Ethylene-α-olefin copolymer, thermoplastic resin composition, and molded article

Abstract

To provide an ethylene-α-olefin copolymer that can produce molded articles with superior surface appearance and a good balance of moldability, mechanical strength, transparency, and blocking resistance compared to conventionally known ethylene-based polymers, a thermoplastic resin composition containing the polymer, and a film obtained from the polymer or the thermoplastic resin composition. [Solution] An ethylene-α-olefin copolymer that is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, and satisfies specific requirements (1) to (5).

Description

[Technical Field]

[0001] The present invention relates to an ethylene-α-olefin copolymer, a thermoplastic resin composition containing the ethylene-α-olefin copolymer, and a molded article containing the same. [Background technology]

[0002] Ethylene polymers are used in a variety of molding methods and applications, and different properties are required of these polymers depending on the molding method and application. For example, in T-die molding, neck-in occurs, where the film edges shrink towards the center. When neck-in occurs, the film width decreases, and the thickness of the film edges becomes thicker than that of the center. Therefore, if the neck-in is large, problems such as poor product yield or inability to produce products of the desired width may occur. In hollow molding, problems such as sagging or breakage of the molten film may occur, and in inflation molding, problems such as wobbling or breakage of the molten film may occur. To suppress these problems, it is necessary to select an ethylene polymer with a high melt tension relative to its molecular weight.

[0003] Long-chain unbranched ethylene polymers obtained using metallocene catalysts exhibit excellent mechanical strength, but have limitations in moldability. For example, neck-in can be large in T-die molding, molten film sagging can occur in hollow molding, and film wrinkling can occur due to molten film movement in inflation molding. High-pressure low-density polyethylene has high melt tension and excellent moldability, but its complex long-chain branching results in inferior mechanical strength, such as tensile strength, tear strength, and impact strength.

[0004] To solve these problems, various ethylene polymers with long-chain branching have been disclosed. Patent Document 1 proposes a composition of an ethylene polymer obtained using a metallocene catalyst and high-pressure low-density polyethylene. However, if the content of high-pressure low-density polyethylene is high, it is expected that the mechanical strength, such as tensile strength, tear strength, or impact strength, will be inferior, and if the content of high-pressure low-density polyethylene is low, the improvement in melt tension will not be sufficient, so deterioration in moldability, such as a large neck-in, is expected.

[0005] Furthermore, Patent Document 2 discloses an ethylene polymer obtained by solution polymerization in the presence of a catalyst consisting of ethylenebis(indenyl)hafnium dichloride and methylalmoxane; Patent Document 3 discloses an ethylene polymer obtained by gas-phase polymerization in the presence of a catalyst consisting of ethylenebis(indenyl)zirconium dichloride and methylalmoxane supported on silica; Patent Document 4 discloses an ethylene polymer obtained by solution polymerization in the presence of a constrained geometric catalyst; and Patent Document 5 discloses an ethylene polymer obtained by gas-phase polymerization in the presence of a catalyst consisting of racemic and meso isomers of Me2Si(2-Me-Ind)2 and methylalmoxane supported on silica. While these ethylene polymers are described as having improved melt tension and excellent moldability compared to linear ethylene polymers without long-chain branching, the neck-in is still large, so the improvement in moldability is insufficient, and the improvement in the blocking resistance of the film is also expected to be insufficient. When using ethylene-based polymers in films, it is common practice to add antiblocking agents to prevent blocking. However, adding large amounts of antiblocking agents is undesirable in certain applications due to increased costs and concerns about the hygiene of the contents. Therefore, there is a demand for films that exhibit excellent blocking resistance without the need for antiblocking agents.

[0006] Patent documents 6, 7, and 8 disclose ethylene polymers in which intrinsic viscosity and weight-average molecular weight satisfy specific relationships, melt tension and shear viscosity satisfy specific relationships, and zero shear viscosity and weight-average molecular weight exhibit specific relationships. These ethylene polymers exhibit improved take-up surging and improved neck-in and inflation moldability in T-die molding compared to conventional ethylene polymers in which long-chain branching is introduced using metallocene catalysts. However, further improvements in mechanical strength and transparency are desired. Although higher external haze due to minute irregularities on the film surface results in superior blocking resistance, a good balance between transparency and blocking resistance is desired from the viewpoint of visibility of contents and inspection of defects in the film. Similarly, improved transparency is desired when ethylene polymers are used in bottles and the like.

[0007] Patent document 9 discloses ethylene-based polymers having specific melting properties and molecular structures. These ethylene-based polymers have improved mechanical strength (dirt impact) and transparency, and the molded films have an excellent balance of mechanical strength, transparency, and blocking resistance. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 7-26079 [Patent Document 2] Japanese Patent Application Publication No. 2-276807 [Patent Document 3] Japanese Patent Application Publication No. 4-213309 [Patent Document 4] International Publication No. 93 / 08221 [Patent Document 5] Japanese Patent Application Publication No. 8-311260 [Patent Document 6] Japanese Patent Publication No. 2006-233207 [Patent Document 7] Japanese Patent Publication No. 2008-31380 [Patent Document 8] Japanese Patent Publication No. 2009-197225 [Patent Document 9] International Publication No. 2022 / 210844 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] However, Patent Document 9 does not mention whether or not fisheye (FE) formation occurs in films manufactured from ethylene-based polymers. If fisheye (FE) formation occurs, it is expected that it will impair the surface appearance of films, sheets, and various containers during molding, leading to problems such as the inability to obtain a uniform printed surface.

[0010] The present invention aims to provide an ethylene-α-olefin copolymer that can produce molded articles with superior surface appearance and a better balance of moldability, mechanical strength, transparency, and blocking resistance compared to conventionally known ethylene-based polymers, a thermoplastic resin composition containing the polymer, and a film obtained from the polymer or the thermoplastic resin composition. [Means for solving the problem]

[0011] As a result of diligent research, the inventors have discovered an ethylene-α-olefin copolymer that possesses specific melting properties and molecular structure, and whose number of fisheyes (FE) when formed into a film falls within a specific range, thereby enabling the production of molded articles with excellent surface appearance and a good balance of moldability, mechanical strength, transparency, and blocking resistance. This has led to the completion of the present invention.

[0012] The present invention relates, for example, to the following [1] to [9]. [1] An ethylene-α-olefin copolymer that is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, and satisfies the following requirements (1) to (5). (1) Density is 890 kg / m³ 3 More than 935kg / m 3 It is within the following range. (2) The melt flow rate (MFR) at 190 °C under a load of 2.16 kg is in the range of 0.1 g / 10 min or more and 100 g / 10 min or less. (3) The ratio [MT / η * (P)] of the melt tension [MT (g)] at 190 °C to the shear viscosity [η * (P)] at 200 °C and an angular velocity of 1.0 rad / s is in the range of 1.20×10 -4 or more and 4.00×10 -4 or less. (4) The zero shear viscosity [η0 (P)] at 200 °C and the weight average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1). 0.01×10 -13 ×Mw 3.4 ≦η0≦3.5×10 -13 ×Mw 3.4 ···(Eq-1) (5) The number of fish eyes (FE: size 100 μm or more) per 3000 cm 2 of a 50-μm-thick film obtained using a T-die film forming machine is 100 or less.

[0013] [2] The ethylene-α-olefin copolymer according to item [1], which further satisfies the following requirement (6). (6) In the powder particle size distribution of the ethylene-α-olefin copolymer before melt kneading, the mass fraction of the powder that does not pass through a No. 10 (2-mm opening) mesh sieve (ASTM E11) with respect to 100% by mass of the powder is 10% by mass or less.

[0014] [3] A thermoplastic resin composition containing the ethylene-α-olefin copolymer according to item [1] or [2] and a thermoplastic resin (excluding the ethylene-α-olefin copolymer).

[0015] [4] A molded article containing the ethylene-α-olefin copolymer according to item [1] or [2].

[0016] A film comprising the ethylene-α-olefin copolymer described in item [5][1] or [2].

[0017] A laminate having a layer comprising the ethylene-α-olefin copolymer described in item [6][1] or [2].

[0018] [7] A method for producing an ethylene-α-olefin copolymer according to item [1] or [2], obtained using a catalyst for polyolefin production comprising a transition metal complex (T) represented by the following general formula [1] and a solid support (S). [ka] (In the general formula [1], M is a transition metal atom of group 4 of the periodic table, n is an integer from 1 to 4 selected such that the transition metal complex (T) is electrically neutral. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can coordinate with a lone pair of electrons, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group, and if n is 2 or more, the multiple groups represented by X may be the same or different from each other, and may bond to each other to form a ring. Q is an atom in Group 14 of the periodic table, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. R 1 ~R 6Adjacent substituents may bond to each other to form a ring which may also have substituents. R 7 ~R 12 Adjacent substituents may bond to each other to form a ring which may also have substituents. R 13 and R 14 These elements may bond to each other to form a ring containing Q, and this ring may have substituents.

[0019] [8] The method for producing an ethylene-α-olefin copolymer according to item [7], wherein the catalyst for producing the polyolefin contains an organoaluminum oxy compound (B-2) and the solid carrier (S) is a porous material.

[0020] [9] The method for producing an ethylene-α-olefin copolymer according to item [8], wherein the particle size dispersion ratio (R10) of the solid carrier (S) measured by the following measurement method is greater than 0% and less than or equal to 95%, and the particle size dispersion ratio (R50) of the solid carrier (S) measured by the following measurement method is greater than 0% and less than or equal to 95%. [Measurement method] Using methanol as the dispersion medium, the solid carrier (S) is dispersed in an ultrasonic homogenizer at an output of 25W for 5 minutes, and the average particle diameter (Dw10) corresponding to 10% of the cumulative mass from the smallest diameter in the particle size distribution and the average particle diameter (Dw50) corresponding to 50% of the cumulative mass from the smallest diameter in the particle size distribution are measured by wet laser diffraction scattering. Similarly, the average particle diameter (Ds10) corresponding to 10% of the cumulative mass from the smallest diameter in the particle size distribution and the average particle diameter (Ds50) corresponding to 50% of the cumulative mass from the smallest diameter in the particle size distribution are measured under the same conditions, except that the dispersion was performed at an output of 40W for 15 minutes. The particle size dispersion ratios (R10) and (R50) are expressed by the following formulas. R10 = Ds10 / Dw10 × 100 R50 = Ds50 / Dsw50 × 100 [Effects of the Invention]

[0021] According to the ethylene-α-olefin copolymer and thermoplastic resin composition containing the polymer of the present invention, it is possible to suitably produce molded articles that have excellent surface appearance and a good balance of moldability, mechanical strength, transparency, and blocking resistance. [Modes for carrying out the invention]

[0022] The ethylene-α-olefin copolymer according to the present invention will be described in detail below. [Ethylene-α-olefin copolymer] The ethylene-α-olefin copolymer according to the present invention is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, and preferably a copolymer of ethylene and an α-olefin having 6 to 10 carbon atoms. Examples of α-olefins having 4 to 10 carbon atoms that can be used in copolymerization with ethylene include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.

[0023] The ethylene-α-olefin copolymer of the present invention has the following properties as shown in requirements (1) to (5). ≪Requirement (1)≫ Density is 890 kg / m³ 3 More than 935kg / m 3 It is within the following range, preferably 900 kg / m 3 More than 930kg / m 3 More preferably, 905 kg / m 3 More than 925kg / m 3 It is within the following range. When the density is above the lower limit, the surface of the molded film is less sticky, and when the density is below the upper limit, the molded film has good low-temperature sealing properties.

[0024] The density of an ethylene-α-olefin copolymer depends on the α-olefin content; the lower the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. The α-olefin content of an ethylene-α-olefin copolymer is determined by the composition ratio of α-olefin to ethylene (α-olefin / ethylene) in the polymerization system (for example, Walter Kaminsky, Macromol. Chem. 193, p.606 (1992)). Therefore, by increasing or decreasing the α-olefin / ethylene ratio, ethylene-α-olefin copolymers with densities within the above range can be produced.

[0025] The density is measured as follows: The strands obtained during MFR measurement are heat-treated at 100°C for 30 minutes, then left at room temperature for 1 hour before being measured using the density gradient tube method.

[0026] ≪Requirement (2)≫ The melt flow rate (MFR) at a load of 2.16 kg at 190°C is in the range of 0.1 g / 10 min to 100 g / 10 min, preferably in the range of 0.3 g / 10 min to 50 g / 10 min, and more preferably in the range of 0.4 g / 10 min to 20 g / 10 min.

[0027] When the melt flow rate (MFR) is above the lower limit, the shear viscosity of the ethylene-α-olefin copolymer is not too high, and the extrusion load is good. When the melt flow rate (MFR) is below the upper limit, the mechanical strength of the ethylene-α-olefin copolymer is good.

[0028] The melt flow rate (MFR) is strongly dependent on molecular weight; a smaller MFR corresponds to a larger molecular weight, and a larger MFR corresponds to a smaller molecular weight. Furthermore, it is known that the molecular weight of ethylene-based polymers is determined by the hydrogen-to-ethylene ratio (hydrogen / ethylene) within the polymerization system (e.g., Kazuo Soga et al., "Catalytic Olefin Polymerization," Kodansha Scientific, 1990, p. 376). Therefore, it is possible to increase or decrease the melt flow rate (MFR) of ethylene-based polymers by increasing or decreasing the hydrogen / ethylene ratio. The melt flow rate (MFR) is measured according to JIS K7210 under conditions of 190°C and a 2.16 kg load.

[0029] ≪Requirement (3)≫ Melt tension at 190°C [MT(g)] and shear viscosity at 200°C and angular velocity 1.0 rad / sec [η] * (P) (P is Poise.) Ratio to [MT / η * (g / P) is 1.20 × 10 -4 The above 4.00 x 10 -4 It is within the following range, preferably 1.30 × 10 -4 The above 3.80 x 10 -4 More preferably 1.40 × 10 -4 The above 3.50 x 10 -4 It is within the following range.

[0030] MT / η * When the value is above the lower limit, ethylene-α-olefin copolymers have high melt tension relative to their molecular weight, resulting in excellent moldability. MT / η * When the value is below the upper limit, ethylene-α-olefin copolymer exhibits excellent mechanical strength.

[0031] MT / η * This depends on the long-chain branching content of the ethylene copolymer; the higher the long-chain branching content, the higher the MT / η ratio. * The larger the value, and the lower the long-chain branching content, the MT / η ratio. *The length becomes smaller. Long-chain branching is defined as a branched structure in an ethylene copolymer with a length greater than or equal to the molecular weight (Me) between entanglement points, and it is known that the introduction of long-chain branching significantly changes the melt properties and moldability of ethylene polymers (for example, Kazuo Matsuura et al., "Polyethylene Technology Reader," Kogyo Chosakai, 2001, pp. 32, 36). MT / η * This can be adjusted by the type of component (T) or solid support (S) of the catalyst for polyolefin production described later. Furthermore, even when using the same catalyst for polyolefin production, it can be adjusted by the polymerization conditions or process, for example, by increasing the ethylene partial pressure, MT / η * It can be lowered.

[0032] The melt tension [MT(g)] is measured as follows: The melt tension (MT) (unit: g) of an ethylene-α-olefin copolymer at 190°C is determined by measuring the stress when stretched at a constant rate. A capillary rheometer is used for the measurement (for example, in the examples described later, a Capillograph 1D capillary rheometer manufactured by Toyo Seiki Seisakusho Co., Ltd. was used). The measurement conditions were: resin temperature 190°C, melting time 6 minutes, barrel diameter 9.55 mmφ, extrusion speed 15 mm / min, winding speed 24 m / min (if the molten filament breaks, reduce the winding speed by 5 m / min increments), nozzle diameter 2.095 mmφ, and nozzle length 8 mm.

[0033] Shear viscosity at 200°C and angular velocity 1.0 rad / sec [η * (P) is measured as follows: Shear viscosity (η * ) is the shear viscosity (η) at a measurement temperature of 200°C. *The angular velocity [ω (rad / sec)] variance of the ethylene-α-olefin copolymer is measured in the range of 0.01 ≤ ω ≤ 100. A viscoelasticity measuring device is used for the measurement (for example, in the example described later, an Anton Paar Physica MCR301 viscoelasticity measuring device was used), a 25 mmφ parallel plate is used as the sample holder, and the sample thickness of the ethylene-α-olefin copolymer is set to approximately 2.0 mm. There are 5 measurement points for each digit of ω. The amount of strain is appropriately selected in the range of 3 to 10% so that the torque can be detected within the measurement range and does not exceed the torque limit.

