen content is expressed as R. eThe base value can be less than 40% by weight. The straight lines in the above formulas (S-c) and (S-d) that are not connected to an atom at one end represent bonds with other atoms not shown.

[0216] In formulas (S-a) and (S-b) above, r represents an integer from 2 to 500, preferably 6 to 300, and particularly preferably 10 to 100. In formulas (S-c) and (S-d) above, s and t each represent an integer greater than 1. r, s, and t are chosen so that the above-mentioned aluminum oxane can substantially maintain a solid state under the adopted reaction environment.

[0217] The aforementioned solid aluminoxane compounds differ from existing known supports for olefin polymerization catalysts. They do not contain inorganic solid components such as silica and alumina, nor organic polymer components such as polyethylene and polystyrene. They are solidified substances with alkyl aluminum compounds as the main component. "Solid state" means that the aluminoxane component substantially maintains a solid state under the reaction environment employed. More specifically, it means that when the aforementioned component (A) is contacted with the aluminoxane component as described below to prepare an olefin polymerization catalyst (e.g., an ethylene polymerization catalyst), and when the prepared olefin polymerization catalyst is used to polymerize olefins (e.g., ethylene) (e.g., suspension polymerization), the aluminoxane component substantially maintains a solid state.

[0218] Visual inspection is the simplest way to determine whether the aforementioned aluminoxane component is in a solid state, but this is often difficult to do, for example, during polymerization. In such cases, it can be determined, for example, by observing the properties of the polymer powder obtained after polymerization or its adhesion to the reactor. Conversely, if the polymer powder has good properties and minimal adhesion to the reactor, even if a small portion of the aforementioned aluminoxane component dissolves slightly in the polymerization environment, it does not deviate from the spirit of the invention. Indicators for judging the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of presence of amorphous polymers. From a quantitative point of view, bulk density is preferred. The aforementioned bulk density is typically in the range of 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

[0219] The solubility of the aforementioned solid aluminum oxane compound in n-hexane at a temperature of 25°C is typically in the range of 0–40 mol%, preferably 0–20 mol%, and particularly preferably 0–10 mol%.

[0220] Regarding the above dissolution ratio, it was determined by adding 2g of solid aluminum oxane compound carrier to 50ml of n-hexane at 25°C and stirring for 2 hours. Then, the solution was partially separated using a G-4 glass filter, and the aluminum concentration in the filtrate was measured. Therefore, the dissolution ratio is determined as the ratio of aluminum atoms present in the filtrate to the atomic weight of aluminum atoms corresponding to 2g of aluminum oxane used.

[0221] As the aforementioned solid aluminum oxane compound, known solid aluminum oxanes can be used without limitation, and solid polyaluminoxane compositions, such as those described in International Publication No. 2014 / 123212, can also be used. Known manufacturing methods include, for example, those described in Japanese Patent Application Publication No. 7-42301, Japanese Patent Application Publication No. 6-220126, Japanese Patent Application Publication No. 6-220128, Japanese Patent Application Publication No. 11-140113, Japanese Patent Application Publication No. 11-310607, Japanese Patent Application Publication No. 2000-38410, Japanese Patent Application Publication No. 2000-95810, and International Publication No. 2010 / 55652.

[0222] The average particle size of the aforementioned solid aluminum oxane compounds is typically in the range of 0.01–50,000 μm, preferably 0.1–1,000 μm, and particularly preferably 1–200 μm. The average particle size of the solid aluminum oxane compounds can be obtained by observing the particles using a scanning electron microscope, measuring the particle size of more than 100 particles, and then weight-averaging the results. First, regarding the particle size d of each particle, the length is measured by sandwiching the particle image with two parallel lines in both the horizontal and vertical directions, and then calculated using the following formula.

[0223] Particle size d = (horizontal length) 2 +(vertical length) 2 ) 0.5

[0224] Next, the weight-average particle size of the solid aluminum oxane compound is calculated using the particle size d and the number of particles n obtained above, by the following formula.

