Ethylene-based resin composition and molded body

Abstract

The present invention provides an ethylene-based resin capable of producing a molded body (particularly a film) having excellent mechanical strength, and excellent balance of transparency and blocking resistance with excellent moldability. The ethylene-based resin composition (Z) of the present invention contains an ethylene-α-olefin copolymer (A) satisfying conditions (1) to (4) and an ethylene-α-olefin copolymer (B) satisfying conditions (a) to (c). (1) Density: 890 to 935 kg / m 3 ; (2) MFR (190°C, 2.16 kg load): 0.1 g / 10 min. or more and less than 3.0 g / 10 min.; (3) MT (melt tension) / η * (shear viscosity): 1.20 x 10 ‑4 ~ 2.90 x 10 ‑ 4 g / P; (4) 0.01 x 10 ‑13 x Mw 3.4 ≤ η0 (zero shear viscosity) ≤ 3.5 x 10 ‑13 x Mw 3.4 ; (a) Density: 890 to 930 kg / m 3 ; (b) MFR (190°C, 2.16 kg load): 0.1 to 10 g / 10 min.; (c) 1.90 x 10 ‑4 x Mw 0.776 ≤ [η] ≤ 2.80 x 10 ‑4 x Mw 0.776 .

Description

TECHNICAL FIELD

[0001] The present application relates to an ethylene-based resin composition and a molded body, a film and a multilayer film containing the same. BACKGROUND

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

[0003] An ethylene-based polymer obtained using a metallocene catalyst having no long chain branch has excellent mechanical strength, but has a problem in moldability. For example, the neck in increases in T-die molding, or the molten film hangs in hollow molding, or the film wrinkles due to the instability of the molten film in blow molding. Although a high-pressure low-density polyethylene has a large melt tension and excellent moldability, the mechanical strength such as tensile strength, tear strength or impact resistance is poor due to the complex long chain branch.

[0004] In order to solve such a problem, various ethylene-based polymers into which a long chain branch is introduced have been developed. Patent Literature 1 proposes a composition of an ethylene-based polymer obtained using a metallocene catalyst and a high-pressure low-density polyethylene. However, in the case where the content of the high-pressure low-density polyethylene is large, it is expected that the mechanical strength such as tensile strength, tear strength or impact resistance is poor, and in the case where the content of the high-pressure low-density polyethylene is small, it is expected that the moldability such as a large neck in due to the insufficient increase in melt tension is poor.

[0005] Further, Patent Document 2 discloses an ethylene-based polymer obtained by solution polymerization in the presence of a catalyst composed of ethylenebis(indenyl)hafnium dichloride and methylaluminoxane; Patent Document 3 discloses an ethylene-based polymer obtained by gas phase polymerization in the presence of a catalyst composed of ethylenebis(indenyl)zirconium dichloride supported on silica and methylaluminoxane; Patent Document 4 discloses an ethylene-based polymer obtained by solution polymerization in the presence of a constrained geometry catalyst; and Patent Document 5 discloses an ethylene-based polymer obtained by gas phase polymerization in the presence of a catalyst composed of racemic and meso isomers of Me2Si(2-Me-Ind)2 supported on silica and methylaluminoxane. It is described that these ethylene-based polymers have improved melt tension and excellent moldability as compared with linear ethylene-based polymers having no long chain branching, but the shrinkage is still large, and therefore it can be expected that they are not sufficient in terms of improvement of moldability, and are also not sufficient in terms of improvement of film blocking resistance. In the case where an ethylene-based polymer is used for a film, an anti-blocking agent is generally added in order to prevent blocking, but in some applications, it is not preferable to add a large amount of an anti-blocking agent from the viewpoint of cost increase and content hygiene. Therefore, a film excellent in blocking resistance even without using an anti-blocking agent is desired.