[0034] The samples used for shear viscosity measurement were prepared using a molding machine (for example, in the example described later, a press molding machine manufactured by Shinto Metal Industries Co., Ltd. was used), with 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°C, cooling time 5 minutes, cooling pressure 100 kgf / cm² 2 The measurement sample is prepared by press-molding it to a thickness of 2 mm under these conditions.

[0035] ≪Requirement (4)≫ The zero shear viscosity [η0(P)] at 200°C and the weight-average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relationship (Eq-1). 0.01 × 10 -13 ×Mw 3.4 ≤η0 ≤ 3.5 × 10 -13 ×Mw 3.4 ...(Eq-1)

[0036] The zero shear viscosity [η0(P)] and weight-average molecular weight (Mw) preferably satisfy the following relationship (Eq-1'). 0.05 × 10 -13 ×Mw 3.4 ≤η0 ≤ 3.0 × 10 -13 ×Mw 3.4 ...(Eq-1')

[0037] The zero shear viscosity [η0(P)] and weight-average molecular weight (Mw) more preferably satisfy the following relationship (Eq-1”). 0.10 × 10 -13 ×Mw 3.4 ≤η0 ≤ 2.5 × 10 -13 ×Mw 3.4 ...(Eq-1)

[0038] When zero shear viscosity [η0(P)] is plotted against weight-average molecular weight (Mw) on a log-log scale, resins whose extensional viscosity does not exhibit strain-curing properties, such as long-chain, unbranched, linear ethylene polymers, follow a power law with a slope of 3.4, whereas resins whose extensional viscosity exhibits strain-curing properties, such as high-pressure low-density polyethylene, exhibit a zero shear viscosity [η0(P)] lower than that of a power law (C Gabriel, H. Munstedt, J. Rheol., 47(3), 619 (2003)).

[0039] When the zero shear viscosity [η0(P)] at 200°C is below the upper limit, the extensional viscosity of the ethylene-α-olefin copolymer exhibits strain rate curing, thus preventing take-up surging during molding.

[0040] Furthermore, when molten resin flows into the die, tensile stress is generated by the extensional flow. When this tensile stress exceeds a critical value, brittle fracture occurs, resulting in unstable flow at the die exit called melt fracture, and minute irregularities are formed on the surface of the molded product (FN Cogswell, Polymer Melt Rheology, Wiley, 1981). When the zero shear viscosity [η0(P)] is within the aforementioned range, the tensile stress becomes large at the strain rate of a typical molding process, and melt fracture occurs in appropriate amounts. Because these melt fractures appropriately form minute irregularities on the film surface, the resulting film has an excellent balance between transparency and blocking resistance.

[0041] The relationship between zero shear viscosity [η0(P)] and weight-average molecular weight (Mw) is thought to depend on the content and length of long-chain branches in the ethylene polymer; the higher the content of long-chain branches and the shorter the length of the long-chain branches, the lower the η0 / Mw ratio. 3.4η0 / Mw shows a small value, and the lower the long-chain branching content and the longer the length of the long-chain branches, the lower the value. 3.4 This is thought to indicate a large value.

[0042] The zero shear viscosity [η0(P)] can be adjusted by the type of component (T) or solid support (S) of the catalyst for polyolefin production, as described below. Furthermore, even when using the same catalyst for polyolefin production, it can be adjusted by the polymerization conditions or process. For example, increasing the ethylene partial pressure can increase the zero shear viscosity [η0(P)].

[0043] The zero shear viscosity [η0(P)] at 200°C is measured as follows: At a measurement temperature of 200°C, shear viscosity (η * The angular velocity ω (rad / sec) variance of the material is measured in the range of 0.01 ≤ ω ≤ 100. A viscoelasticity measuring device (for example, in the example described later, an Anton Paar Physica MCR301 viscoelasticity measuring device) is used for the measurement, a 25 mmφ parallel plate is used as the sample holder, and the sample thickness of the ethylene-α-olefin copolymer is set to approximately 2.0 mm. There are 5 measurement points for each digit of ω. The amount of strain is appropriately selected in the range of 3 to 10% so that the torque can be detected within the measurement range and does not exceed the torque limit. The ethylene-α-olefin copolymer sample used for shear viscosity measurement was prepared using a molding machine (for example, in the example described later, a press molding machine manufactured by Shinto Metal Industries Co., Ltd. was used), with 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°C, cooling time 5 minutes, cooling pressure 100 kgf / cm² 2 The measurement sample is prepared by press-molding it to a thickness of 2 mm under these conditions.

[0044] The zero shear viscosity (η0) is obtained by the Carreau model of the following equation using the nonlinear least squares method to obtain the experimentally measured rheological curve [shear viscosity (η) * It is calculated by fitting it to the angular velocity (ω) variance of ). η * =η0[1+(λω)] a ] (n-1) / a [λ represents a parameter with the dimension of time, a represents the fitting parameter, and n represents the power law index of the material.] Furthermore, the fitting using the nonlinear least squares method is performed so that d in the following equation is minimized.

[0045]

number

[0046] Weight-average molecular weight (Mw), etc., are measured by gel permeation chromatography (GPC) as follows. A differential refractometer and a capillary viscometer were used as detectors, the column temperature was set to 145°C, o-dichlorobenzene was used as the mobile phase, the flow rate was 1.0 mL / min, the sample concentration was 0.1% by mass, 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 device, two Agilent PLgel Olexis analytical columns were used, and standard polystyrene from Tosoh Corporation was used. Molecular weight calculations were performed by calculating the measured viscosity from a viscometer and refractometer, and determining the number-average molecular weight (Mn), weight-average molecular weight (Mw), Z-average molecular weight (Mz), and molecular weight distribution (Mw / Mn and Mz / Mw) from the measured universal calibration.

[0047] ≪Requirement (5)≫ A 50 μm thick film obtained using a T-die film deposition machine was measured over 3000 cm². 2The number of fish eyes (FE: size 100 μm or larger) per unit is usually 100 or less, preferably 70 or less, more preferably 50 or less, and even more preferably 25 or less, and in one embodiment it may be 1 or more. 3000cm of 50μm thick film 2 If the number of fisheyes (FE) per mold exceeds 100, the appearance of the resulting molded product may be poor. By keeping the number of fisheyes (FE) within the above range, a molded product with a good appearance can be obtained.

[0048] The number of fisheyes (FE) can be adjusted by the mass fraction of the large particle size component, as described below. By reducing the mass fraction of the large particle size component, the number of fisheyes (FE) generated during molding can be reduced.

[0049] The number of fisheye (FE) cells in ethylene-α-olefin copolymers is measured as follows. The number of fisheyes (FE) on a 50 μm thick film fabricated using a 25 mmφ T-die film deposition machine manufactured by Plastics Engineering Laboratory Co., Ltd. was measured using a Fisheye Counter (trademark) manufactured by Hutech Co., Ltd. as a gel counter, under detection parameters of width 0.1 mm and length 0.1 mm. The number of measurements was calculated per unit area of ​​film (3000 cm²). 2 This is expressed as the number of fisheyes (FE: size 100 μm or larger) per unit area. The film production conditions are as follows: T-die film forming machine: Manufactured by Plastics Engineering Laboratory Co., Ltd. Model: GT-25-A Screw diameter: 25mm, L / D=24 Screw rotation speed: 60 rpm Cylinder temperature settings: C1=170℃, C2=200℃ Head temperature setting: 200℃ T-die temperature setting: D1~D3 = 200℃ T-die width: 230mm, lip opening = 1mm Film winding speed: 4m / s Roll temperature: 60℃ The gel counter's configuration is as follows: Device configuration (1) Receiver (4096 pixels) (2) Floodlight (3) Signal Processing Device (4) Pulse generator (5) Inter-device cables

[0050] The ethylene-α-olefin copolymer of the present invention preferably has the properties shown in the following requirement (6). ≪Requirement (6)≫ In the powder particle size distribution of the ethylene-α-olefin copolymer before melt mixing, the mass fraction of powder that does not pass through a No. 10 (mesh opening 2 mm) mesh sieve (ASTM E11) relative to 100% by mass of powder is 10% by mass or less, preferably 7% by mass or less, more preferably 4% by mass or less, and in one embodiment it may be 0.1% by mass or more.

[0051] If the mass fraction of powder that does not pass through a No. 10 (2 mm mesh opening) mesh sieve (ASTM E11) of the ethylene-α-olefin copolymer before melt mixing (hereinafter also referred to as "large particle size component") exceeds 10% by mass, the appearance of the resulting molded product may be poor. By keeping the mass fraction of the large particle size component within the above range, the occurrence of fish eyes (FE) when molded into film is suppressed.

[0052] The ethylene-α-olefin copolymer before melt mixing is a powdered ethylene-α-olefin copolymer obtained by polymerization. Because the volume of the large particle size components is larger than that of the small particle size components, it takes longer for them to completely melt during melt mixing. Therefore, it is presumed that in ethylene-α-olefin copolymers with a large amount of large particle size components, insufficient melting occurs, leading to non-uniformity within the system and the formation of fish eyes (FE).

[0053] The mass fraction of large particle size components was determined by using a vibrating sieve (speed: 80) of a Retsch KS1000, vibrating a No. 10 (mesh opening 2 mm) mesh sieve (ASTM E11) on which the sample was placed for 2 minutes, and then measuring the mass of the powder that did not pass through.

[0054] The mass fraction of large particle size components can be adjusted by the type of component (T) or solid support (S) of the catalyst for polyolefin production described later. Furthermore, even when using the same catalyst for polyolefin production, it can be adjusted by the polymerization conditions or process; for example, the mass fraction of large particle size components can be suppressed by lowering the ethylene partial pressure.

[0055] The ethylene-α-olefin copolymer more preferably has one or more of the properties shown in requirements (7) to (9) below, more preferably two or more, and particularly preferably all of them. ≪Requirement (7)≫ The melting curve obtained by differential scanning calorimetry (DSC) shows multiple peaks. When there are multiple peaks, there is a large amount of low-melting-point components, resulting in excellent heat sealability at low temperatures.

[0056] Differential scanning calorimetry (DSC) is performed using a differential scanning calorimeter (for example, in the example described later, a Diamond DSC manufactured by PerkinElmer was used) as follows. Approximately 5 mg of the sample is placed in an aluminum pan, heated to 200°C at a rate of 10°C / min, held at 200°C for 10 minutes, then cooled to -30°C at a rate of 10°C / min, and then heated back up to 200°C at a rate of 10°C / min to obtain an endothermic curve. If this endothermic curve has two or more peaks, it means that the melting curve obtained by differential scanning calorimetry (DSC) also has multiple peaks.

[0057] The number of peaks in the melting curve in DSC can be adjusted according to the type of component (T) of the catalyst for polyolefin production or solid carrier (S) described below. Also, even when using the same catalyst for polyolefin production, it can be adjusted by increasing or decreasing the composition ratio of α-olefin and ethylene in the polymerization system.

[0058] ≪Requirement (8)≫ The intrinsic viscosity [η] (dl / g) measured in decalin at 135°C and the weight-average molecular weight (Mw) measured by the GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-2). 0.70×10 -4 ×Mw 0.776 ≦[η]≦1.65×10 -4 ×Mw 0.776 ···(Eq-2)

[0059] The intrinsic viscosity [η] (dl / g) and the weight-average molecular weight (Mw) preferably satisfy the following relational expression (Eq-2’). 0.70×10 -4 ×Mw 0.776 ≦[η]≦1.45×10 -4 ×Mw 0.776 ···(Eq-2’)

[0060] The intrinsic viscosity [η] (dl / g) and the weight-average molecular weight (Mw) more preferably satisfy the following relational expression (Eq-2”). 0.80×10 -4 ×Mw 0.776 ≦[η]≦1.35×10 -4 ×Mw 0.776 ···(Eq-2”)<00006​​It is known that when long-chain branching is introduced into ethylene polymers, the intrinsic viscosity [η](dl / g) is lower relative to the molecular weight compared to straight-chain ethylene polymers without long-chain branching (e.g., Walther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched Polymer II, p.137 (1999)). Therefore, when the intrinsic viscosity [η](dl / g) is below the upper limit, ethylene-α-olefin copolymers have numerous long-chain branches and exhibit excellent moldability and fluidity.

[0062] The intrinsic viscosity [η](dl / g) can be adjusted by the type of component (T) or solid support (S) of the catalyst for polyolefin production described later. Furthermore, even when using the same catalyst for polyolefin production, it can be adjusted by the polymerization conditions or process; for example, increasing the ethylene partial pressure can increase the intrinsic viscosity [η](dl / g).

[0063] The intrinsic viscosity [η](dl / g) is measured using decalin solvent as follows. Approximately 20 mg of the sample is dissolved in 15 mL of decalin, and the specific viscosity ηsp is measured in an oil bath at 135°C. After diluting this decalin solution by adding 5 mL of decalin solvent, the specific viscosity ηsp is measured again in the same manner. This dilution procedure is repeated two more times, and the intrinsic viscosity [η] (unit: dl / g) is determined by extrapolating the concentration (C) to 0 as shown in the formula below, using the value of ηsp / C. [η] = lim(ηsp / C) (C→0) The weight-average molecular weight (Mw) is measured by the method described in requirement (4) above.

[0064] ≪Requirement (9)≫ 1 The total number of vinyl, vinylidene, disubstituted internal olefins, and trisubstituted internal olefins measured by 1H-NMR (hereinafter also simply referred to as "total number of vinyl, vinylidene, disubstituted internal olefins, and trisubstituted internal olefins") is in the range of 0.1 to 1.0.

[0065] The total number of vinyl, vinylidene, 2-substituted internal olefins, and 3-substituted internal olefins preferably satisfies the following relational expression (Eq-3’). 0.2 ≤ the total number of vinyl, vinylidene, 2-substituted internal olefins, and 3-substituted internal olefins ≤ 1.0 ··· (Eq-3’)

[0066] The total number of vinyl, vinylidene, 2-substituted internal olefins, and 3-substituted internal olefins more preferably satisfies the following relational expression (Eq-3”). 0.3 ≤ the total number of vinyl, vinylidene, 2-substituted internal olefins, and 3-substituted internal olefins ≤ 1.0 ··· (Eq-3”)

[0067] The number of vinyl, vinylidene, 2-substituted internal olefins, and 3-substituted internal olefins in the polymer is 1 the number per 1000 carbon atoms contained in the polymer, measured by the H-NMR method. It is known that the production amount ratio and the number of vinyl, vinylidene, 2-substituted internal olefins, and 3-substituted internal olefins increase or decrease depending on the transition metal compound used (H. SAIKI, S. MAKOTO, T. MASAO, S. MORIHIKO, Y. AKIHIRO, J. Polym. Sci., A: Polym. Chem., 38, 4641 (2000)). These can be adjusted by the type of component (T) or solid carrier (S) of the catalyst for producing polyolefins described later. Also, even when using the same catalyst for producing polyolefins, it can be adjusted by the polymerization conditions or the polymerization process. For example, it can also be increased or decreased by increasing or decreasing the ethylene partial pressure.

[0068] When the total number of vinyl, vinylidene, disubstituted internal olefins, and trisubstituted internal olefins is 0.1 or more, long-chain branching is easily formed in the ethylene-α-olefin copolymer, and the ethylene-α-olefin copolymer exhibits excellent moldability. Furthermore, when the total number of vinyl, vinylidene, disubstituted internal olefins, and trisubstituted internal olefins is 1.0 or less, the ethylene-α-olefin copolymer becomes less susceptible to oxidation of the molten film during molding, resulting in excellent heat sealability.

[0069] 1 The total number of vinyl, vinylidene, disubstituted internal olefins, and trisubstituted internal olefins, as measured by 1H-NMR (500 MHz), is determined using a nuclear magnetic resonance spectrometer (for example, in the examples described later, a Bruker AVANCE III (cryoprobe) type nuclear magnetic resonance spectrometer) as follows. The measurement mode will be single pulse, with a pulse width of 45°. The number of points will be 32k, the observation range will be 20ppm (-6 to 14ppm), the repetition time will be 7 seconds, and the number of cumulative measurements will be 64. 20 mg of the sample will be dissolved in 40.6 mL of orthodichlorobenzene-d, and then measured at 120°C. 1 In the 1H-NMR spectrum, the number of double bonds and total double bonds were calculated from the signal integral values ​​derived from various double bonds (vinyl, vinylidene, internal olefin) in the range of 4.5 ppm to 5.8 ppm. 1 The relative value of the total number of carbon atoms is calculated from the total integral value of the H signal, and the number of various double bonds per 1000 polymer carbon atoms is then calculated.