[0225] Average particle size = Σnd 4 / Σnd 3

[0226] The aforementioned solid aluminum oxane compounds are desired to have a specific surface area of ​​50–1000 m². 2 / g, preferably 100-800m 2 / g, with a pore volume of 0.1–2.5 cm³. 3 / g.

[0227] Examples of the aforementioned inorganic halides include MgCl2, MgBr2, MnCl2, and MnBr2. These inorganic halides can be used directly or after being pulverized using a ball mill or vibratory mill. Furthermore, substances that precipitate as particulates after dissolving the inorganic halide in a solvent such as an alcohol can also be used.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] Chemical treatment of clay and clay minerals is also preferred. Chemical treatments include surface treatments to remove surface impurities and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In acid treatment, in addition to removing surface impurities, the surface area can be increased by dissolving cations such as Al, Fe, and Mg in the crystalline structure. In alkali treatment, the crystalline structure of the clay is destroyed, resulting in changes in the clay structure. Furthermore, salt treatment and organic matter treatment can form ionic complexes, molecular complexes, and organic derivatives, altering the surface area or interlayer distance.

[0233] Ion-exchangeable layered compounds are layered compounds in which the exchangeable ions between the layers are exchanged with other large ions, thereby expanding the interlayer space. These large ions act as pillars supporting the layered structure and are usually called pillars. Furthermore, the introduction of other substances into the interlayer space of a layered compound is called intercalation. Examples of guest compounds for intercalation include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides (where R is a hydrocarbon group, etc.) such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3, and [Al...]. 13 O4(OH) 24 ] 7+ [Zr4(OH)] 14 ] 2+ [Fe3O(OCOCH3)6] + These include metal hydroxide ions, etc. These compounds can be used alone or in combination of two or more. Furthermore, when these compounds are intercalated, polymers obtained by hydrolyzing metal alkoxides such as Si(OR)4, Al(OR)3, and Ge(OR)4 (where R is a hydrocarbon group, etc.), colloidal inorganic compounds such as SiO2, etc., can also coexist. Additionally, oxides formed by heating and dehydration after intercalating the aforementioned metal hydroxide ions into the interlayer can be cited as examples of support structures.

[0234] Clay, clay minerals, and ion-exchange layered compounds can be used directly or after processing such as ball milling and sieving. Alternatively, they can be used after adding water and allowing adsorption, or after heat dehydration. Furthermore, one type can be used alone, or two or more types can be used in combination.

[0235] 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.

[0236] From the viewpoint of preventing foreign matter during molding, porous oxides are preferred as the aforementioned solid carrier (S).

[0237] <Ingredient (C)>

[0238] 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).

[0239] R a m Al(OR b ) n H p X q …(3)

[0240] 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.

[0241] M a AlR a 4…(4)

[0242] In equation (4), M a Represents Li, Na, or K, R a This indicates a hydrocarbon group with 1 to 15 carbon atoms.

[0243] R a r M b R b s X t …(5)

[0244] In equation (5), R a and R bM represents hydrocarbon groups with 1 to 15 carbon atoms, respectively. b The atoms are 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.

[0245] Among the above organometallic compounds (c-1), the compounds shown in the above formula (3) are preferred. Specifically, examples include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, and trialkylaluminum.

[0246] Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, and dimethyl aluminum bromide;

[0247] Alkyl sesquihalides of aluminum, such as methyl sesquichloride, ethyl sesquichloride, isopropyl sesquichloride, butyl sesquichloride, and ethyl sesquichloride aluminum bromide;

[0248] Alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide;

[0249] Hydrogenated alkyl aluminum, including dimethylaluminum, diethylaluminum, diisopropylaluminum, di-n-butylaluminum, diisobutylaluminum, diisohexylaluminum, diphenylaluminum, dicyclohexylaluminum, di-sec-heptylaluminum, and di-sec-nonylaluminum;

[0250] Alkoxydialkylaluminum, ethoxydiethylaluminum, methoxydiisopropylaluminum, ethoxydiisobutylaluminum, etc.