[0006] Patent Documents 6, 7, 8 and 9 disclose ethylene-based polymers, ethylene-based resin compositions in which the intrinsic viscosity and the weight average molecular weight satisfy a specific relationship, or the melt tension and the shear viscosity satisfy a specific relationship, or the zero shear viscosity and the weight average molecular weight exhibit a specific relationship. The draw resonance of these ethylene-based polymers is improved, and the shrinkage in T-die molding and the blow molding property are improved as compared with existing ethylene-based polymers into which long chain branching is introduced using a metallocene catalyst. However, further improvement of mechanical strength and improvement of transparency are still desired. Although the external haze is high due to slight unevenness on the surface of the film, and thus the blocking resistance is excellent, from the viewpoint of recognition of contents and inspection of defects in the film, a film excellent in the balance between transparency and blocking resistance is still desired. Also, in the case where an ethylene-based polymer is used as a bottle or the like, improvement of transparency is also desired.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 7-26079

[0010] Patent Document 2: Japanese Patent Application Laid-Open (JP-A) No. 2-276807

[0011] Patent Document 3: Japanese Patent Application Laid-Open (JP-A) No. 4-213309

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

[0013] Patent Literature 5: Japanese Patent Application Laid-Open (JP-A) No. 8-311260

[0014] Patent Literature 6: Japanese Patent Application Laid-Open (JP-A) No. 2006-233207

[0015] Patent Literature 7: Japanese Patent Application Laid-Open (JP-A) No. 2009-197225

[0016] Patent Literature 8: International Publication No. 2013 / 099927

[0017] Patent Literature 9: Japanese Patent Application Laid-Open (JP-A) No. 2014-177506 SUMMARY

[0018] PROBLEMS TO BE SOLVED BY THE INVENTION

[0019] In view of such prior art, a first object of the present application is to provide an ethylene resin composition which can produce a molded body (e.g., a film and a multilayer film having the film, hereinafter the same) excellent in mechanical strength with excellent moldability as compared with the ethylene resin known in the art, and a molded body obtained from the ethylene resin composition.

[0020] Further, a second object of the present application is to provide an ethylene resin composition which can produce a molded body excellent in mechanical strength and in the balance between transparency and blocking resistance with excellent moldability as compared with the ethylene resin known in the art, and a molded body obtained from the ethylene resin composition.

[0021] Further, a third object of the present application is to provide an ethylene resin composition which can produce a molded body excellent in mechanical strength with particularly excellent moldability as compared with the ethylene resin known in the art, and a molded body obtained from the ethylene resin composition.

[0022] MEANS FOR SOLVING THE PROBLEMS

[0023] The present inventors have conducted intensive studies, and as a result, have found that a composition containing two kinds of ethylene-based polymers having specific melting properties and molecular structures can solve the first object, i.e., can produce a molded body (e.g., a film and a multilayer film having the film) excellent in mechanical strength with excellent moldability (i.e., the melt film stability at the time of blow molding is excellent, the draw down at the time of T-die molding is small, and draw fluctuation does not occur), thereby completing the present application.

[0024] The application solving the first object, for example, relates to the following [1].

[0025] [1] An ethylene resin composition (Z) containing:

[0026] an ethylene-α-olefin copolymer (A) which is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, satisfies the following conditions (1) to (4); and

[0027] an ethylene-α-olefin copolymer (B) which is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, satisfies the following conditions (a) to (c).

[0028] (1) the density is in the range of 890 kg / m 3 above 935 kg / m 3 below.

[0029] (2) the melt flow rate (MFR) under a load of 2.16 kg at 190°C is in the range of 0.1 g / 10 minutes or more and less than 3.0 g / 10 minutes.

[0030] (3) the ratio (MT / η * (g / P)) of the melt tension at 190°C (MT (g)) to the shear viscosity at 200°C, angular velocity 1.0 rad / sec (η * (P)) is in the range of 1.20 x 10 -4 or more and 2.90 x 10 -4 or less.

[0031] (4) the zero shear viscosity at 200°C (η0 (P)) and the weight average molecular weight (Mw) measured by the GPC-Viscosity Detector method (GPC-VISCO) satisfy the following relational expression (Eq-1).

[0032] 0.01 x 10 -13 x Mw 3.4 ≤ η0 ≤ 3.5 x 10 -13 x Mw 3.4 (Eq-1)

[0033] (a) the density is in the range of 890 kg / m 3 above 930 kg / m 3 below.

[0034] (b) the melt flow rate (MFR) under a load of 2.16 kg at 190°C is in the range of 0.1 g / 10 minutes or more and 10 g / 10 minutes or less.

[0035] (c) the intrinsic viscosity ([η]) (dl / g) measured in decahydronaphthalene at 135°C and the weight average molecular weight (Mw) measured by the GPC-Viscosity Detector method (GPC-VISCO) satisfy the following relational expression (Eq-4).