[0070] [Method for producing ethylene-α-olefin copolymer] From the viewpoint of efficient polymerization, a preferred method for producing ethylene-α-olefin copolymers is to polymerize ethylene with an α-olefin having 4 to 10 carbon atoms in the presence of a polyolefin production catalyst consisting of the following components. The details of the polyolefin production catalyst used in the production of ethylene-α-olefin copolymers will be described below.

[0071] ≪Catalysts for Polyolefin Production≫ The catalyst for polyolefin production comprises the following components (T) and a solid support (S). <Ingredients (T)> The transition metal complex (T) contained in the aforementioned catalyst for the production of polyolefins (hereinafter also referred to as "component (T)") is represented by the following general formula [1].

[0072] [ka]

[0073] ≪M, n, X≫ In general formula [1], M is a transition metal atom of group 4 of the periodic table, preferably a zirconium atom or a hafnium atom, and more preferably a zirconium atom. n is an integer from 1 to 4, preferably 1 or 2, and more preferably 2, selected such that the transition metal complex (T) is electrically neutral. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can coordinate with a lone pair of electrons, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group. Preferably, X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group, and more preferably a halogen atom. If n is 2 or greater, the multiple X elements may be identical or different from each other, and they may be joined together to form a ring. Furthermore, if there are multiple such rings, these rings may be identical or different from each other.

[0074] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, preferably chlorine or bromine, and more preferably chlorine.

[0075] Examples of the hydrocarbon group include: Linear or branched alkyl groups such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butan-2-yl group), tert-butyl group (2-methylpropane-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbuta-2-yl group), and 4,4-dimethylpentyl group; Vinyl group, allyl group, propenyl group (propa-1-en-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl group (propa-1,2-dien-1-yl group), buta-3-en-1-yl group, clotyl group (buta-2-en-1-yl group), buta-3-en-2-yl group, metharyl group (2-methylallyl group), buta-1,3-dienyl group, pen Linear or branched alkenyl groups or unsaturated double bond-containing groups such as ta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group (3-methylbuta-3-en-1-yl group), 2-methylbuta-3-en-1-yl group, penta-4-en-2-yl group, and prenyl group (3-methylbuta-2-en-1-yl group); Linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl groups, propa-2-in-1-yl groups, and propargyl groups (propa-1-in-1-yl groups); Aromatic linear or branched alkyl groups and unsaturated double bond-containing groups such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-iso-propylbenzyl group), 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, and benzhydryl group (diphenylmethyl group); Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norborneyl group, 1-adamantyl group, 2-adamantyl group, and other cyclic saturated hydrocarbon groups; Aromatic substituents include phenyl group, tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3,5,6-tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, and ferrocenyl group. Among the hydrocarbon groups mentioned above, methyl, iso-butyl, neopentyl, siamyl, benzyl, phenyl, tolyl, xylyl, mesityl, and cumenyl groups are preferred.

[0076] Examples of the halogen-containing groups include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, and hexachloroantimonate anion. Among the halogen-containing groups, the pentafluorophenyl group is preferred.

[0077] Examples of the silicon-containing groups include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris(trimethylsilyl)silyl group, and trimethylsilylmethyl group. Among the silicon-containing groups mentioned above, the trimethylsilylmethyl group is preferred.

[0078] Examples of the oxygen-containing groups include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group, benzyloxy group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,4,6-trimethylphenoxy group, 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, and periodate anion. Among the oxygen-containing groups, methoxy groups, ethoxy groups, iso-propoxy groups, and tert-butoxy groups are preferred.

[0079] Examples of the aforementioned sulfur-containing groups include mesyl group (methanesulfonyl group), phenylsulfonyl group, tosyl group (p-toluenesulfonyl group), trifuryl group (trifluoromethanesulfonyl group), nonafuryl group (nonafluorobutanesulfonyl group), mesylate group (methanesulfonate group), tosylate group (p-toluenesulfonate group), triflate group (trifluoromethanesulfonate group), and nonaflate group (nonafluorobutanesulfonate group). Among the aforementioned sulfur-containing groups, triflate (trifluoromethanesulfonate) is preferred.

[0080] Examples of the nitrogen-containing groups include amino groups, cyano groups, methylamino groups, dimethylamino groups, ethylamino groups, diethylamino groups, allylamino groups, diallylamino groups, benzylamino groups, dibenzylamino groups, pyrrolidinyl groups, piperidinyl groups, morpholyl groups, pyrrolyl groups, and bistrifurylimide groups. Among the nitrogen-containing groups, dimethylamino group, diethylamino group, pyrrolidinyl group, pyrrolyl group, and bistrifurylimide group are preferred.

[0081] Examples of the phosphorus-containing group include the hexafluorophosphate anion.

[0082] Examples of the boron-containing groups include tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl))borate anion, (benzyl)(tris(pentafluorophenyl))borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, and groups represented by BR4 (where R independently represents hydrogen, an alkyl group, an optionally substituted aryl group, or a halogen atom).

[0083] Examples of the aforementioned aluminum-containing group are: [ka] Examples of groups that can form (M represents M in the general formula (1) above) are represented by AlR4 (where R represents hydrogen, an alkyl group, an optionally substituted aryl group, or a halogen atom, etc.).

[0084] Examples of the aforementioned conjugated diene derivative groups include metallocyclopentene groups such as 1,3-butadienyl group, isoprenyl group (2-methyl-1,3-butadienyl group), piperilenyl group (1,3-pentadienyl group), 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, and cyclopentadienyl group.

[0085] Examples of neutral ligands that can coordinate with a lone pair of electrons include ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; amines such as triethylamine and diethylamine; heterocyclic compounds such as pyridine, picoline, lutidine, oxazoline, oxazole, thiazole, imidazole, and thiophene; and organophosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, and tri-tert-butylphosphine.

[0086] ≪Q≫ In the general formula [1] above, Q is an atom of Group 14 of the periodic table, such as a carbon atom, a silicon atom, a germanium atom, or a tin atom, preferably a carbon atom or a silicon atom, and more preferably a silicon atom.

[0087] ≪R 1 ~R 14 ≫ In the above general formula [1], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 These are, independently, a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. R 1 ~R 14 Examples of hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 20 carbon atoms, and more specifically, specific examples of the hydrocarbon groups listed as examples of X above can be cited. The C1-C40 hydrocarbon group is preferably a C1-C20 hydrocarbon group (excluding aromatic hydrocarbon groups) or a C6-C40 aromatic hydrocarbon group. The C1-C20 hydrocarbon group is preferably an aliphatic or alicyclic hydrocarbon group. The C1-C20 hydrocarbon group also includes substituents having an aromatic structure, such as arylalkyl groups.

[0088] Examples of the hydrocarbon group having 1 to 40 carbon atoms are: Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group, 1-dodecanyl group, 1-eicosanyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group, tert-pentyl group (1,1-dimethylpropyl group), siamyl group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group (2-methylpentan-2-yl group), 3-methylpentane Linear or branched alkyl groups having 1 to 40 carbon atoms, such as -2-yl group, 4-methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, 3,3-dimethylbuta-2-yl group, hexane-3-yl group, 2-methylpentan-3-yl group, heptane-4-yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,3,3-trimethylbutan-2-yl group, and 2,4,4-trimethylpentan-2-yl group; Vinyl group, allyl group, propenyl group, iso-propenyl group, allenyl group, buta-3-en-1-yl group, clotyl group, buta-3-en-2-yl group, methallyl group, buta-1,3-dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group, 2-methylbuta-3-en-1-yl group, penta-4-en-2-yl group, prenyl group, 2-methylbuta-2-en-1- Iyl group, penta-3-en-2-yl group, 2-methyl-buta-3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl group (2-methyl-buta-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hexa-5-en-1-yl group, hexa-4-en-1-yl group, hexa-3-en- 1-yl group, hexa-2-en-1-yl group, 4-methyl-penta-4-en-1-yl group, 3-methyl-penta-4-en-1-yl group, 2-methyl-penta-4-en-1-yl group, hexa-5-en-2-yl group, 4-methyl-penta-3-en-1-yl group, 3-methyl-penta-3-en-1-yl group, 2,3-dimethyl-buta-2-en-1-yl group, 2-methylpenta-4-en-2-yl group, 3-ethylpenta-1-en-3 -yl group, hexa-3,5-dien-1-yl group, hexa-2,4-dien-1-yl group, 4-methylpenta-1,3-dien-1-yl group, 2,3-dimethylbuta-1,3-dien-1-yl group, hexa-1,3,5-trien-1-yl group, 2-(cyclopentadienyl)propan-2-yl group, 2-(cyclopentadienyl)ethyl group, etc., linear or branched alkenyl groups or unsaturated double bond-containing groups with 2 to 40 carbon atoms; Ethynyl group, propa-2-in-1-yl group, propargyl group, buta-1-in-1-yl group, buta-2-in-1-yl group, buta-3-in-1-yl group, penta-1-in-1-yl group, penta-2-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methylbuta-1-in-1-yl group, penta-3-in-2-yl group, 2-methylbuta-3-yl Linear or branched alkynyl groups or unsaturated triple bond-containing groups with 2 to 40 carbon atoms, such as 1-yl group, penta-4-in-2-yl group, hexa-1-in-1-yl group, 3,3-dimethylbuta-1-in-1-yl group, 2-methylpenta-3-in-2-yl group, 2,2-dimethylbuta-3-in-1-yl group, hexa-4-in-1-yl group, and hexa-5-in-1-yl group; Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cumyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl group (2-phenylpropan-2-yl group), 2-(4-methylphenyl)propan-2-yl group, 2-(3,5-dimethylphenyl)propan-2-yl group, 2-(4-tert-butylphenyl)propan-2-yl group, 2-(3,5-di-tert-butylphenyl)propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1, 6-dien-4-yl group, 1,2,3-triphenylpropane-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-buta-3-en-1-yl group, 1,1,2-triphenylethyl group, trityl group (triphenylmethyl group), tri-(4-methylphenyl)methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2-(2-methylphenyl)ethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, 2-methyl-1-phenylpropane-2-yl group, 3-phenylpropyl group, cinnamyl group (3-phenylallyl group), neophyll group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propane-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(tetrahydro-1-indacenyl)propane-2-yl group, (tetrahydro-1-indacenyl) Aromatic linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, such as diphenylmethyl group, 2-(tetrahydro-1-indacenyl)ethyl group, 2-(1-benzoindenyl)propan-2-yl group, (1-benzoindenyl)diphenylmethyl group, 2-(1-benzoindenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, 2-(1-azlenyl)propan-2-yl group, (1-azlenyl)diphenylmethyl group, and 2-(1-azlenyl)ethyl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl Syl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl- tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octane-1-yl group, bicyclo[2.2.2]octane-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl), 1 -(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl), 1-(3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, azurenyl group, and other cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms; Examples include aromatic substituents with 6 to 40 carbon atoms, such as phenyl, tolyl, xylyl, mesityl, cumenyl, juryl, 2,6-di-iso-propylphenyl, 2,4,6-tri-iso-propylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, allylphenyl, (buta-3-en-1-yl)phenyl, (buta-2-en-1-yl)phenyl, methallylphenyl, prenylphenyl, 4-adamantylphenyl, 3,5-diadamantylphenyl, naphthyl, biphenyl, terphenyl, binaphthyl, acenaphthalenyl, phenanthryl, anthracenyl, pyrenyl, and ferrocenyl groups.

[0089] Among the linear or branched alkyl groups having 1 to 40 carbon atoms, the following are particularly important: methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, pentan-3-yl group, iso-hexyl group, 1,1-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, heptane-4 -yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,4,4-trimethylpentan-2-yl group, etc. are preferred, and methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, iso-propyl group, tert-butyl group, neopentyl group, 2,4-dimethylpentan-2-yl group, 2,4,4-trimethylpentan-2-yl group are more preferred.

[0090] Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl groups, allyl groups, buta-3-en-1-yl groups, clotyl groups, methallyl groups, penta-4-en-1-yl groups, prenyl groups, penta-1,4-dien-3-yl groups, hexa-5-en-1-yl groups, 2-methylpenta-4-en-2-yl groups, 2-(cyclopentadienyl)propane-2-yl groups, and 2-(cyclopentadienyl)ethyl groups are preferred, with vinyl groups, allyl groups, buta-3-en-1-yl groups, penta-4-en-1-yl groups, prenyl groups, and hexa-5-en-1-yl groups being more preferred.

[0091] Among the aromatic linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, there are benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-t The following are preferred: ert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neophyll group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, and more preferably, benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, and cinnamyl group.

[0092] Among the aforementioned cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzyl The following are preferred: a cycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, pentarenyl group, indenyl group, fluorenyl group, etc., and more preferably cyclopentyl group, cyclopentenyl group, 1-methylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, and 1-adamantyl group. Among the aromatic substituents having 6 to 40 carbon atoms, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamanthylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, and ferrocenyl group are preferred, and phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamanthylphenyl group, naphthyl group, biphenyl group, phenanthryl group, and anthracenyl group are more preferred.

[0093] Examples of the halogen-containing groups include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group, chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, Examples include trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert-butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoromethylenedioxyphenyl group, bistrifluoromethylphenyliminomethyl group, trifluoromethylthio group, and the like. Among the halogen-containing groups, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, pentafluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxy group, pentafluorophenoxy group, bistrifluoromethylphenoxy group, bistrifluoromethylphenoxy group, difluoromethylenedioxyphenyl group, and trifluoromethylthio group are preferred, and trifluoromethyl group, fluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, pentafluorobiphenyl group, trifluoromethoxy group, and pentafluorophenoxy group are more preferred.

[0094] Examples of the silicon-containing groups include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris(trimethylsilyl)silyl group, cyclopentadienyldimethylsilyl group, di-n-butyl(cyclopentadienyl)silyl group, cyclopentadienyldiphenylsilyl group, indenyldimethylsilyl group, and di-n-butyl(indenyl Examples include silyl groups, indenyldiphenylsilyl groups, fluorenyldimethylsilyl groups, di-n-butyl(fluorenyl)silyl groups, fluorenyldiphenylsilyl groups, 4-trimethylsilylphenyl groups, 4-triethylsilylphenyl groups, 4-tri-iso-propylsilylphenyl groups, 4-tert-butyldiphenylsilylphenyl groups, 4-triphenylsilylphenyl groups, 4-tris(trimethylsilyl)silylphenyl groups, and 3,5-bis(trimethylsilyl)phenyl groups. Among the silicon-containing groups mentioned above, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl group, indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-triphenylsilylphenyl group, and 3,5-bis(trimethylsilyl)phenyl group are preferred, and trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, and 3,5-bis(trimethylsilyl)phenyl group are more preferred.

[0095] Examples of the oxygen-containing groups include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group, methallyloxy group, prenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, allyloxyethyl group, benzyloxyethyl group, phenoxyethyl group, methoxypropyl group, and Examples include lyloxypropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxyvinyl group, methoxyallyl group, allyloxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, di-iso-propoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydrofuryl group, pyranyl group, tetrahydropyranyl group, furyl group, benzofuryl group, and dibenzofuryl group. Among the oxygen-containing groups mentioned above, methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyloxy group, benzyloxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxy Siphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydropyranyl group, furyl group, benzofuryl group, dibenzofuryl group, etc. are preferred, and methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, benzofuryl group, dibenzofuryl group, etc. are more preferred.