[0251] Examples of formula (4) above can include lithium aluminum hydride, etc. Examples of formula (5) above can include dialkyl zinc compounds as described in Japanese Patent Application Publication No. 2003-171412, etc., and can also be used in combination with phenolic compounds, etc.

[0252] As the aforementioned organoaluminum oxide compound (c-2), an organoaluminum oxide compound prepared from trialkylaluminum or tricycloalkylaluminum is preferred, and an aluminum oxane prepared from trimethylaluminum or triisobutylaluminum, such as methylaluminoxane, is particularly preferred. Such organoaluminum oxide compounds can be used alone or in combination of two or more.

[0253] As the compound (c-3) that reacts with the above-mentioned component (A) to form an ion pair, it may be a Lewis acid, an ionic compound, a borane compound, a carborane compound, a heteropoly compound, or a homopoly compound as described in Japanese Patent Application Publications Nos. 1-501950, 1-502036, 3-179005, 3-179006, 3-207703, 3-207704, and US5321106.

[0254] When the catalyst (X) for olefin polymerization is used in conjunction with organoaluminum oxides such as methylaluminoxane as co-catalyst components, it not only exhibits very high polymerization activity for olefin compounds, but also reacts with active hydrogen in a solid support, making it easy to prepare a solid support component containing co-catalyst components. Therefore, the preferred component (C) contains at least an organoaluminum oxide compound (C-2).

[0255] <Instructions for use and order of addition of each ingredient>

[0256] Catalyst (X) for olefin polymerization can be prepared by mixing and contacting components (A) and (S), and optionally (C), in an inert hydrocarbon.

[0257] As a method to bring the components into contact, focusing on the contact sequence, examples can be listed as follows:

[0258] (i) A method for bringing component (S) into contact with component (A);

[0259] (ii) A method for bringing component (S) into contact with component (C) and then into contact with component (A);

[0260] (iii) A method for bringing component (A) into contact with component (C) and then into contact with component (S);

[0261] (iv) A method for bringing component (S) into contact with component (C), and then into contact with a mixture of component (A) and component (C);

[0262] (v) A method of bringing component (S) into contact with component (C), then into contact with component (C), and then into contact with a mixture of component (A) and component (C).

[0263] When multiple components (C) are used, these components (C) may be the same or different from each other. Of the methods described above, (i), (ii), and (iii) are preferred.

[0264] In the methods described above, which illustrate the contact sequence, in steps involving contact between component (S) and component (C), and in steps involving contact between component (S) and component (A), the coexistence of component (G) suppresses scaling during the polymerization reaction or improves the particulate properties of the resulting polymer. As component (G), compounds with polar functional groups can be used, preferably non-ionic surfactants, and more preferably polyoxyethylene blocks, higher aliphatic amides, polyoxyethylene, polyoxyethylene alkyl ethers, alkyl diethanolamines, polyoxyalkylene alkylamines, glycerol fatty acid esters, and N-acyl amino acids. One or more of these can be used.

[0265] Solvents used in the preparation of catalyst (X) for olefin polymerization can include inert hydrocarbon solvents, specifically aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as vinyl chloride, chlorobenzene, and dichloromethane, or mixtures thereof.

[0266] When component (C) and component (S) come into contact, chemical bonds form through the reaction between reaction sites in component (C) and reaction sites in component (S), forming a contact material between component (C) and component (S). The contact time between component (C) and component (S) is typically 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is typically -50 to 200°C, preferably -20 to 120°C. During the initial contact of component (C) and component (S) proceeding rapidly, component (S) often disintegrates due to the exothermic reaction or reaction energy, resulting in a deteriorated morphology of the obtained solid catalyst component. This makes continuous operation difficult when using it for polymerization due to poor polymer morphology. Therefore, in the initial contact of component (C) and component (S), it is preferable to contact at a lower temperature to suppress exothermic reaction, or to control the exothermic reaction and proceed at a rate that can maintain the initial contact temperature. The same applies to the case of contacting component (C) with component (S) and then contacting component (C) again. The contact weight ratio of component (C) to component (S) (weight of component (C) / weight of component (S)) can be arbitrarily selected. When the contact weight ratio is high, more component (A) can be contacted, which can improve the catalytic activity per unit weight of solid catalyst component.