[0036] 1.90 x 10 -4 x Mw 0.776≤ [η] ≤ 2.80 x 10 -4 x Mw 0.776 (Eq-4)

[0037] Further, the inventors of the present application found that the composition containing the above two kinds of ethylene-based polymers in a specific ratio in the ethylene-based resin composition (Z) of the above [1] can solve the second problem, that is, can produce a molded body having excellent mechanical strength and an excellent balance of transparency and blocking resistance with excellent moldability. The present application solving the second problem, for example, relates to the following [2].

[0038] [2] The ethylene-based resin composition (Z) according to the above [1], wherein the mass fraction (W A ) of the ethylene-a-olefin copolymer (A) is 1 mass% or more and 50 mass% or less, the mass fraction (W B ) of the ethylene-a-olefin copolymer (B) is 50 mass% or more and 99 mass% or less (wherein the total of W A and W B is 100 mass%).

[0039] Further, the inventors of the present application found that the composition containing the above two kinds of ethylene-based polymers in a specific ratio in the ethylene-based resin composition (Z) of the above [1] can solve the third problem, that is, can produce a molded body having excellent mechanical strength with particularly excellent moldability. The present application solving the third problem, for example, relates to the following [3].

[0040] [3] The ethylene-based resin composition (Z) according to the above [1], wherein the mass fraction (W A ) of the ethylene-a-olefin copolymer (A) exceeds 50 mass% and is 99 mass% or less, the mass fraction (W B ) of the ethylene-a-olefin copolymer (B) is 1 mass% or more and less than 50 mass% (wherein the total of W A and W B is 100 mass%).

[0041] The present application, for example, also relates to the following [4] to

[12] .

[0042] [4] The ethylene-based resin composition (Z) according to any one of the above [1] to [3], wherein the ethylene-a-olefin copolymer (A) satisfies the following condition (5).

[0043] (5) The number average molecular weight (Mn), the weight average molecular weight (Mw), and the Z average molecular weight (Mz) measured by the GPC-Viscosity Detector method (GPC-VISCO) satisfy the following relational expression (Eq-2).

[0044] - 7.0 < Mz / Mw - Mw / Mn < 2.0... (Eq-2)

[0045] [5] The ethylene-based resin composition (Z) according to any one of the above [1] to [4], wherein the ethylene-α-olefin copolymer (A) further satisfies the following condition (6).

[0046] (6) The ratio Mz / Mw of the Z-average molecular weight (Mz) to the weight average molecular weight (Mw) measured by the GPC-Viscosity Detector method (GPC-VISCO) is in the range of 4.0 or more and 15.0 or less.

[0047] [6] The ethylene-based resin composition (Z) according to any one of the above [1] to [5], wherein the ethylene-α-olefin copolymer (A) further satisfies the following condition (7).

[0048] (7) The intrinsic viscosity [[η] (dl / g)] measured in decahydronaphthalene at 135°C and the weight average molecular weight (Mw) measured by the GPC-Viscosity Detector method (GPC-VISCO) satisfy the following relational expression (Eq-3).

[0049] 0.7 x 10 -4 ≤ Mw 0.776 ≤ [η] ≤ 1.65 x 10 -4 × Mw 0.776 ... (Eq-3)

[0050] [7] The ethylene-based resin composition (Z) according to any one of the above [1] to [6], wherein the ethylene-α-olefin copolymer (A) satisfies the following condition (8).

[0051] (8) The total (number / 1000C) of the vinyl group, the vinylidene group, the 2-substituted internal olefin, and the 3-substituted internal olefin per 1000 carbon atoms measured by 1 H-NMR is in the range of 0.1 or more and 1.0 or less.

[0052] [8] The ethylene-based resin composition (Z) according to any one of the above [1] to [7], wherein the ethylene-α-olefin copolymer (A) satisfies the following condition (9).

[0053] (9) The melting curve obtained by the Differential Scanning Calorimetry (DSC) has multiple peaks.

[0054] [9] The ethylene-based resin composition (Z) according to any one of the above [1] to [8], which further contains a thermoplastic resin (but excluding the ethylene-α-olefin copolymer (A) and the ethylene-α-olefin copolymer (B)).

[0055]

[10] A molded body containing the ethylene-based resin composition (Z) described in any one of the above [1] to [9].

[0056]

[11] A film containing the ethylene-based resin composition (Z) described in any one of the above [1] to [9].