[0096] Examples of the nitrogen-containing groups include amino groups, dimethylamino groups, diethylamino groups, allylamino groups, diallylamino groups, didecylamino groups, benzylamino groups, dibenzylamino groups, pyrrolidinyl groups, piperidinyl groups, molyphoyl groups, azepinyl groups, dimethylaminomethyl groups, dibenzylaminomethyl groups, pyrrolidinylmethyl groups, dimethylaminoethyl groups, benzylaminomethyl groups, benzylaminoethyl groups, pyrrolidinylethyl groups, dimethylaminovinyl groups, benzylaminovinyl groups, pyrrolidinylvinyl groups, dimethylaminopropyl groups, benzylaminopropyl groups, pyrrolidinylpropyl groups, dimethylaminoallyl groups, benzylaminoallyl groups, pyrrolidinylallyl groups, aminophenyl groups, dimethylaminophenyl groups, 3,5-dimethyl-4-dimethylaminophenyl groups. Examples include 3,5-di-iso-propyl-4-dimethylaminophenyl group, jurolidinyl group, tetramethyljurolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenylpyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, and benzoxazolyl group. Among the nitrogen-containing groups mentioned above, amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, jurolidinyl group, tetramethyljurolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolyl Phenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, etc. are preferred, and amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, jurolidinyl group, tetramethyljurolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, and imidazolyl group are more preferred.

[0097] Examples of the sulfur-containing groups include methylthio group, ethylthio group, benzylthio group, phenylthio group, naphthylthio group, methylthiomethyl group, benzylthiomethyl group, phenylthiomethyl group, naphthylthiomethyl group, methylthioethyl group, benzylthioethyl group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, benzylthiopropyl group, phenylthiopropyl group, naphthylthiopropyl group, methylthioallyl group, benzylthioallyl group, and phenyl Examples include thioallyl group, naphthylthioallyl group, mercaptophenyl group, methylthiophenyl group, thienylphenyl group, methylthienylphenyl group, benzothienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, dithiolanyl group, dithianyl group, oxathiolanyl group, oxathianyl group, thiazolyl group, benzothiazolyl group, and thiazolidinyl group. Among the sulfur-containing groups mentioned above, thienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenofuryl group, benzodithienyl group, thiazolyl group, and benzothiazolyl group are preferred.

[0098] R 1 ~R 6 Among adjacent substituents (e.g., R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , and R 5 and R 6These rings may bond to each other to form a ring which may have substituents. In this case, the ring formed is preferably a 5-8 membered ring consisting of saturated hydrocarbons (excluding the hydrocarbon of the indenyl ring portion) or unsaturated hydrocarbons which may have substituents and fuse with the indenyl ring portion. If there are multiple rings, they may be the same or different from each other. The present invention is not particularly limited as long as it achieves its effects, but the ring is more preferably a 5 or 6 membered ring. In this case, the structure formed by combining the ring and the indenyl ring portion of the parent nucleus may include, for example, a substituted benzoindenyl ring, a substituted tetrahydroindacene ring, or a substituted cyclopentatetrahydronaphthalene, with substituted benzoindenyl rings and substituted tetrahydroindacene rings being preferred.

[0099] R 7 ~R 12 Among adjacent substituents (e.g., R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , and R 11 and R 12 These rings may bond to each other to form a ring which may have substituents. In this case, the ring formed is preferably a 5-8 membered ring consisting of saturated hydrocarbons (excluding the hydrocarbon of the indenyl ring portion) or unsaturated hydrocarbons which may have substituents and fuse with the indenyl ring portion. If there are multiple rings, they may be the same or different from each other. The present invention is not particularly limited as long as it achieves its effects, but the ring is more preferably a 5 or 6 membered ring. In this case, examples of structures formed by combining the ring and the indenyl ring portion of the parent ring include a substituted benzoindenyl ring, a substituted tetrahydroindacene ring, a substituted cyclopentatetrahydronaphthalene, a substituted tetrahydrofluorene ring, and a substituted fluorene ring, with substituted benzoindenyl rings and substituted tetrahydroindacene rings being preferred.

[0100] R 13 and R 14These may bond to each other to form a ring containing Q. In this case, the formed ring is preferably a saturated or unsaturated ring of 3 to 8 members, which may have substituents. While not particularly limited as long as the effects of the present invention are achieved, the ring is preferably a 4 to 6 member ring, in which case R 13 and R 14 Examples of structures combining Q include a substituted cyclobutane ring, a substituted cyclopentane ring, a substituted fluorene ring, a substituted silacyclobutane (silate) ring, a substituted silacyclopentane (silorane) ring, a substituted silacyclohexane (silinane), and a substituted silafluorene ring, with the substituted cyclopentane ring, substituted silacyclobutane ring, and substituted silacyclopentane ring being preferred.

[0101] R 1 and R 6 Each of these is independently preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, and more preferably a hydrogen atom.

[0102] R 2 ~R 5 and R 7 ~R 14 Each of these is independently preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, and more preferably 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. 7 , R 9 and R 12 In at least one of these, the oxygen-containing group, nitrogen-containing group, or sulfur-containing group may be a heterocyclic aromatic group as described later.

[0103] Preferred embodiment of the transition metal complex (T) A preferred embodiment of the transition metal complex (T) is, in the general formula [1], M is a zirconium atom or a hafnium atom, X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group, Q is a carbon atom or a silicon atom, and R 1 ~R 6 and R 8 ~R 14 However, each is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, R 7 However, examples include transition metal complexes (T-1) which are heterocyclic aromatic groups that may have substituents, and whose parent skeleton is a five-membered ring containing at least one hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an atom selected from the group consisting of nitrogen, oxygen, and sulfur. More preferred embodiments include the following general formula [1], where Q is a silicon atom and R 1 and R 6 However, it is a hydrogen atom, R 2 ~R 5 and R 7 ~R 14 However, these can be independently transition metal complexes (T-2) that consist of 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.

[0104] In the transition metal complex (T-1), R 7 , R 9 and R 12 One of the options is a heterocyclic aromatic group which may have substituents and whose parent skeleton is a five-membered ring (hereinafter also referred to as a "hetero-five-membered ring") containing at least one atom selected from the group consisting of nitrogen, oxygen, and sulfur. For example, a group represented by the following general formulas [4a] to [4h] is an example.

[0105] [ka]

[0106] In the above general formulas [4a] to [4h], Ch is an oxygen atom or a sulfur atom, and R d Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different. In addition, the dashed lines in the general formulas [4a] to [4h] indicate the bonding site with the indenyl ring.

[0107] Examples of the hydrocarbon groups having 1 to 20 carbon atoms include the above-mentioned R 1 ~R 14 Among the examples of hydrocarbon groups having 1 to 40 carbon atoms, those having 1 to 20 carbon atoms are particularly noteworthy, and preferably include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctenyl group, norbornyl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, and 3-phenyl Examples of groups include propyl group, cinnamyl group, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, and ferrocenyl group. More preferably, examples include methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, allyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, biphenyl group, and terphenyl group.

[0108] Rd Each is independent of the adjacent R d They may bond with each other and fuse to form saturated or unsaturated hydrocarbon groups that constitute a 5- to 8-membered ring together with the atoms of the heterogeneous 5-membered ring, which may have substituents. The 5- to 8-membered ring is not particularly limited as long as it achieves the effects of the present invention, but is preferably a 5 or 6-membered ring. In this case, examples of structures formed by combining this ring with the heterogeneous 5-membered ring of the parent nucleus include a benzofuran ring, a benzothiophene ring, an indole ring, a carbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, and a benzopyrazole ring.

[0109] Among the heterocyclic aromatic groups represented by the general formulas [4a] to [4h], the heterocyclic aromatic group represented by the general formula [4a] is preferred. Among the heterocyclic aromatic groups represented by the general formula [4a], the 2-furyl group, the 5-methyl-2-furyl group, the 2-thienyl group, and the 5-methyl-2-thienyl group are preferred.

[0110] Examples of transition metal complexes (T) Specific examples of the transition metal complex (T) are shown below, but the scope of the present invention is not particularly limited by these examples.

[0111] For convenience, the ligand structure of the transition metal complex (T) excluding the MXn (metal portion) portion is referred to as the 2-indenyl ring portion, the 1-indenyl ring portion, and the indenyl ring portion R. 1 , R 6 and R 8 Substituents, indenyl ring portion R 2 , R 5 , R 9 , and R 12 Substituents, indenyl ring portion R 3 , R 4 , R 10 , and R 11 Substituents, 1-indenyl ring portion R 7 The structure is divided into seven parts: substituents and bridging regions. The abbreviation for the 2-indenyl ring portion is α, the abbreviation for the 1-indenyl ring portion is β, and the abbreviation for the indenyl ring portion is R. 1 , R6 and R 8 The abbreviation for the substituent is γ, and the indenyl ring portion is R. 2 , R 5 , R 9 , and R 12 The abbreviation for substituent is δ, and the indenyl ring portion is R. 3 , R 4 , R 10 , and R 11 The substituent is abbreviated as ε, and the 1-indenyl ring portion is R. 7 The abbreviation for substituents is ζ, and the abbreviation for the structure of the bridging portion is η. The abbreviations for each substituent are shown in [Table 1] to [Table 7].

[0112] [Table 1]

[0113] [Table 2] The dashed lines in [Table 1] to [Table 2] indicate the connection points with the bridged sections.

[0114] [Table 3] R in [Table 3] above 1 , R 6 and R 8 The substituents may be identical or different from one another in their combination.

[0115] [Table 4] R in [Table 4] above 2 , R 5 , R 9 , and R 12 The substituents may be identical or different from one another in their combination.

[0116] [Table 5] R in [Table 5] above 3 , R 4 , R10 , and R 11 The substituents may be identical or different from one another in their combination.

[0117] [Table 6]

[0118] [Table 7]

[0119] Specific examples of the metallic part MXn include TiF2, TiCl2, TiBr2, TiI2, Ti(Me)2, Ti(Bn)2, Ti(Allyl)2, Ti(CH2-tBu)2, Ti(1,3-butadienyl), Ti(1,3-pentadienyl), Ti(2,4-hexadienyl), Ti(1,4-diphenyl-1,3-pentadienyl), and Ti(CH2-S i(Me)3)2, Ti(OMe)2, Ti(OiPr)2, Ti(NMe2)2, Ti(OMs)2, Ti(OTs)2, Ti(OTf)2, 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, HfF2, HfCl2, HfBr2, HfI2, Hf(Me)2, Hf(Bn)2, Hf(Allyl)2, Hf(C Examples include H2-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, and Hf(OTf)2. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si(Me)3 is a trimethylsilyl group, OME is a methoxy group, OiPr is an iso-propoxy group, NMe2 is a dimethylamino group, OMs is a methanesulfonate group, OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

[0120] According to the above notation, 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 is R 1 , R 6 and R 8 All substituents are the γ-1,2-indenyl ring portion R in [Table 3]. 2 and R 5All substituents are the δ-1,2-indenyl ring moiety R in [Table 4] 3 and R 4 All substituents are the ε-1,1-indenyl ring moiety R in [Table 5] 7 The substituent is ζ-30, 1-indenyl ring portion R in [Table 6] 9 The substituent is δ-38, 1-indenyl ring portion R in [Table 4] 12 When the substituent is composed of δ-3 from [Table 4] and the bridging portion is composed of η-20 from [Table 7], and the metal portion MXn is ZrCl2, the compound represented by the following formula [5] is an example.

[0121] [ka]

[0122] Furthermore, 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 the γ-1,2-indenyl ring portion R in [Table 3]. 2 and R 5 All substituents are the δ-2,2-indenyl ring moiety R in [Table 4] 3 and R 4 All substituents are the ε-1,1-indenyl ring moiety R in [Table 5] 7 When the substituent is composed of ζ-1 from [Table 6] and the bridging portion is composed of η-4 from [Table 7], and the metal portion MXn is Zr(NMe2)2, the compound represented by the following formula [6] is an example.

[0123] [ka]

[0124] Furthermore, the 2-indenyl ring portion is α-3 in [Table 1], the 1-indenyl ring portion is β-1 in [Table 2], and the 2-indenyl ring portion is R 1 and R 6 The substituents are all γ-2 and the indenyl ring portion R in [Table 3]. 2 , R5 and R 12 When all the substituents are δ-1 in [Table 4], and the R7 substituent of the 1-indenyl ring moiety is ζ-12 in [Table 6], and the R of the 1-indenyl ring moiety 8 When the substituent is γ-1 in [Table 3], and the R of the 1-indenyl ring moiety 9 When the substituent is δ-42 in [Table 4], and the R of the 1-indenyl ring moiety 10 When the substituent is ε-3 in [Table 5], and the R of the 1-indenyl ring moiety 11 When the substituent is ε-12 in [Table 5], and the bridging moiety is η-31 in [Table 7], and MXn of the metal moiety is HfMe2, the compound represented by the following formula [7] is exemplified.

[0125]

Chemical formula

[0126] Also, when the 2-indenyl ring moiety is α-1 in [Table 1], and the 1-indenyl ring moiety is β-1 in [Table 2], and the R of the 2-indenyl ring moiety 1 and R 6 When all the substituents are γ-1 in [Table 3], and the R of the 2-indenyl ring moiety 2 When the substituent is δ-7 in [Table 4], and the R of the 2-indenyl ring moiety 3 , R 4 , R 10 and R 11 When all the substituents are ε-1 in [Table 5], and the R of the 2-indenyl ring moiety 5 When the substituent is δ-2 in [Table 4], and the R of the 1-indenyl ring moiety 7 When the substituent is ζ-1 in [Table 6], and the R of the 1-indenyl ring moiety 8 When the substituent is γ-9 in [Table 3], and the R of the 1-indenyl ring moiety 9 and R 12 When all the substituents are δ-1 in [Table 4], and the bridging moiety is η-29 in [Table 7], and MXn of the metal moiety is Ti(1,3-pentadienyl), the compound represented by the following formula [8] is exemplified.

[0127]

Chemical formula

[0128] Furthermore, the transition metal complex (T) has two planes (front and back) for the indenyl ring portion that bonds to the central metal, flanking the bridging portion. Therefore, when there is no plane of symmetry for the 2-indenyl ring portion, there are two structural isomers, as shown by the following general formulas [9a] or [9b].

[0129] [ka]

[0130] Similarly, substituent R in the crosslinked portion 13 and R 14 Even when they are not identical, there are two structural isomers, for example, represented by the following general formulas [10a] or [10b].

[0131] [ka]

[0132] The purification, separation, or selective production of these structural isomer mixtures is possible by known methods, and the production method is not particularly limited. Known production methods include those listed above as methods for producing transition metal complexes (T), as well as methods disclosed in Japanese Patent Publication No. 10-109996, "Organometallics 1999, 18, 5347," "Organometallics 2012, 31, 4340," and Japanese Patent Publication No. 2011-502192.

[0133] Within the range of the transition metal complex (T), one transition metal complex may be used alone, two or more may be used in combination, a mixture of structural isomers may be used, one structural isomer may be used alone, or a mixture of two or more structural isomers may be used. In this case, the transition metal complex (T) may be any of the above embodiments.

[0134] <Method for producing transition metal complexes (T)> The transition metal complex (T) can be produced using conventionally known methods, and examples of typical synthesis routes are shown below, but the production method is not particularly limited. Note that in the following [Equations 1] to [Equations 5], R 1 ~R 14 Q, M, X, and n are equivalent to those described in the general formula [1] above.

[0135] The substituted indene compounds used as starting materials can be produced by known methods, and the production method is not particularly limited. Examples of known production methods include, for example, "Organometallics 1994, 13, 954," "Organometallics 2006, 25, 1217," JP 2006-509059, "Bioorg.Med.Chem. 2008, 16, 7399," WO2009 / 080216, "Organometallics 2011, 30, 5744," JP 2011-500800, "Organometallics 2012, 31, 4962," and "Chem.Eur.J." Examples of manufacturing methods disclosed in Japanese Patent Publication No. 2012, 18, 4174, Japanese Patent Publication No. 2012-012307, Japanese Patent Publication No. 2012-121882, Japanese Patent Publication No. 2014-196319, Japanese Patent Publication No. 2014-513735, Japanese Patent Publication No. 2015-063495, Japanese Patent Publication No. 2016-501952, etc.

[0136] Of the aforementioned substituted indene compounds, those that are unsubstituted at the 2-position can be brominated at the 2-position by known methods as described below, and the manufacturing method is not particularly limited.

[0137] [ka]

[0138] In the above [Formula 1], NBS represents N-bromosuccinimide, and PTSA represents p-toluenesulfonic acid or its monohydrate. In the indene compound, there are 5-membered ring partial double bond position isomers, and a mixture of these isomers may also be used. As known production methods, for example, in addition to the JP-A Nos. 2012-121882 and 2015-063495 described above, production methods disclosed in JP-A No. 2014-111568 and the like can be mentioned.