[0267] The contact weight ratio of component (C) to component (S) [= weight of component (C) / weight of component (S)] is preferably 0.05 to 3.0, and particularly preferably 0.1 to 2.0.

[0268] When the contact material of component (C) and component (S) comes into contact with component (A), the contact time is typically from 1 minute to 20 hours, preferably from 1 minute to 10 hours, and the contact temperature is typically in the range of -50 to 200°C, preferably from -50 to 100°C.

[0269] Component (C-1) is typically used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000, in a molar ratio of component (C-1) to all transition metal atoms (M) in component (A) [(C-1) / M].

[0270] The component (C-2) is usually used in an amount of 10 to 500,000, preferably 20 to 100,000, with a molar ratio of component (C-2) (in aluminum atom conversion) to all transition metal atoms (M) in component (A).

[0271] Component (C-3) is usually used in an amount of 1 to 10, preferably 1 to 5, in which the molar ratio of component (C-3) to all transition metal atoms (M) in component (A) [(C-3) / M].

[0272] The ratio of all transition metal atoms (M) in component (C) to those in component (A) can be determined using inductively coupled plasma light emission analysis (ICP). In ethylene polymerization, the olefin polymerization catalyst (X) can be used directly, or it can be prepolymerized with an olefin to form a prepolymer catalyst (XP) before use.

[0273] The prepolymer catalyst (XP) can be prepared by prepolymerizing ethylene or the like in an inert hydrocarbon solvent in the presence of an olefin polymerization catalyst (X). This can be carried out using any batch, semi-continuous, or continuous method, and can be performed under reduced pressure, normal pressure, or pressurized conditions. Furthermore, it is desirable to produce 0.01 to 1000 g, preferably 0.1 to 800 g, and more preferably 0.2 to 500 g of prepolymer catalyst (XP) per 1 g of solid catalyst component through prepolymerization.

[0274] After the prepolymer catalyst (XP) generated in an inert hydrocarbon solvent is separated from the suspension, it is resuspended in an inert hydrocarbon. Ethylene can be introduced into the resulting suspension, or it can be introduced into the suspension after drying.

[0275] The prepolymerization temperature is -20 to 80°C, preferably 0 to 60°C, and the prepolymerization time is 0.5 to 100 hours, preferably 1 to 50 hours. Prepolymerization preferably uses olefins with ethylene as the main component.

[0276] The form of the solid catalyst component used in prepolymerization can be any of the forms described without limitation. Furthermore, component (C) is used as needed, preferably the organometallic compound (c-1) shown in formula (3) above. When using component (C), it is used in an amount where the molar ratio (Al / M) of aluminum atoms (Al) in component (C) to transition metal atoms (M) in component (A) is 0.1 to 10000, preferably 0.5 to 5000.

[0277] Regarding the concentration of the catalyst (X) for olefin polymerization in the prepolymerization system, it is typically 1 to 1000 g / L, and more preferably 10 to 500 g / L, based on the catalyst / polymerization volume ratio. During prepolymerization, the aforementioned component (G) can coexist to suppress scaling or improve particulate properties.

[0278] In addition, in order to improve the flowability of the prepolymer catalyst (XP) and suppress hot spots, agglomeration, or polymer block formation during polymerization, the component (G) can be brought into contact with the prepolymer catalyst (XP) temporarily generated through prepolymerization.

[0279] The temperature at which the above-mentioned component (G) is brought into contact is typically -50 to 50°C, preferably -20 to 50°C, and the contact time is typically 1 minute to 20 hours, preferably 5 minutes to 10 hours.

[0280] When the catalyst (X) for olefin polymerization is brought into contact with the component (G), the component (G) is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 0.4 to 5 parts by weight, relative to 100 parts by weight of the catalyst (X) for olefin polymerization.

[0281] The mixing and contact of catalyst (X) and component (G) for olefin polymerization can be carried out in an inert hydrocarbon solvent, and the same solvents as those mentioned above can be listed as inert hydrocarbon solvents.