[0139] The 2-position brominated substituted indene compound and the 4-position brominated substituted indene compound can produce the corresponding coupling product by a known method such as the Suzuki-Miyaura coupling reaction using the following palladium catalyst, etc., and the production method is not particularly limited.

[0140]

Chemical formula

[0141] Similarly, there are 5-membered ring partial double bond position isomers in the indene compound, and a mixture of these isomers may also be used. In addition, various boronic acid esters, boroxines, and other boron compounds may be used instead of the boronic acid. The reaction mixture of the halogen compound, the metal reagent, and then the boron compound may be used without isolation and purification. A nickel catalyst or an iron catalyst may be used instead of the palladium catalyst. As known production methods, for example, in addition to those described above, JP-A No. 2014-196274 and the like can be mentioned.

[0142] Furthermore, instead of the Suzuki-Miyaura coupling reaction with boron compounds, the following methods may be used to produce the coupling product: Negishi coupling with organozinc reagents, the Mizoroki-Heck reaction with alkene compounds, the Hiyama coupling with organosilicon compounds, the Sonogashira-Hagiwara coupling with terminal alkyne compounds, the Migita-Kosugi-Stille coupling with organotin compounds, the Kumada-Tamao-Corriu coupling with organomagnesium compounds, the Buchwald-Hartwig coupling, the Goldberg amination reaction, or the Ullmann ether synthesis reaction. Known production methods, in addition to those mentioned above, include, for example, those described in Japanese Patent Publication No. Hei 8-183814, Japanese Patent Publication No. 2005-529865, and Japanese Patent Publication No. 2006-509046. For the production of the coupling product, the aforementioned 2-position unsubstituted indene compound and an aromatic halide may be used, and known methods such as a palladium-catalyzed direct coupling reaction may be employed.

[0143] [ka]

[0144] In the above [Formula 3], Ar represents an aromatic substituent, and a mixture of positional isomers of the indene compound's five-membered ring partial double bond may be used. Known production methods include, for example, Japanese Patent Publication No. 2000-512661 and Japanese Patent Application Publication No. 2014-201519. Transition metal complexes (T) and precursor compounds (ligands) can be produced by known methods using various substituted indene compounds produced by the aforementioned methods. When Q is a silicon atom, a germanium atom, or a tin atom, they can be produced by the following methods, and the production method is not particularly limited.

[0145] [ka]

[0146] In the above [Formula 4], in the synthesis of the precursor compound (ligand), the organomagnesium reagent prepared from the 2-brominated indene compound and the organolithium reagent prepared from the substituted 1-indene compound are preferably reacted stepwise with a chloride containing Q, and the order of these reactions is not limited to any particular sequence. After the first reaction with the organometallic reagent, the by-product inorganic compounds may be removed under an inert atmosphere, or the reaction product may be isolated by distillation, crystallization, or washing before use. During the second reaction with the organometallic reagent, it is preferable to add 0.1 to 5.0 equivalents of DMI (1,3-dimethyl-2-imidazolidinone), DMPU (N,N'-dimethylpropylene urea), or HMPA (hexamethylphosphate triamide) relative to the organometallic reagent, more preferably DMI in an amount of 1.0 equivalent. Note that there are positional isomers of the 5-membered ring partial double bond of the indene compound in the substituted indene compound and the precursor compound (ligand), and a mixture of these isomers may be used.

[0147] Known methods for producing transition metal complexes (T) and precursor compounds (ligands) include, in addition to those mentioned above, Japanese Patent Publication No. 11-315089, Japanese Patent Publication No. 2001-302687, Japanese Patent Publication No. 2001-220404, "Journal of Polymer Science, Japan 2002, 59, 243," Japanese Patent Publication No. 2003-522194, "Macromolecules 2004, 37, 2342," Japanese Patent Publication No. 2007-320935, and Japanese Patent Publication No. 2011-126813.

[0148] If Q is a carbon atom, it can be manufactured by the following methods, and the manufacturing method is not particularly limited.

[0149] [ka]

[0150] In the above [Formula 5], the base is a basic substance capable of generating an indenyl anion, and examples include organometallic compounds such as sodium hydride, n-butyllithium, and Grignard reagents, inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as diethylamine and pyrrolidine, but are not particularly limited. In the presence of a basic substance, a flubene compound can be synthesized from a substituted 1-indene compound and a carbonyl compound by known methods, and a precursor compound (ligand) can be produced by reaction with an organomagnesium reagent prepared from a 2-brominated substituted indene compound. Note that there are positional isomers of the 5-membered ring partial double bond of the indene compound in the substituted indene compound and the precursor compound (ligand), but a mixture of these isomers may be used.

[0151] Known methods for producing transition metal complexes (T) and precursor compounds (ligands) include, in addition to those mentioned above, "Macromolecules 2003, 36, 9325," "Organometallics 2004, 23, 5332," "Eur.J.Inorg.Chem. 2005, 1003," and "Eur.J.Inorg.Chem. 2009, 1759."

[0152] <Solid carrier (S)> The catalyst for polyolefin production of the present invention contains a solid carrier (S) (hereinafter also referred to as "carrier (S)" or "component (S)") whose particle size dispersion ratio (R10), as measured by the following measurement method, is greater than 0% and 95% or less, and whose particle size dispersion ratio (R50), as measured by the following measurement method, is greater than 0% and 95% or less. [Measurement method] Using methanol as the dispersion medium, the solid carrier (S) is dispersed in an ultrasonic homogenizer at an output of 25W for 5 minutes, and the average particle diameter (Dw10) corresponding to 10% of the cumulative mass from the smallest diameter in the particle size distribution and the average particle diameter (Dw50) corresponding to 50% of the cumulative mass from the smallest diameter in the particle size distribution are measured by wet laser diffraction scattering. Similarly, the average particle diameter (Ds10) corresponding to 10% of the cumulative mass from the smallest diameter in the particle size distribution and the average particle diameter (Ds50) corresponding to 50% of the cumulative mass from the smallest diameter in the particle size distribution are measured under the same conditions, except that the dispersion was performed at an output of 40W for 15 minutes. The particle size dispersion ratios (R10) and (R50) are expressed by the following formulas. R10 = Ds10 / Dw10 × 100 R50 = Ds50 / Dw50 × 100

[0153] The particle size dispersion ratio (R10) of the solid carrier (S) is preferably 20% to 87.5%, more preferably 40% to 85%, even more preferably 60% to 82.5%, and particularly preferably 70% to 80%. The particle size dispersion ratio (R50) of the solid carrier (S) is preferably 20% to 87.5%, more preferably 40% to 85%, even more preferably 60% to 82.5%, and particularly preferably 70% to 82%. When the particle size dispersion ratio (R10) and particle size dispersion ratio (R50) of the solid carrier (S) are within the above range, it is preferable because the rate of decay of polymerization activity is large, and abnormal polymerization can be suppressed.

[0154] The solid carrier (S) is an inorganic compound or an organic compound, and is in the form of granular or fine particles, preferably a porous material. The inorganic compound is preferably a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral, or an ion-exchangeable layered compound.

[0155] Specifically, the porous oxide can be SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or composites or mixtures containing these. Furthermore, natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc., can be used. Among these, porous oxides mainly composed of SiO2 and / or Al2O3 are preferred.

[0156] The porous oxide may contain small amounts of carbonates, sulfates, nitrates, and oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O.

[0157] The properties of the porous oxide vary depending on the type and manufacturing method, but the porous oxide preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, more preferably 50 to 100 μm, and even more preferably 60 to 80 μm, and a specific surface area of ​​50 to 1000 m². 2 / g, preferably 100-700m 2 / g, more comfortable 200~500m 2 / g, more preferably 300-400m 2 It is in the range of / g, and the pore volume is 0.3-3.0 cm³. 3 / g, preferably 0.5-2.0cm 3 It is in the range of / g. Such porous oxides are used after being calcined as needed at 100-1000°C, preferably 150-700°C, and more preferably 170-500°C.

[0158] Examples of the solid aluminoxane compound include aluminoxanes having a structure represented by the following general formula (Sa) or (Sb), and aluminoxanes having a repeating unit represented by the following general formula (Sc) and a repeating unit represented by the following general formula (Sd) as part of their structure, selected from at least one of these.

[0159] [ka]

[0160] In the general formula (Sa)~(Sd), R e Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, examples of hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, and ethylphenyl group. Methyl group, ethyl group, and isobutyl group are preferred, and methyl group is particularly preferred. Also, R e A portion of it is substituted with halogen atoms such as chlorine and bromine, and the halogen content is R e The amount may be 40% by mass or less based on the standard. In (Sc) and (Sd), lines where one side is not connected to an atom indicate a bond with another atom not shown.

[0161] In the general formulas (Sa) and (Sb), r is an integer between 2 and 500, preferably between 6 and 300, and particularly preferably between 10 and 100. In the general formulas (Sc) and (Sd), s and t are each integers of 1 or more. r, s, and t are selected so that the aluminoxane can maintain a substantially solid state under the reaction environment in which it is used.

[0162] Unlike conventionally known olefin polymerization catalyst supports, the solid aluminoxane compound does not contain inorganic solid components such as silica or alumina, or organic polymer components such as polyethylene or polystyrene, and is solidified with alkylaluminum compounds as the main component. "Solid state" means that the aluminoxane component maintains a substantially solid state under the reaction environment in which it is used. More specifically, this means that the aluminoxane component maintains a substantially solid state when preparing a catalyst for polyolefin production by contacting the transition metal complex (T) and the aluminoxane component as described later, and when polymerizing olefins (e.g., suspension polymerization) using the prepared catalyst for polyolefin production.

[0163] The simplest way to determine whether the aluminoxane component is in a solid state is by visual inspection, but this is often difficult, for example, during polymerization. In such cases, it is possible to determine this from, for example, the properties of the polymer powder obtained after polymerization or the degree of adhesion to the reactor. Conversely, if the properties of the polymer powder are good and there is little adhesion to the reactor, even if some of the aluminoxane component dissolves under the polymerization environment, it does not deviate from the spirit of the present invention. Indicators for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of presence of amorphous polymers, but polymer bulk density is preferred from the viewpoint of quantitative accuracy. The bulk density is usually in the range of 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

[0164] The dissolution rate of the solid aluminoxane compound in n-hexane held at a temperature of 25°C is typically in the range of 0 to 40 mol%, preferably 0 to 20 mol%, and particularly preferably 0 to 10 mol%.

[0165] The aforementioned dissolution ratio is determined by adding 2 g of a solid aluminoxane compound support to 50 ml of n-hexane maintained at 25°C, stirring for 2 hours, then separating the solution using a G-4 glass filter, and measuring the aluminum concentration in the filtrate. Therefore, the dissolution ratio is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of aluminoxane used.

[0166] As the solid aluminoxane compound, any known solid aluminoxane can be used without limit, and for example, the solid polyaluminoxane composition described in International Publication No. 2014 / 123212 can be used. Known manufacturing methods include, for example, those described in Japanese Patent Publication No. 7-42301, Japanese Patent Publication No. 6-220126, Japanese Patent Publication No. 6-220128, Japanese Patent Publication No. 11-140113, Japanese Patent Publication No. 11-310607, Japanese Patent Publication No. 2000-38410, Japanese Patent Publication No. 2000-95810, and International Publication No. 2010 / 55652.

[0167] The average particle size of the solid aluminoxane compound is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1,000 μm, and particularly preferably 1 to 200 μm. The average particle size of the solid aluminoxane compound is determined by observing the particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and weight averaging them. First, the particle size of each particle is determined by measuring the length of two parallel lines that sandwich the particle image horizontally and vertically, and using the following formula. Particle size = ((horizontal length)) 2 + (vertical length) 2 ) 0.5

[0168] Next, the weight-average particle size of the solid aluminoxane compound can be calculated using the particle size obtained above, according to the following formula. Average particle diameter=Σnd 4 / Σnd 3 (n: number of particles, d: particle size) The solid aluminoxane compound has a specific surface area of ​​50 to 1000 m². 2 / g, preferably 100-800m 2 The density is / g, and the pore volume is 0.1-2.5 cm³. 3 It is preferable that the value be / g.

[0169] Examples of inorganic halides include MgCl2, MgBr2, MnCl2, and MnBr2. The inorganic halides may be used as is, or they may be ground using a ball mill or vibration mill before use. Alternatively, the inorganic halides can be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

[0170] The aforementioned clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystalline structure in which planes formed by ionic bonds are stacked parallel to each other with weak bonding forces, and the ions it contains are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Furthermore, these clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural sources; artificially synthesized materials can also be used.

[0171] Furthermore, examples of clay, clay minerals, or ion-exchangeable layered compounds include ionic crystalline compounds having layered crystalline structures such as hexagonal close-packing type, antimony type, CdCl2 type, and CdI2 type.

[0172] Furthermore, clays and clay minerals include kaolin, bentonite, kibushi clay, gylome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, lyokdiite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. 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.

[0173] Such clays, clay minerals, or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc / g or more, and particularly preferably 0.3 to 5 cc / g, as measured by the mercury intrusion method for pores with a radius of 20 Å or more. Here, the pore volume is measured in the range of pore radii from 20 to 30,000 Å by the mercury intrusion method using a mercury porosimeter. When using a support material with a pore volume of less than 0.1 cc / g and a radius of 20 Å or more, it tends to be difficult to obtain high polymerization activity.

[0174] It is also preferable to subject the aforementioned clay and clay minerals to chemical treatment. Chemical treatments can include surface treatments to remove impurities adhering to the surface, and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment removes surface impurities and increases the surface area by dissolving cations such as Al, Fe, and Mg in the crystalline structure. Alkali treatment destroys the crystalline structure of the clay, leading to a change in its structure. Salt treatment and organic treatment can form ionic complexes, molecular complexes, and organic derivatives, thereby altering the surface area and interlayer distance.

[0175] The aforementioned ion-exchangeable layered compound may be a layered compound in which the interlayers are expanded by utilizing ion exchange properties and exchanging the exchangeable ions between layers with other large, bulky ions. Such bulky ions play a supporting role in the layered structure and are usually called pillars. The introduction of another substance between the layers of a layered compound in this way is called intercalation. Possible guest compounds for intercalation include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.), and [Al 13 O4(OH) 24 ] 7+ [Zr4(OH) 14 ] 2+ [Fe3O(OCOCH3)6] + Examples include metal hydroxide ions. These compounds can be used individually or in combination of two or more. Furthermore, when intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides (where R represents a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, or colloidal inorganic compounds such as SiO2 can also be present. In addition, as pillars, oxides produced by heating and dehydrating after intercalating the above-mentioned metal hydroxide ions between layers can also be used.

[0176] The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as is, or after being subjected to treatments such as ball milling or sieving. Alternatively, they may be used after being newly treated with water adsorption or heat dehydration. Furthermore, they may be used individually or in combination of two or more.

[0177] Of these, clay or clay minerals are preferred, with montmorillonite, vermiculite, pectolite, teniolite, and synthetic mica being particularly preferred. Examples of the organic compound that can be used as the solid carrier (S) include granular or particulate solids having a particle size in the range of 1 to 300 μm. Specifically, polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, polymers produced mainly from vinylcyclohexane or styrene, and modified products thereof can be exemplified.

[0178] <Compound (B)> The catalyst for producing polyolefin of the present invention preferably further comprises (B-1) An organometallic compound represented by the following general formula (B-1a), (B-1b) or (B-1c) (hereinafter also referred to as "component (B-1)"). R a m Al(OR<​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​is selected from Mg, Zn, and Cd, X represents a halogen atom, and r is 0 <r≦2、sは0≦s≦1、tは0≦t≦1であり、かつr+s+t=2である。〕 (B-2) Organoaluminum oxy compounds (hereinafter also referred to as "component (B-2)"), and (B-3) At least one compound (B) selected from the group consisting of compounds that react with a transition metal complex (T) to form an ion pair (hereinafter also referred to as "component (B-3)") (hereinafter also referred to as "component (B)"). Includes.

[0179] As the organometallic compound (B-1), any compound disclosed in Japanese Patent Publication No. 11-315109 or European Patent No. 0874005 by the present applicant can be used without limitation. The organometallic compound (B-1) is preferably one represented by general formula (B-1a), specifically trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and dimethylaluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; methylaluminum dichloride; and ethylaluminum dichloride. Examples include alkylaluminum dihalides such as lydes, isopropylaluminum dichloride, and ethylaluminum dibromide; dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride, and di-sec-nonylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, and diisobutylaluminum ethoxide.

[0180] These can be used individually or in combination of two or more types. The organoaluminum oxy compound (B-2) is preferably an aluminoxane prepared from trialkylaluminum or tricycloalkylaluminum, and particularly preferably an organoaluminum oxy compound prepared from trimethylaluminum or triisobutylaluminum. Such organoaluminum oxy compounds can be used individually or in combination of two or more.

[0181] As the compound (B-3) that reacts with the transition metal complex (T) to form an ion pair, Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Application Publication No. 3-179005, Japanese Patent Application Publication No. 3-179006, Japanese Patent Application Publication No. 3-207703, Japanese Patent Application Publication No. 3-207704, and U.S. Patent No. 5321106, etc., as well as heteropoly compounds and isopoly compounds can be used without limitation.

[0182] In the aforementioned catalyst for polyolefin production, when an organoaluminum oxy compound (B-2) such as methylaluminoxane is used in combination as a co-catalyst component, it not only exhibits very high catalytic activity for olefins, but also reacts with active hydrogen in the solid support to easily prepare a solid support component containing the co-catalyst component. Therefore, it is preferable to use the organoaluminum oxy compound (B-2) as component (B).

[0183] <How to use and the order of addition for each ingredient> The aforementioned catalyst for polyolefin production can be produced by a step of prepolymerizing a solid catalyst component (Sa) containing a transition metal complex (T) and a solid support (S). Specifically, it can be prepared by mixing and contacting component (T) and component (S), and optionally component (B), in an inert hydrocarbon.

[0184] Regarding methods for bringing each component into contact, focusing on the order of contact, for example, (i) A method of bringing component (T) into contact with component (S). (ii) A method in which component (S) is brought into contact with component (B), and then component (T) is brought into contact with component (S). (iii) A method in which component (T) is brought into contact with component (B), and then component (S) is brought into contact with component (T). (iv) A method in which component (S) is brought into contact with component (B), and then a mixture of component (T) and component (B) is brought into contact. (v) A method in which component (S) is brought into contact with component (B), then component (B) is brought into contact again, and then a mixture of component (T) and component (B) is brought into contact. These are some examples. If multiple types of component (B) are used, those components (B) may be the same or different. Of the above methods, (i), (ii), and (iii) are preferred.

[0185] In each of the methods described above for the contact sequence configuration, in the step involving contact between component (S) and component (T), if two or more types of component (T) are used, the order of contact with component (S) is arbitrary, and two or more types of component (T) may be brought into contact in any order, or they may be brought into contact simultaneously.

[0186] The solid catalyst component (Sa) used in the method for producing a polyolefin catalyst of the present invention is obtained by contacting component (S) and component (T) in an inert hydrocarbon at a temperature preferably between -50°C and 200°C, more preferably between -20°C and 150°C, even more preferably between 0°C and 100°C, and particularly preferably between 15°C and 30°C. The contact time is preferably 0.01 to 48 hours, more preferably 0.1 to 24 hours, even more preferably 0.3 to 6 hours, and particularly preferably 0.5 to 2 hours.

[0187] When preparing the solid catalyst component (Sa), component (T) is used in an amount of preferably 1 μmol to 1.0 mmol, more preferably 3 μmol to 0.5 mmol, even more preferably 5 μmol to 0.3 mmol, and particularly preferably 10 μmol to 0.1 mmol per gram of component (S).

[0188] In each of the methods described above regarding the contact sequence configuration, the presence of component (G) in the steps involving contact between component (S) and component (B), and in the steps involving contact between component (S) and component (T), suppresses fouling during the polymerization reaction and improves the particle properties of the resulting polymer. As component (G), a compound having a polar functional group can be used, and nonionic surfactants are preferred, with polyalkylene oxide blocks, higher aliphatic amides, polyalkylene oxides, polyalkylene oxide alkyl ethers, alkyldiethanolamines, polyoxyalkylene alkylamines, glycerin fatty acid esters, and N-acyl amino acids being more preferred. These may be used individually or in combination of two or more. An example of alkyldiethanolamine is Electro Stripper® EA (manufactured by Kao Corporation).

[0189] Examples of solvents used in the preparation of the catalyst for the production of polyolefins 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; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; or mixtures thereof.

[0190] During the contact between component (B) and component (S), chemical bonding occurs through the reaction between the reaction sites in component (B) and component (S), forming a contact product between component (B) and component (S). The contact time between component (B) and component (S) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is usually -50 to 200°C, preferably -20 to 120°C. If the initial contact between component (B) and component (S) is carried out too rapidly, the reaction heat and reaction energy will cause component (S) to disintegrate, degrading the morphology of the resulting solid catalyst component (Sa). If this is used for polymerization, poor polymer morphology often makes continuous operation difficult. Therefore, in the initial contact between component (B) and component (S), it is preferable to contact them at a lower temperature to suppress reaction heat, or to control the reaction heat and react at a rate that allows the initial contact temperature to be maintained. The same applies when component (B) and component (S) are brought into contact, and then component (B) is brought into contact again. The contact mass ratio between component (B) and component (S) (mass of component (B) / mass of component (S)) can be arbitrarily selected, but a higher contact mass ratio allows for contact with more component (T), thereby improving the catalytic activity per unit mass of the solid catalyst component (Sa).

[0191] The contact mass ratio between component (B) and component (S) [= mass of component (B) / mass of component (S)] is preferably 0.05 to 3.0, and particularly preferably 0.1 to 2.0. When the contact material of component (B) and component (S) is brought into contact with component (T), the contact time is usually 1 minute to 20 hours, preferably 1 minute to 10 hours, more preferably 10 minutes to 7 hours, and even more preferably 30 minutes to 5 hours, and the contact temperature is usually in the range of -50 to 200°C, preferably -50 to 100°C, preferably -20 to 150°C, more preferably 0 to 100°C, and even more preferably 15 to 30°C.

[0192] Component (B-1) is used in such an amount that the molar ratio [(B-1) / M] of component (B-1) to the total transition metal atoms (M) in component (T) is typically 0.01 to 100,000, preferably 0.05 to 50,000.

[0193] Component (B-2) is used in such an amount that the molar ratio [(B-2) / M] of component (B-2) (in terms of aluminum atoms) to the total transition metal atoms (M) in component (T) is typically 10 to 500,000, preferably 20 to 100,000, more preferably 50 to 10,000, and even more preferably 100 to 1,000.

[0194] Component (B-3) is used in an amount such that the molar ratio [(B-3) / M] of component (B-3) to the total transition metal atoms (M) in component (T) is usually 1 to 10, preferably 1 to 5. The ratio of component (B) to the total number of transition metal atoms (M) in component (T) can be determined by inductively coupled plasma atomic emission spectrometry (ICP).

[0195] <Catalyst for Polyolefin Production> For the production of polyolefins, the aforementioned catalyst for polyolefin production can be used as is, but it can also be used after prepolymerizing the catalyst for polyolefin production with an olefin to form a prepolymerized solid catalyst component.

[0196] The prepolymerized solid catalyst component can be prepared by prepolymerizing ethylene, etc., in an inert hydrocarbon solvent in the presence of the polyolefin production catalyst, and can be carried out by batch, semi-continuous, or continuous methods, and can be carried out under reduced pressure, atmospheric pressure, or pressurized pressure. Furthermore, it is desirable that the prepolymerization produces 0.01 to 1000 g, preferably 0.1 to 800 g, and more preferably 0.2 to 500 g of the prepolymerized solid catalyst component per 1 g of solid catalyst component (Sa).

[0197] The prepolymerization solid catalyst component, generated in an inert hydrocarbon solvent, may be separated from the suspension and then resuspended in the inert hydrocarbon to introduce the olefin into the resulting suspension. Alternatively, the olefin may be introduced after drying.

[0198] 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. For prepolymerization, an olefin mainly composed of ethylene is preferably used. The supply rate of the olefin to be prepolymerized is preferably 0.05 to 10 L / hr, more preferably 0.1 to 7 L / hr, and even more preferably 0.5 to 4 L / hr per 1 g of solid catalyst component (Sa).

[0199] The amount of olefin to be prepolymerized is preferably 1 g to 50 g, more preferably 1.5 g to 30 g, and even more preferably 2 g to 20 g, per 1 g of solid catalyst component (Sa).

[0200] If the amount of olefin prepolymerization is small, the release of transition metal components from the solid catalyst component (Sa) in the subsequent polymerization reaction is promoted. If the amount of prepolymerization is large, the charging of the prepolymerization components may increase the likelihood of electrostatic adhesion during prepolymerization.

[0201] The solid catalyst component (Sa) used for prepolymerization can be any of the forms already described without limitation. In addition, component (B) can be used as needed, and in particular, the organoaluminum compound [B-1a] represented by general formula (B-1a) is preferably used. When component (B) is used, it is used in an amount such that the molar ratio (Al / M) of aluminum atoms (Al) in component (B) to transition metal atoms (M) in the transition metal complex (T) is 0.1 to 10,000, preferably 0.5 to 5,000.

[0202] The concentration of the polyolefin production catalyst in the prepolymerization system is preferably 1 to 1000 grams / liter, and more preferably 10 to 500 grams / liter, in terms of the catalyst / polymerization volume ratio. During prepolymerization, component (G) may be present for the purpose of suppressing fouling or improving particle properties.

[0203] Furthermore, to improve the fluidity of the prepolymerization solid catalyst component and to suppress the generation of heat spots, sheeting, and polymer clumps during polymerization, component (G) may be brought into contact with the prepolymerization solid catalyst component that has been produced by prepolymerization.

[0204] The temperature at which the above component (G) is brought into contact is usually -50 to 50°C, preferably -20 to 50°C, and the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 10 hours. When bringing the polyolefin production catalyst into contact with component (G), component (G) is used in an amount of 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass, more preferably 0.4 to 5 parts by mass, and even more preferably 0.6 to 2 parts by mass, per 100 parts by mass of the polyolefin production catalyst.

[0205] The mixing contact between the polyolefin production catalyst and component (G) can be carried out in an inert hydrocarbon solvent, and examples of inert hydrocarbon solvents are the same as those described above. In the method for producing polyolefins according to the present invention, a dried prepolymerization solid catalyst component (hereinafter also referred to as "dried prepolymerization catalyst") can be used as the catalyst for polyolefin production. The drying of the prepolymerization solid catalyst component is usually carried out after removing hydrocarbons, which are the dispersion medium, from the obtained suspension of the prepolymerization catalyst by filtration or the like.

[0206] The prepolymerization solid catalyst component is dried by maintaining it at a temperature of 70°C or lower, preferably in the range of 20 to 50°C, under the flow of an inert gas. The volatile component content of the resulting dried prepolymerization catalyst is preferably 2.0% by mass or less, preferably 1.0% by mass or less. A lower volatile component content is preferable, and there is no particular lower limit, but practically, it is 0.001% by mass. The drying time is usually 1 to 48 hours, depending on the drying temperature.

[0207] The aforementioned dried prepolymerization catalyst has excellent fluidity, allowing for stable supply to the polymerization reactor. Furthermore, using the aforementioned dried prepolymerization catalyst eliminates the need to introduce the solvent used for suspension into the gas-phase polymerization system, thus enabling stable polymerization.

[0208] <Method for producing polyolefins> The present invention provides a method for producing polyolefins, characterized by polymerizing ethylene or copolymerizing ethylene with an olefin having 3 to 20 carbon atoms in the presence of the polyolefin production catalyst of the present invention. In the present invention, the ethylene content in the polyolefin is preferably 70 mol% or more (with the total monomer units being 100 mol%).

[0209] Polymerization methods include liquid-phase polymerization methods such as solution polymerization and suspension polymerization, and gas-phase polymerization methods, with suspension polymerization and gas-phase polymerization methods being preferred.

[0210] 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 ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof.

[0211] When polymerizing polyolefins using the aforementioned catalyst for polyolefin production, component (T) is typically 1 × 10⁻¹⁶ per liter of reaction volume. -12 ~1 × 10 -1 Moles, preferably 1 × 10⁻⁶ -8 ~1 × 10 -2 It is used in an amount that equals moles. Preferably, component (B) is used, and more preferably, the compound represented by general formula (B-1a) or component (B-2) is used.

[0212] When polymerizing olefins, the polymerization temperature is usually lower limit 60°C, preferably 70°C, and particularly preferably 75°C. Higher temperatures are advantageous in terms of heat removal and other aspects in industrial-scale production. The upper limit is usually 250°C, preferably 200°C, and the polymerization pressure is usually atmospheric pressure ~100 kg / cm². 2 Preferably, at atmospheric pressure ~50 kg / cm² 2 That is the case.

[0213] Polymerization reactions can be carried out using batch, semi-continuous, or continuous methods. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions. The molecular weight of the polyolefin obtained by the polyolefin production method according to the present invention can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. During polymerization, component (G) can be added for the purpose of suppressing fouling or improving particle properties.

[0214] In the present invention, the monomer supplied to the polymerization reaction is either ethylene alone or ethylene and an olefin having 3 to 20 carbon atoms. Specific examples of olefins having 3 to 20 carbon atoms include α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, as well as cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0215] Furthermore, small amounts of styrene, vinylcyclohexane, dienes, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc., or polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid, etc., may be supplied within the limits that do not impair the effects of the present invention.

[0216] The above ethylene-α-olefin copolymer may contain biomass-derived monomers (ethylene, α-olefin). The monomers constituting the ethylene-α-olefin copolymer may consist solely of biomass-derived monomers, solely of fossil fuel-derived monomers, or may contain both biomass-derived monomers and fossil fuel-derived monomers.

[0217] The above biomass-derived monomers are monomers derived from any renewable natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, whether plant-derived or animal-derived, and are carbon-based. 14 1 × 10¹¹ C isotopes -12 It contains biomass-derived monomers in a certain proportion, and the biomass carbon concentration (pMC) measured in accordance with ASTM D6866 is approximately 100 pMC. Biomass-derived monomers are obtained by conventionally known methods. It is preferable that the above ethylene-α-olefin copolymer contains biomass-derived monomers from the viewpoint of reducing environmental impact (mainly greenhouse gas reduction). If the polymer production conditions such as polymerization catalyst and polymerization process polymerization temperature are the same, even if the raw material monomer contains biomass-derived monomers, 14 1 × 10¹¹ C isotopes -12 ~1 × 10 -14 Aside from the small proportions it contains, its molecular structure is equivalent to that of an ethylene-α-olefin copolymer composed of fossil fuel-derived monomers. Therefore, its performance is considered to be the same.

[0218] The above ethylene-α-olefin copolymer may contain monomers derived from chemical recycling (e.g., ethylene, α-olefin, etc.). The monomers constituting the ethylene-α-olefin copolymer may consist solely of monomers derived from chemical recycling, solely of monomers derived from fossil fuels, or may include monomers derived from chemical recycling, monomers derived from fossil fuels, and / or monomers derived from biomass. Monomers derived from chemical recycling can be obtained by conventionally known methods. It is preferable for the above ethylene-α-olefin copolymer to contain monomers derived from chemical recycling from the viewpoint of reducing environmental impact (mainly waste reduction). Since monomers derived from chemical recycling are monomers obtained by depolymerizing polymers such as waste plastics back to monomer units such as ethylene through depolymerization, thermal decomposition, etc., and monomers produced using such monomers as raw materials, even if monomers derived from chemical recycling are included as raw material monomers for the ethylene-α-olefin copolymer, the molecular structure is equivalent to that of an ethylene-α-olefin copolymer consisting of monomers derived from fossil fuels, provided that the polymer production conditions such as polymerization catalyst, polymerization process, and polymerization temperature are the same. Therefore, the performance is also considered to be unchanged.

[0219] <Other thermoplastic resins> Furthermore, the ethylene-α-olefin copolymer according to the present invention may also contain thermoplastic resins other than the ethylene-α-olefin copolymer of the present invention (hereinafter referred to as "other thermoplastic resins"). The ethylene-based resin composition obtained as a thermoplastic resin composition by blending the above ethylene-α-olefin copolymer with "other thermoplastic resins" exhibits excellent moldability and mechanical strength.