[0282] In the method for manufacturing ethylene-based polymers according to the present invention, the catalyst (X) used for olefin polymerization can be a prepolymer catalyst (XP) that has been dried (hereinafter also referred to as "dried prepolymer catalyst"). The drying of the prepolymer catalyst (XP) is usually carried out after removing hydrocarbons, which serve as the dispersion medium, from the suspension of the obtained prepolymer catalyst by means of filtration or the like.

[0283] The drying of the prepolymer catalyst (XP) is carried out by maintaining the prepolymer catalyst (XP) at a temperature below 70°C, preferably between 20 and 50°C, under the flow of an inactive gas. The resulting dried prepolymer catalyst preferably has a volatile content of less than 2.0% by weight, preferably less than 1.0% by weight. Lower volatile content in the dried prepolymer catalyst is better, with no particular lower limit, but in practice, it is 0.001% by weight. The drying time also depends on the drying temperature and is typically 1 to 48 hours.

[0284] The aforementioned dry prepolymer catalyst exhibits excellent flowability, thus enabling a stable supply to the polymerization reactor. Furthermore, when using the aforementioned dry prepolymer catalyst, polymerization can proceed stably without the need for a suspending solvent in the gas-phase polymerization system.

[0285] [Manufacturing methods for vinyl polymers]

[0286] The method for manufacturing the ethylene-based polymer according to the present invention will now be described. The ethylene-based polymer is obtained by polymerizing (homogenizing or copolymerizing) ethylene in the presence of the olefin polymerization catalyst (X) described above. By using the olefin polymerization catalyst (X), it is possible to efficiently manufacture low-density ethylene-based copolymers with high polymerization activity, excellent molding processability and mechanical strength, and a large number of long branches. The ethylene-based polymer of the present invention refers to a polymer in which the ethylene content is 10 mol% or more.

[0287] In this invention, polymerization can be carried out by liquid-phase polymerization methods such as solution polymerization and suspension polymerization or gas-phase polymerization, but it is preferred to use the above-mentioned prepolymer catalyst (XP) in suspension polymerization and gas-phase polymerization.

[0288] Specific examples of inert hydrocarbon media used in liquid-phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as vinyl chloride, chlorobenzene, and dichloromethane; and mixtures thereof. Additionally, olefins themselves can also be used as solvents in liquid-phase polymerization.

[0289] When using the above-mentioned catalyst for olefin polymerization to polymerize ethylene, the composition (A) is typically 1 × 10⁻⁶ per liter of reaction volume. -12 ~1×10 -1 mole, preferably 1×10 -8 ~1×10 -2 The amount used is in molar quantities. Furthermore, it is preferred to use the organoaluminum compound represented by formula (3) in component (C), particularly (c-1).

[0290] Furthermore, the polymerization temperature of ethylene using the aforementioned prepolymer catalyst (XP) is typically in the range of -50 to +200°C, preferably 0 to 170°C, and particularly preferably 60 to 170°C. The polymerization pressure is typically atmospheric pressure to 100 kgf / cm². 2 Preferred atmospheric pressure ~50 kgf / cm 2 Under these conditions, polymerization reactions can be carried out in any manner, including batch, semi-continuous, and continuous processes. Furthermore, polymerization can be divided into two or more stages with different reaction conditions.

[0291] The molecular weight of the resulting polymer can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. Generally, the more low molecular weight components there are, the more they adhere to the reactor walls and agitator, burdening the cleaning process and sometimes leading to reduced productivity. During polymerization, components (G) can be coexisted to inhibit scaling or improve particulate properties.

[0292] Furthermore, in this invention, the monomer supplied for the copolymerization reaction together with ethylene is one or more monomers selected from α-olefins having 4 to 10 carbon atoms, preferably α-olefins having 6 to 10 carbon atoms. Specific examples of α-olefins having 4 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene. Moreover, without impairing the effects of this invention, monomers other than ethylene and α-olefins having 4 to 10 carbon atoms may be supplied, or they may not be supplied at all.