[0220] The blend ratio (mass of ethylene-α-olefin copolymer / mass of other thermoplastic resin) of the present invention between the ethylene-α-olefin copolymer and other thermoplastic resins is typically 99.9 / 0.1~0.1 / 99.9, preferably 90 / 10~10 / 90, and more preferably 70 / 30~30 / 70.

[0221] Other thermoplastic resins include crystalline thermoplastic resins such as polyolefins other than the ethylene-α-olefin copolymer of the present invention (hereinafter also referred to as "other polyolefins"), polyamides, polyesters, and polyacetals; and amorphous thermoplastic resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate, polyphenylene oxide, and polyacrylate. Polyvinyl chloride is also preferred. Furthermore, the other thermoplastic resin may be polyester, polyamide, polyurethane, polylactic acid, or polycarbonate containing biomass-derived monomers or chemically recycled monomers.

[0222] Other polyolefins mentioned above include, specifically, ethylene polymers, propylene polymers, butene polymers, 4-methyl-1-pentene polymers, 3-methyl-1-butene polymers, and hexene polymers. Among these, ethylene polymers, propylene polymers, and 4-methyl-1-pentene polymers are preferred. In the case of ethylene polymers, conventional ethylene polymers or ethylene-polar group-containing vinyl copolymers may be used, but conventional ethylene polymers are more preferred. The ethylene polymers and propylene polymers may each contain biomass-derived monomers.

[0223] The other polyolefins mentioned above may each be polyolefins containing biomass-derived monomers. The monomers constituting the other polyolefins may consist solely of biomass-derived monomers, solely of fossil fuel-derived monomers, or may contain both biomass-derived monomers and fossil fuel-derived monomers.

[0224] The other polyolefins mentioned above may each be polyolefins containing monomers derived from chemical recycling. The monomers constituting the other polyolefins may consist solely of monomers derived from chemical recycling, solely of monomers derived from fossil fuels, or may include monomers derived from chemical recycling, monomers derived from fossil fuels, and / or monomers derived from biomass.

[0225] The ethylene-α-olefin copolymer of the present invention may contain, as necessary, additives such as weather-resistant stabilizers, heat-resistant stabilizers, antistatic agents, anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbers, and antioxidants, to the extent that the objectives of the present invention are not impaired. The total content of these additives is generally 10 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, based on 100 parts by mass of the total components of the ethylene-α-olefin copolymer other than the additives.

[0226] [Application] By processing the ethylene-α-olefin copolymer of the present invention or a thermoplastic resin composition containing the ethylene-α-olefin copolymer, a molded article, preferably a film, can be obtained that has excellent surface appearance and a good balance of moldability, mechanical strength, transparency, and blocking resistance.

[0227] The ethylene-α-olefin copolymer or thermoplastic resin composition containing the ethylene-α-olefin copolymer of the present invention can be processed by general film molding, sheet molding, blow molding, injection molding, and extrusion molding. Film molding methods include extrusion lamination, T-die film molding, and inflation molding (air cooling, water cooling, multi-stage cooling, high-speed processing). The resulting film can be used as a single layer, but various functions can be added by creating multilayer films. Co-extrusion is one molding method used in this case. On the other hand, lamination molding methods such as extrusion lamination and dry lamination allow for lamination with paper and barrier films (aluminum foil, vapor-deposited film, coating film, etc.) that are difficult to co-extrude. The production of high-performance products by co-extrusion in multilayer films using blow molding, injection molding, and extrusion molding is possible, similar to film molding.

[0228] 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 infusion bags, blow bottles, gasoline tanks, injection molded products such as tubes, pipes, wire coatings, tear-off caps, and daily necessities, as well as fibers and large molded products by rotational molding.

[0229] 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 such as liquid packaging bags, liquid soup packaging bags, liquid paper containers, laminated raw materials, special-shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, wrap films, sugar bags, oil packaging bags, and food packaging films, as well as protective films, infusion bags, agricultural materials, etc. It is also suitable for clean films used in packaging for bag-in-boxes, semiconductor materials, pharmaceuticals, food, etc. In addition, the above film can be laminated with a substrate such as nylon, polyester, or polyolefin film to be used as a multilayer film.

[0230] The raw materials for the substrate of the multilayer film may include ethylene polymers and propylene polymers containing biomass-derived monomers. [Examples]

[0231] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples.

[0232] [Physical property measurement and evaluation] In the following examples, various physical properties of ethylene-α-olefin copolymers, etc., were measured using the method described in [Modes for Carrying Out the Invention], and the following methods were used as evaluation methods not described in [Modes for Carrying Out the Invention].

[0233] Inflation molding evaluation: A film with a thickness of 40 μm was obtained from the polymer using a 50 mmφ extruder and a Sumitomo Heavy Industries Modern Co., Ltd. inflation molding machine with a die diameter of 100 mm, under the conditions of a die temperature of 190°C, an extrusion rate of 29 kg / hr, and a tube width of 320 mm. The following parameters were measured for the obtained film.

[0234] <Bubble Stability> The stability of the bubbles (molten film) during inflation molding was visually confirmed. The meaning of the symbols (evaluation results) in Table 10 is as follows. ○: The bubble (molten film) is stable. ×: The bubble (molten film) is unstable and shakes violently.

[0235] <Hayes> The total haze of the obtained film was measured in accordance with JIS 7136.

[0236] <Internal haze> The obtained film was placed in a cell filled with cyclohexanol and measured in accordance with JIS 7136.

[0237] <Gloss 20°> In accordance with JIS Z8741, the gloss of the film obtained at an incident angle of 20° was measured.

[0238] <Tensile modulus> In accordance with JIS K6781, measurements were taken of the obtained film in both the MD and TD directions at a test speed of 200 mm / min.

[0239] <Dirt Impact> In accordance with ASTM D1709 A method, the obtained film was clamped using an air clamp system, and a hemispherical dart was dropped from a certain height. The load at which the film was 50% destroyed was read from the graph.

[0240] <Blocking power> Two tubular films were stacked together, with their inner surfaces facing each other. A 10 kg load was applied to the resulting test specimen at 50°C and aged for three days. After that, the specimen was cut into 200 mm wide strips, and the force required to separate them at 23°C and 200 mm / min was measured as the blocking force.

[0241] <Particle size dispersion ratio> Using a Microtrac MT3300EXII from Microtrac, methanol (Fujifilm Wako Pure Chemical Industries, Ltd., reagent grade) was used as the dispersion medium. The solid support (S) was dispersed using the instrument's built-in ultrasonic homogenizer at an output of 25W for 5 minutes. The particle size corresponding to 10% of the cumulative mass from the smallest diameter in the particle size distribution (Dw10) and the particle size corresponding to 50% of the cumulative mass from the smallest diameter in the particle size distribution (Dw50) were measured by wet laser diffraction scattering. Similarly, the 10% cumulative mass diameter (Ds10) and the 50% cumulative mass diameter (Ds50) were measured under the same conditions, except that the dispersion was performed at an output of 40W for 15 minutes. The particle size dispersion ratios (R10) and (R50) are expressed by the following formulas. R10 = Ds10 / Dw10 × 100 R50 = Ds50 / Dw50 × 100

[0242] [Raw materials used] The transition metal compounds (T) and solid supports (S) used in the examples are as follows. The solid supports (S) were all dried at 200°C for 10 hours before being used in the examples. Transition metal complex (T-1): Dimethylsilylene (2-indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-7-methoxy-1-indenyl) zirconium dichloride [Synthesized by the method described in Japanese Patent Publication No. 2019-059933.] Transition metal complex (T-2): Bis(1-n-butyl-3-methylcyclopentadienyl)zirconium dichloride [Synthesized by the same method as described in Japanese Patent Publication No. 2000-514494.] Solid carrier (S-1): Sylopol 2326 manufactured by W.R. Grace (porous material, R10=76%, R50=80%) Solid carrier (S-2): Sylopol 2408HT manufactured by W.R. Grace (porous material, R10=95%, R50=95%) Solid carrier (S-3): P-10 manufactured by Fuji Silicia Co., Ltd. (porous material, R10=100%, R50=100%)

[0243] <Preparation of Catalyst (XP-1) for Polyolefin Production> In a 1000 mL reactor with a stirrer, 54.9 g of solid support (S-1) was suspended in 350 mL of toluene under a nitrogen atmosphere, and then cooled to 0-5°C. To this suspension, 27.4 mL of a 1.0 mol / L diisobutylaluminum hydride toluene solution was added dropwise over 30 minutes, while maintaining the system temperature at 0-5°C. After continuing contact at 0-5°C for 30 minutes, 149.6 mL of a methylaluminoxane toluene solution (3.0 mmol / mL in terms of Al atoms) was added dropwise over 30 minutes, while maintaining the system temperature at 0-5°C. After continuing contact at 0-5°C for 30 minutes, the system temperature was raised to 95°C over approximately 1.5 hours, and then continued contact at 95°C 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 total volume of 300 mL of toluene slurry. A sample of the obtained slurry was taken and its concentration was examined. The slurry concentration was 268.0 g / L and the Al concentration was 1.49 mol / L.

[0244] 205.2 mL of toluene and 280.0 mL of the above-mentioned toluene slurry (solid content = 75.0 g) were charged into a 2000 mL stirred reactor with a sufficient nitrogen purging. Next, 209.2 mL of a 0.008 mol / L toluene solution of the transition metal complex (T-1) was added, and the mixture was contacted at a system temperature of 20-25°C for 1 hour. After removing the supernatant by decantation, the mixture was washed twice with hexane to prepare a total volume of 1635 mL of solid catalyst slurry.

[0245] The prepared solid catalyst slurry was cooled to 10°C under a nitrogen atmosphere, and 68.1 mL of a 1.0 mol / L diisobutylaluminum hydride hexane solution was added. While maintaining the system temperature at 10-15°C, ethylene was continuously supplied to the system under atmospheric pressure for several minutes, followed by the addition of 0.86 mL of 1-hexene. Then, ethylene supply was started at 37.8 g / h, and prepolymerization was carried out at a system temperature of 32-37°C. 0.86 mL of 1-hexene was added every hour for a total of five times from the start of prepolymerization, and the ethylene supply was stopped when it reached 226.5 g after 6 hours from the start of prepolymerization. The supernatant was then removed by decantation and washed four times with hexane. Further hexane was added to bring the total volume to 1095 mL, obtaining the prepolymerization catalyst hexane slurry.

[0246] The prepared prepolymerization catalyst hexane slurry was heated to 35°C under a nitrogen atmosphere, and 306.6 mL of a 10 mg / mL hexane solution of Electro Stripper (registered trademark) EA (manufactured by Kao Corporation) was added. The mixture was then contacted at 32-37°C for 2 hours. Next, it was transferred to a 1000 mL glass filter that had been thoroughly purged with nitrogen, and the pressure was reduced to -68 kPaG over approximately 1 hour. Once -68 kPaG was reached, it was vacuum-dried for approximately 2 hours to obtain the catalyst for polyolefin production (XP-1).

[0247] <Preparation of Catalyst (XP-2) for Polyolefin Production> In a 1000 mL reactor with a stirrer, 69.9 g of solid support (S-2) was suspended in 400 mL of toluene under a nitrogen atmosphere, and then cooled to 0-5°C. To this suspension, 34.9 mL of a 1.0 mol / L diisobutylaluminum hydride toluene solution was added dropwise over 30 minutes, while maintaining the system temperature at 0-5°C. After continuing contact at 0-5°C for 30 minutes, 169.0 mL of a methylaluminoxane toluene solution (3.0 mmol / mL in terms of Al atoms) was added dropwise over 30 minutes, while maintaining the system temperature at 0-5°C. After continuing contact at 0-5°C for 30 minutes, the system temperature was raised to 95°C over approximately 1.5 hours, and then contact was maintained at 95°C 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 total volume of 400 mL of toluene slurry. A sample of the obtained slurry was taken and its concentration was examined. The slurry concentration was 242.0 g / L and the Al concentration was 1.21 mol / L.

[0248] In a 2000 mL stirred reactor that had been thoroughly purged with nitrogen, 192.8 mL of toluene and 330.0 mL of the above-mentioned toluene slurry (solid content = 79.9 g) were charged. Next, 265.1 mL of a 0.006 mol / L toluene solution of the transition metal complex (T-1) was added, and the mixture was contacted at a system temperature of 20-25°C for 1 hour. After removing the supernatant by decantation, the mixture was washed twice with hexane to prepare a total volume of 1635 mL of solid catalyst slurry.

[0249] The prepared solid catalyst slurry was cooled to 10°C under a nitrogen atmosphere, and 72.4 mL of a 1.0 mol / L diisobutylaluminum hydride hexane solution was added. While maintaining the system temperature at 10-15°C, ethylene was continuously supplied to the system under atmospheric pressure for several minutes, followed by the addition of 0.91 mL of 1-hexene. Then, ethylene supply was started at 40.0 g / h, and prepolymerization was carried out at a system temperature of 32-37°C. 0.91 mL of 1-hexene was added every hour for a total of five times from the start of prepolymerization, and the ethylene supply was stopped when it reached 240.1 g after 6 hours from the start of prepolymerization. The supernatant was then removed by decantation and washed four times with hexane. Further hexane was added to bring the total volume to 1163 mL, obtaining the prepolymerization catalyst hexane slurry.

[0250] The prepared prepolymerization catalyst hexane slurry was heated to 35°C under a nitrogen atmosphere, and 320.6 mL of a 10 mg / mL hexane solution of Electro Stripper (registered trademark) EA (manufactured by Kao Corporation) was added. The mixture was then contacted at 32-37°C for 2 hours. Next, it was transferred to a 1000 mL glass filter that had been thoroughly purged with nitrogen, and the pressure was reduced to -68 kPaG over approximately 1 hour. Once -68 kPaG was reached, it was vacuum-dried for approximately 2 hours to obtain the catalyst for polyolefin production (XP-2).

[0251] <Synthesis of Catalyst (XP-3) for Polyolefin Production> In a 270 L reactor equipped with a stirrer, 10 kg of solid carrier (S-3) was suspended in 77 L of toluene under a nitrogen atmosphere, and then cooled to 0-5°C. 20.4 L of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) was added dropwise to this suspension over 30 minutes. During this time, the temperature in the system was maintained at 0-5°C. The reaction continued at 0-5°C for 30 minutes, then the temperature was raised to 95-100°C over approximately 1.5 hours, and the reaction continued at 95-100°C for 4 hours. After cooling to room temperature, the supernatant was removed by decantation, and the mixture was washed twice with toluene to prepare a total volume of 58.0 L of toluene slurry. A sample of the obtained slurry components was taken and its concentration was examined, revealing a slurry concentration of 248.0 g / L and an Al concentration of 1.21 mol / L.

[0252] Next, 6.1 L of the toluene slurry obtained above and 21.9 L of toluene were charged into a 114 L stirrer with a sufficient nitrogen purging. 5.4 L of an 8 mM toluene solution of a transition metal compound (T-1) was added, and the mixture was contacted 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 of 30.9 L of slurry. While adjusting the obtained slurry to 10-15°C, 3.1 L of a 0.92 M hexane solution of diisobutylaluminum hydride was added, and ethylene gas was supplied at a flow rate of 0.74 kg / h. After adding 34.3 mL of 1-hexene, the temperature was increased, and 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. Six hours after the start of ethylene supply, when the ethylene supply reached 4.5 kg, the ethylene supply was stopped. Subsequently, the system was thoroughly purged with nitrogen, the supernatant was removed by decantation, and after washing four times with hexane, a total volume of 21.9 L of slurry was prepared. While maintaining the obtained slurry at 35-40°C, 6.1 L of a 10 mg / mL hexane solution of Electro Stripper (registered trademark) EA (manufactured by Kao Corporation) was added and contacted for 2 hours. The entire obtained slurry was placed in a 43 L evaporative dryer with a stirrer under a nitrogen atmosphere, and the inside of the dryer was reduced to -68 kPaG over approximately 60 minutes. Once -68 kPaG was reached, it was vacuum dried for approximately 4.3 hours to remove volatile components from hexane and the prepolymerization catalyst. The pressure was further reduced to -100 kPaG, and once -100 kPaG was reached, it was vacuum dried for 8 hours to obtain the catalyst for polyolefin production (XP-3).