[0293] By blending the ethylene-α-olefin copolymer involved in this invention with thermoplastic resins other than the ethylene-α-olefin copolymer involved in this invention (hereinafter referred to as "other thermoplastic resins"), a thermoplastic resin composition with excellent moldability and excellent mechanical strength can be obtained. The blending ratio of the ethylene-α-olefin copolymer of this invention to other thermoplastic resins (mass of ethylene-α-olefin copolymer / mass of other thermoplastic resins) is typically 99.9 / 0.1 to 0.1 / 99.9.

[0294] Other thermoplastic resins that can be used include crystalline thermoplastic resins such as polyolefins, polyamides, polyesters, and polyacetals; and non-crystalline thermoplastic resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate, polyphenylene ether, and polyacrylate. Polyvinyl chloride is also preferred.

[0295] Examples of the aforementioned polyolefins include ethylene-based polymers, propylene-based polymers, butene-based polymers, 4-methyl-1-pentene-based polymers, 3-methyl-1-butene-based polymers, and hexene-based polymers. Among these, ethylene-based polymers, propylene-based polymers, and 4-methyl-1-pentene-based polymers are preferred. When ethylene-based polymers are used, they can be existing ethylene-based polymers or ethylene-vinyl copolymers containing polar groups, with existing ethylene-based polymers being more preferred. The ethylene-based polymers and propylene-based polymers can be ethylene-based polymers and propylene polymers containing monomers derived from biomass, respectively.

[0296] In the ethylene-α-olefin copolymer of the present invention, without prejudice to the purpose of the present invention, additives such as weather stabilizers, heat stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents, and antioxidants may be added as needed.

[0297] The ethylene-α-olefin copolymer of the present invention may 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 solely derived from biomass, solely derived from fossil fuels, or may contain both. The term "monomer derived from biomass" refers to monomers formed from all renewable natural raw materials and their residues, including fungi, yeast, algae, and bacteria, of plant or animal origin, with a carbon content of 1 × 10⁻⁶. -12 The proportion of the ethylene-α-olefin copolymer is approximately 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 ethylene-α-olefin copolymer of the present invention comprises structural units derived from monomers derived from biomass.

[0298] [use]

[0299] By processing the ethylene-α-olefin copolymer of the present invention or a thermoplastic resin composition containing the ethylene-α-olefin copolymer, a molded body with excellent mechanical strength and a good balance of transparency and anti-blocking properties can be obtained with excellent moldability, preferably a film.

[0300] The ethylene-α-olefin copolymer or thermoplastic resin composition containing the ethylene-α-olefin copolymer of the present invention can be processed by conventional film forming or sheet forming, blow molding, injection molding, and extrusion molding. In film forming, extrusion lamination, T-film forming, and blow molding (air cooling, water cooling, multi-stage cooling, high-speed processing) are examples. The resulting film can be used as a single layer, but by forming multiple layers, various functions can be further imparted. Co-extrusion is an example of the forming method used in this case. On the other hand, by using lamination lamination or dry lamination, it is possible to laminate with paper or barrier films (aluminum foil, vapor-deposited film, coating film, etc.) that are difficult to co-extrude. The preparation of high-functional articles through multilayering via blow molding, injection molding, or co-extrusion in extrusion molding can be performed in the same way as film forming.

[0301] Examples of molded articles obtained by processing the ethylene-α-olefin copolymer of the present invention or a thermoplastic resin composition containing the ethylene-α-olefin copolymer include films, sheets, blow-molded infusion bags, blow-molded bottles, gasoline cans, tubes, pipes, wire sheaths, tear-off caps, daily necessities, etc., fibers, and large molded articles obtained by rotational molding.

[0302] Furthermore, the film obtained by processing the ethylene-α-olefin copolymer of the present invention or a thermoplastic resin composition containing the ethylene-α-olefin copolymer is suitable for various packaging films, protective films, infusion bags, agricultural materials, etc., such as water-containing packaging bags, liquid soup packaging bags, liquid paper containers, laminated base films, specially shaped liquid packaging bags (stand-up pouches, etc.), standard bags, heavy-duty packaging bags, sealing films, sugar bags, oil-containing packaging bags, and food packaging. It is also suitable for transparent films used in packaging bags-in-box, semiconductor materials, pharmaceuticals, food, etc. Moreover, the above-mentioned film can be laminated with substrates such as nylon, polyester, and polyolefin films to form multilayer films.

[0303] The raw materials for the substrate of multilayer membranes can include ethylene-based polymers and propylene-based polymers containing monomers derived from biomass.

[0304] Example

[0305] The present invention will now be described in more detail through embodiments. However, the present invention is not limited to the embodiments described below.

[0306] [Measurement and Evaluation Methods]

[0307] In the following examples, various physical properties of ethylene-α-olefin copolymers, etc., were measured according to the methods described in the [Specific Embodiments]. As an evaluation method not described in the [Specific Embodiments], the following method was used.

[0308] blown molding evaluation:

[0309] 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.

[0310] [Haze]

[0311] The total haze of the obtained membrane was measured in accordance with JIS 7136.

[0312] [Internal Haze]

[0313] The obtained membrane was placed in a sample cell filled with cyclohexanol and measured according to JIS 7136.

[0314] [Gloss level 20°]

[0315] The gloss of the obtained film was measured at an incident angle of 20° in accordance with JIS Z8741.

[0316] [Tensive Modulus of Elasticity]

[0317] The MD and TD directions of the obtained membrane were measured according to JIS K6781 at a test speed of 200 mm / min.

[0318] [Dart Impact]

[0319] 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.

[0320] [Adhesive force]

[0321] Two tubular membranes were overlapped to obtain a test piece. The test piece was then subjected to a 10 kg load at 50 °C and cured for 3 days. Afterward, the test piece was cut into 200 mm wide pieces, and the force required to pull it apart at 23 °C and 200 mm / min was measured as the adhesive force.

[0322] [Ingredients Used]

[0323] The transition metal compound (A), transition metal compound (B), and component (G) used in the examples are as follows.

[0324] 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.]

[0325] Transition metal compound (B-1): dimethylmethylenesilyl(3-n-propylcyclopentadienyl)(cyclopentadienyl)zirconium dichloride [synthesized according to the method described in Japanese Patent No. 5455354.]

[0326] 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.]

[0327] Ingredient (G-1): Lauryl diethanolamine (manufactured by Kao Corporation)

[0328] Ingredient (G-2): EMULGEN (registered trademark) 108 (manufactured by Kao Corporation)

[0329] <Synthesis of Prepolymer Catalyst (XP-1)>

[0330] 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 of the system 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.

[0331] 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.

[0332] <Synthesis of Prepolymer Catalyst (XP-2)>

[0333] 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 of the system 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.

[0334] 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. 0.6 L of an 8 mM toluene solution of transition metal compound (B-1) and 3.9 L of an 8 mM toluene solution of transition metal compound (B-2) were added. After contacting the system at 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 29.8 L. While adjusting the temperature of the obtained slurry 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 0.91 kg / hr. After 5 hours of ethylene supply, when the ethylene supply reached 4.6 kg, 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 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.

[0335] <Synthesis of Prepolymer Catalyst (XP-3)>

[0336] In the synthesis of the prepolymer catalyst (XP-2), the amount of 8 mM toluene solution of transition metal compound (B-1) added was changed to 1.1 L and the amount of 8 mM toluene solution of transition metal compound (B-2) added was changed to 3.4 L. Otherwise, the same operation was performed as in the synthesis of the prepolymer catalyst (XP-2) to obtain 6.1 kg of prepolymer catalyst (XP-3).

[0337] <Manufacturing of Vinyl Polymers>

[0338] [Example 1]

[0339] 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 prepolymerization catalyst, and Electrostripper (registered trademark) EA were continuously supplied under the polymerization conditions shown in Table 8 to reach a stable state. The polymerization reactants were continuously removed from the reactor and dried using a drying device to obtain ethylene-based polymer powder.