[0253] <Preparation of Catalyst (XP-4) for Polyolefin Production> In a 1000 mL reactor with a stirrer, 44.6 g of solid support (S-3) was suspended in 250 mL of toluene under a nitrogen atmosphere, and then cooled to 0-5°C. 22.7 mL of a 1.0 mol / L diisobutylaluminum hydride toluene solution was added dropwise to this suspension over 30 minutes, while maintaining the system temperature at 0-5°C. After continuing contact at 0-5°C for 30 minutes, 136.4 mL of a methylaluminoxane toluene solution (3.5 mmol / mL in terms of Al atoms) was added dropwise over 30 minutes, while maintaining the system temperature at 0-5°C. After continuing contact at 0-5°C for 30 minutes, the system temperature was raised to 95°C over approximately 1.5 hours, and then contact was maintained at 95°C 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 total volume of 200 mL of toluene slurry. A sample of the obtained slurry was taken and its concentration was examined. The slurry concentration was 255.0 g / L and the Al concentration was 1.27 mol / L.

[0254] 981.1 mL of toluene and 184.4 mL of the above-mentioned toluene slurry (solid content = 61.7 g) were charged into a 2000 mL stirred reactor that had been thoroughly purged with nitrogen. Next, 205.5 mL of a 0.006 mol / L toluene solution of the transition metal complex (T-1) was added, and the mixture was contacted at a system temperature of 20-25°C for 1 hour. After removing the supernatant by decantation, the mixture was washed twice with hexane to prepare a total volume of 1390 mL of solid catalyst slurry. The prepared solid catalyst slurry was cooled to 10°C under a nitrogen atmosphere, and 55.6 mL of a 1.0 mol / L diisobutylaluminum hydride hexane solution was added. While maintaining the system temperature at 10-15°C, ethylene was continuously supplied to the system under atmospheric pressure for several minutes, followed by the addition of 0.70 mL of 1-hexene. Then, ethylene supply was started at 30.8 g / h, and prepolymerization was carried out at a system temperature of 32-37°C. 0.70 mL of 1-hexene was added every hour for a total of five times from the start of prepolymerization, and the ethylene supply was stopped when it reached 184.9 g after 6 hours from the start of prepolymerization. The supernatant was then removed by decantation and washed four times with hexane. Further hexane was added to bring the total volume to 893.6 mL, obtaining the prepolymerization catalyst hexane slurry.

[0255] The prepared prepolymerization catalyst hexane slurry was heated to 35°C under a nitrogen atmosphere, and 250.2 mL of a 10 mg / mL hexane solution of Electro Stripper (registered trademark) EA (manufactured by Kao Corporation) was added. The mixture was then contacted at 32-37°C for 2 hours. The mixture was then transferred to a 1000 mL glass filter that had been thoroughly purged with nitrogen, and the pressure was reduced to -68 kPaG over approximately 1 hour. Once -68 kPaG was reached, the mixture was vacuum-dried for approximately 2 hours to obtain the catalyst for polyolefin production (XP-4).

[0256] <Preparation of Catalyst (XP-5) for Polyolefin Production> In a 270 L reactor equipped with a stirrer, 10 kg of solid support (S-3) was suspended in 77 L of toluene under a nitrogen atmosphere, and then cooled to 0-5°C. 20.4 L of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) was added dropwise to this suspension over 30 minutes. During this time, the temperature in the system was maintained at 0-5°C. The reaction continued at 0-5°C for 30 minutes, then the temperature was raised to 95-100°C over approximately 1.5 hours, and the reaction continued at 95-100°C for 4 hours. After cooling to room temperature, the supernatant was removed by decantation, and the mixture was washed twice with toluene to prepare a total volume of 58.0 L of toluene slurry. A sample of the obtained slurry components was taken and its concentration was examined, revealing a slurry concentration of 265.0 g / L and an Al concentration of 1.29 mol / L.

[0257] 234.7 mL of toluene and 250.0 mL of the above-mentioned toluene slurry (solid content = 66.1 g) were charged into a 2000 mL stirred reactor with a sufficient nitrogen purging. Next, 250.0 mL of a 0.010 mol / L toluene solution of the transition metal complex (T-2) was added, and the mixture was contacted at a system temperature of 20-25°C for 1 hour. After removing the supernatant by decantation, the mixture was washed twice with hexane to prepare a total volume of 1494 mL of solid catalyst slurry.

[0258] The prepared solid catalyst slurry was cooled to 10°C under a nitrogen atmosphere, and 125.3 mL of a 1.0 mol / L diisobutylaluminum hydride hexane solution was added. While maintaining the system temperature at 10-15°C, ethylene was continuously supplied to the system under atmospheric pressure for several minutes, followed by the addition of 3.0 mL of 1-hexene. Then, ethylene supply was started at 31.6 g / h, and prepolymerization was carried out at a system temperature of 32-37°C. 3.0 mL of 1-hexene was added every hour for a total of five times from the start of prepolymerization, and the ethylene supply was stopped when it reached 189.5 g after 6 hours from the start of prepolymerization. The supernatant was then removed by decantation and washed four times with hexane. Further hexane was added to bring the total volume to 1270 mL, obtaining the prepolymerization catalyst hexane slurry.

[0259] The prepared prepolymerization catalyst hexane slurry was heated to 35°C under a nitrogen atmosphere, and 268.8 mL of a 10 mg / mL hexane solution of Electro Stripper (registered trademark) EA (manufactured by Kao Corporation) was added. The mixture was then contacted at 32-37°C for 2 hours. Next, it was transferred to a 1000 mL glass filter that had been thoroughly purged with nitrogen, and the pressure was reduced to -68 kPaG over approximately 1 hour. Once -68 kPaG was reached, it was vacuum-dried for approximately 2 hours to obtain the catalyst for polyolefin production (XP-5).

[0260] <Preparation of Catalyst (XP-6) for Polyolefin Production> In a 1000 mL reactor with a stirrer, 54.9 g of solid support (S-1) was suspended in 350 mL of toluene under a nitrogen atmosphere, and then cooled to 0-5°C. To this suspension, 27.4 mL of a 1.0 mol / L diisobutylaluminum hydride toluene solution was added dropwise over 30 minutes, while maintaining the system temperature at 0-5°C. After continuing contact at 0-5°C for 30 minutes, 149.6 mL of a methylaluminoxane toluene solution (3.0 mmol / mL in terms of Al atoms) was added dropwise over 30 minutes, while maintaining the system temperature at 0-5°C. After continuing contact at 0-5°C for 30 minutes, the system temperature was raised to 95°C over approximately 1.5 hours, and then continued contact at 95°C 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 total volume of 300 mL of toluene slurry. A sample of the obtained slurry was taken and its concentration was examined. The slurry concentration was 268.0 g / L and the Al concentration was 1.49 mol / L.

[0261] 245.9 mL of toluene and 270.0 mL of the above-mentioned toluene slurry (solid content = 72.4 g) were charged into a 2000 mL stirred reactor that had been thoroughly purged with nitrogen. Next, 312.7 mL of a 0.010 mol / L toluene solution of the transition metal complex (T-2) was added, and the mixture was contacted at a system temperature of 20-25°C for 1 hour. After removing the supernatant by decantation, the mixture was washed twice with hexane to prepare a total volume of 1638 mL of solid catalyst slurry.

[0262] The prepared solid catalyst slurry was cooled to 10°C under a nitrogen atmosphere, and 137.6 mL of a 1.0 mol / L diisobutylaluminum hydride hexane solution was added. While maintaining the system temperature at 10-15°C, ethylene was continuously supplied to the system under atmospheric pressure for several minutes, followed by the addition of 3.3 mL of 1-hexene. Then, ethylene supply was started at 34.6 g / h, and prepolymerization was carried out at a system temperature of 32-37°C. 3.3 mL of 1-hexene was added every hour for a total of five times from the start of prepolymerization, and the ethylene supply was stopped when it reached 207.9 g after 6 hours from the start of prepolymerization. The supernatant was then removed by decantation and washed four times with hexane. Further hexane was added to bring the total volume to 1053 mL, obtaining the prepolymerization catalyst hexane slurry.

[0263] The prepared prepolymerization catalyst hexane slurry was heated to 35°C under a nitrogen atmosphere, and 294.9 mL of a 10 mg / mL hexane solution of Electro Stripper (registered trademark) EA (manufactured by Kao Corporation) was added. The mixture was then contacted at 32-37°C for 2 hours. Next, it was transferred to a 1000 mL glass filter that had been thoroughly purged with nitrogen, and the pressure was reduced to -68 kPaG over approximately 1 hour. Once -68 kPaG was reached, it was vacuum-dried for approximately 2 hours to obtain the catalyst for polyolefin production (XP-6).

[0264] <Production of ethylene-α-olefin copolymer> [Example 1] Ethylene-α-olefin copolymer was produced by a gas-phase polymerization process using a fluidized bed gas-phase polymerization reactor. 24 kg of spherical ethylene polymer particles with an average particle size of 900 μm were introduced into the reactor, and nitrogen was supplied to form a fluidized bed. Ethylene, hydrogen, 1-hexene, a catalyst for polyolefin production (XP-1), and Electro Stripper® EA (manufactured by Kao Corporation) were then continuously supplied under the polymerization conditions shown in Table 8 to maintain a steady state. The polymerization reaction product was continuously withdrawn from the reactor and dried in a drying apparatus to obtain ethylene-α-olefin copolymer powder. To the obtained ethylene-α-olefin copolymer powder, 850 ppm of Sumirizer GP (manufactured by Sumitomo Chemical Co., Ltd.) and 210 ppm of calcium stearate (manufactured by Nitto Chemical Industries, Ltd.) were added as heat-resistant stabilizers. Using a twin-screw co-direction 46 mmφ extruder manufactured by Ikegai Co., Ltd., the mixture was melt-kneaded under conditions of a set temperature of 200°C and a screw rotation speed of 300 rpm, then extruded into strands and cut to obtain pellets. The obtained pellets were used as measurement samples for physical property measurements and FE count measurement. The measurement results are shown in Table 9. Furthermore, the inflation molding evaluation described above was performed using the obtained pellets. The results are shown in Table 10.

[0265] [Examples 2-3, Comparative Examples 2-4] Except for changing the polymerization conditions as shown in Table 8, ethylene-α-olefin copolymer powder was produced in the same manner as in Example 1. The physical properties of the pellets obtained by melt-kneading were evaluated, the number of FE particles was measured, and inflation molding was evaluated. The results are shown in Tables 9 and 10.

[0266] [Comparative Example 1] An ethylene-α-olefin copolymer powder was obtained in the same manner as in Example 1, except that the polymerization conditions were changed as shown in Table 8. The obtained ethylene-α-olefin copolymer powder was melt-kneaded using a twin-screw, 100 mmφ extruder manufactured by Kobe Steel, Ltd., under conditions of an extrusion rate of 364 kg / h and a screw rotation speed of 351 rpm. The resulting powder was then extruded into strands and cut to obtain pellets. The obtained pellets were subjected to physical property evaluation, measurement of FE count, and inflation molding evaluation in the same manner as in Example 1. The results are shown in Tables 9 and 10.

[0267] [Comparative Examples 5-6] Except for changing the polymerization conditions as shown in Table 8, ethylene-α-olefin copolymer powder was produced in the same manner as in Example 1, and the physical properties of the pellets obtained by melt-kneading were evaluated, and the number of FE particles was measured. Inflation molding was also performed in the same manner as in Example 1, but the bubble stability was poor, and a stable film could not be obtained. The results are shown in Tables 9 and 10.

[0268] [Table 8]

[0269] [Table 9]

[0270] [Table 10]

[0271] As shown in Table 9, the films made of ethylene-α-olefin copolymers of Examples 1 to 3 according to the present invention have a lower number of fisheye (FE) particles and a superior film appearance compared to the films made of ethylene-α-olefin copolymers of Comparative Examples 1 to 4, because the mass fraction of large particle size components of the ethylene-α-olefin copolymer before melt kneading is 10% by mass or less. Furthermore, while the ethylene-α-olefin copolymers of Comparative Examples 5 and 6 failed to satisfy specific physical properties, resulting in poor bubble stability and difficulty in inflation molding, the ethylene-α-olefin copolymer according to the present invention exhibits good bubble stability during inflation molding and superior moldability.

Claims

1. An ethylene-α-olefin copolymer that is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, and satisfies the following requirements (1) to (5). (1) Density is 890 kg / m³ 3 More than 935kg / m 3 It is within the following range. (2) The melt flow rate (MFR) at 190°C with a 2.16 kg load is in the range of 0.1 g / 10 min to 100 g / 10 min. (3) Melt tension at 190°C [MT(g)] and shear viscosity at 200°C and angular velocity 1.0 rad / sec [η * (P)) Ratio to [MT / η * (g / P) is 1.20 × 10 -4 The above 4.00 x 10 -4 It is within the following range. (4) Zero shear viscosity at 200°C [η 0 The weight-average molecular weight (Mw) measured by (P) and the GPC-viscosity detector method (GPC-VISCO) satisfies the following relation (Eq-1). 0.01×10 -13 ×Mw 3.4 ≦η 0 ≦3.5×10 -13 ×Mw 3.4 ・・・(Eq-1) (5) 3000 cm of a 50 μm thick film obtained using a T-die film deposition machine 2 The number of fish eyes (FE: size 100 μm or larger) per sample is 100 or less.

2. Furthermore, the ethylene-α-olefin copolymer according to claim 1 satisfies the following requirement (6). (6) In the powder particle size distribution of the ethylene-α-olefin copolymer before melt mixing, the mass fraction of powder that does not pass through a No. 10 (mesh opening 2 mm) mesh sieve (ASTM E11) relative to 100% by mass of powder is 10% by mass or less.

3. A thermoplastic resin composition comprising the ethylene-α-olefin copolymer and the thermoplastic resin (excluding the ethylene-α-olefin copolymer) according to claim 1 or 2.

4. A molded article comprising the ethylene-α-olefin copolymer according to claim 1 or 2.

5. A film comprising the ethylene-α-olefin copolymer according to claim 1 or 2.

6. A laminate having a layer containing the ethylene-α-olefin copolymer according to claim 1 or 2.

7. A method for producing an ethylene-α-olefin copolymer according to claim 1 or 2, obtained using a catalyst for polyolefin production comprising a transition metal complex (T) represented by the following general formula [1] and a solid support (S). 【Chemistry 1】 (In general formula [1], M is a transition metal atom of group 4 of the periodic table, n is an integer from 1 to 4 selected such that the transition metal complex (T) is electrically neutral. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can coordinate with a lone pair of electrons, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group, and if n is 2 or more, the multiple groups represented by X may be the same or different from each other, and may bond to each other to form a ring. Q is an atom in Group 14 of the periodic table, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. R 1 ~R 6 Adjacent substituents may bond to each other to form a ring which may also have substituents. R 7 ~R 12 Adjacent substituents may bond to each other to form a ring which may also have substituents. R 13 and R 14 These elements may be bonded to each other to form a ring containing Q, and this ring may have substituents.

8. The method for producing an ethylene-α-olefin copolymer according to claim 7, wherein the catalyst for producing polyolefins contains an organoaluminum oxy compound (B-2), and the solid carrier (S) is a porous material.

9. A method for producing an ethylene-α-olefin copolymer according to claim 8, wherein the particle size dispersion ratio (R10) of the solid carrier (S) measured by the following measurement method is greater than 0% and less than or equal to 95%, and the particle size dispersion ratio (R50) of the solid carrier (S) measured by the following measurement method is greater than 0% and less than or equal to 95%. [Measurement method] Using methanol as the dispersion medium, the solid carrier (S) is dispersed in an ultrasonic homogenizer at an output of 25 W for 5 minutes, and the average particle diameter (Dw10) corresponding to 10% of the cumulative mass from the smallest diameter in the particle size distribution and the average particle diameter (Dw50) corresponding to 50% of the cumulative mass from the smallest diameter in the particle size distribution are measured by wet laser diffraction scattering. Similarly, the average particle diameter (Ds10) corresponding to 10% of the cumulative mass from the smallest diameter in the particle size distribution and the average particle diameter (Ds50) corresponding to 50% of the cumulative mass from the smallest diameter in the particle size distribution are measured under the same conditions, except that the dispersion was performed at an output of 40 W for 15 minutes. The particle size dispersion ratios (R10) and (R50) are expressed by the following formulas. R10=Ds10 / Dw10×100 R50=Ds50 / Dsw50×100

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