[0340] The obtained ethylene polymer powder was mixed with 850 ppm of Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.) and 210 ppm of calcium stearate (manufactured by Nitto Kasei Corporation) as heat stabilizers, and a twin-screw co-rotating extruder (manufactured by Ikegai Co., Ltd.) was used. The material was melt-blended in an extruder at a set temperature of 200°C and a screw speed of 300 rpm, then extruded into strands and cut into granules. The granules were used as samples for physical property testing. The results are shown in Table 9.

[0341] The obtained pellets were then used for the blow molding evaluation described above. The results are shown in Table 10.

[0342] [Examples 2-5, Comparative Examples 1-2]

[0343] Except for the changes in polymerization conditions shown in Table 8, the same procedure as in Example 1 was followed to obtain ethylene-based polymer powders, and various measurements and evaluations were performed. The results are shown in Tables 9 and 10. In Table 8, CHEMISTAT (registered trademark) 2500 (manufactured by Sanyo Chemical Industry Co., Ltd.) is listed as a component not used in Example 1.

[0344] [Comparative Example 3]

[0345] The low-density polyethylene SUNTEC-LD M2504 manufactured by Asahi Kasei Corporation (density: 927 kg / m³) was produced using the high-pressure process. 3MFR: 0.4 g / 10 min), and blow molding was performed in the same manner as in Example 1. The evaluation results of blow molding are shown in Table 10.

[0346] [Comparative Example 4]

[0347] The low-density polyethylene SUNTEC-LD M2102 manufactured by Asahi Kasei Corporation (density: 922 kg / m³) was produced using the high-pressure process. 3 MFR: 0.2 g / 10 min), and blow molding was performed in the same manner as in Example 1. The melt film ruptured, and a film with a thickness of 40 μm could not be collected.

[0348] [Table 8]

[0349]

[0350] [Table 9]

[0351]

[0352] [Table 10]

[0353]

[0354] As shown in Table 10, compared with Comparative Examples 1 and 2, the films of the Examples have excellent transparency; compared with Comparative Example 3, the films of the Examples have excellent mechanical strength (dart impact); and compared with Comparative Example 4, the polymers of the Examples have excellent moldability.

Claims

1. An ethylene-α-olefin copolymer which is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, the ethylene-α-olefin copolymer being characterized in that: (1) to (6) below are satisfied, (2) a melt flow rate (MFR) under a load of 2.16 kg at 190°C is in a range of 0.1 g / 10 minutes or more and less than 3.0 g / 10 minutes; (1) density in the range of 890 kg / m 3 above 925 kg / m 3 below the range of 925 kg / m (5) a number average molecular weight (Mn), a weight average molecular weight (Mw), and a Z average molecular weight (Mz) measured by a GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-2), -7.0 < Mz / Mw - Mw / Mn < 2.0 (Eq-2); (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 1.20 x 10 * -4 -4 above 2.90 x 10 -13 below;​​ (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-VISCO method (GPC-VISCO), 0.01 x 10 -13 × Mw 3.4 ≤ η0≤ 3.5 x 10 -13 × Mw 3.4 (Eq-1); (6) a melting curve obtained by differential scanning calorimetry (DSC) has a plurality of peaks.

2. The ethylene-α-olefin copolymer according to claim 1, characterized in that: (7) below is further satisfied, (7) a 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 a range of 4.0 or more and 15.0 or less.

3. The ethylene-α-olefin copolymer according to claim 1 or 2, characterized in that: (8) below is further satisfied, (8) an intrinsic viscosity [[η] (dl / g)] measured in decahydronaphthalene at 135°C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-3), 4. A thermoplastic resin composition, characterized by: comprising the ethylene-α-olefin copolymer 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.

5. A film, characterized by: comprising the ethylene-α-olefin copolymer according to any one of claims 1 to 3.

6. A multilayer film, characterized by: having a layer comprising the ethylene-α-olefin copolymer according to any one of claims 1 to 3. ​ 0.7 x 10 -4 x Mw 0.776 ≤ [η] ≤ 1.65 x 10 -4 x Mw 0.776 (Eq-3). ​ ​ ​ ​ ​ ​

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