[0057]

[12] A multilayer film comprising a layer formed of the ethylene-based resin composition (Z) described in any one of the above [1] to [9].

[0058] Effects of the Invention

[0059] With the ethylene-based resin composition (Z) according to the present invention, a molded body (particularly, a film) having excellent mechanical strength can be suitably produced with excellent moldability.

[0060] Further, with the ethylene-based resin composition (Z) according to the above [2] of the present invention, a molded body (particularly, a film) having excellent mechanical strength and having an excellent balance between transparency and blocking resistance can be suitably produced with excellent moldability.

[0061] Further, with the ethylene-based resin composition (Z) according to the above [3] of the present invention, a molded body (particularly, a film) having excellent mechanical strength can be suitably produced with particularly excellent moldability. DETAILED DESCRIPTION

[0062] The ethylene-based resin composition (Z) according to the present invention, and the ethylene-α-olefin copolymer (A) and the ethylene-α-olefin copolymer (B) as its constituent components will be described in detail below.

[0063] 〔Ethylene-based resin composition (Z)〕

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

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

[0066] The ethylene-α-olefin copolymer (A) has the following characteristics (1) to (4).

[0067] (1) The density is 890 kg / m 3 935 kg / m 3 Preferably, 900 kg / m 3 925 kg / m 3 More preferably, 905 kg / m3 The above 922 kg / m 3 The following ranges.

[0068] When the density is above the lower limit, the stickiness of the surface of the film obtained by molding the ethylene-based resin composition (Z) is less; when the density is below the upper limit, the impact strength of the film obtained by molding the ethylene-based resin composition (Z) is good, and the mechanical strength such as heat-seal strength, bag breaking strength of a bag formed from the film is good.

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

[0070] The density was measured as described below.

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

[0072] (2) The melt flow rate (MFR) is in the range of 0.1 g / 10 minutes or more and less than 3.0 g / 10 minutes, preferably 0.3 g / 10 minutes or more and 2.5 g / 10 minutes or less, more preferably 0.5 g / 10 minutes or more and 2.0 g / 10 minutes or less.

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

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

[0075] (3) The ratio of the melt tension (MT (g)) to the shear viscosity (η * (P) (P is Poise) at 200°C and an angular velocity of 1.0 rad / sec (MT / η * (g / P)) is in the range of 1.20 x 10 -4 ~ 2.90 x 10 -4 , preferably 1.30 x 10 -4 ~ 2.70 x 10 -4 , more preferably 1.30 x 10 -4 ~ 2.45 x 10 -4 .

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

[0077] MT / η * Depending on the long-chain branch content of the ethylene-based polymer, the more the long-chain branch content, the larger the MT / η * , and the less the long-chain branch content, the smaller the MT / η * . The long-chain branch is defined as a branch structure of a length of the molecular weight (Me) or more between entanglement points contained in the ethylene-based polymer, and it is known that by introducing the long-chain branch, the melt properties and the mold processability of the ethylene-based polymer are significantly changed (for example, Matsuura and Samukawa, eds., "Polyethylene Technology Reader," Industrial Investigation Association, 2001, p. 32, 36).

[0078] MT / η * ​The composition (A) of the catalyst (X) for olefin polymerization, as described later, or the type of solid support (S) can be adjusted. Furthermore, even when using the same catalyst (X) for olefin polymerization, adjustments can be made through polymerization conditions or processes; for example, by increasing the partial pressure of ethylene, the MT / η ratio can be adjusted. * The decrease. Based on the manufacturing conditions of Manufacturing Example 3 described later, it is possible to obtain MT / η near the lower limit. * According to the manufacturing conditions of manufacturing example 5 described later, MT / η near the upper limit can be obtained. * .

[0079] Melt tension (MT(g)) was measured as described below. Melt tension (MT) (unit: g) is determined by measuring the stress when stretched at a certain speed. The measurement was performed using a capillary rheometer (for example, in the embodiments described later, a Capilograph 1D capillary rheometer manufactured by Toyo Seiki Co., Ltd. was used). The conditions were set as follows: resin temperature 190°C, melting time 6 minutes, and tube diameter... Extrusion speed 15 mm / min, winding speed 24 m / min (decrease winding speed by 5 m / min when molten wire breaks), nozzle diameter Nozzle length 8mm.

[0080] Shear viscosity at 200℃ and angular velocity of 1.0 rad / s [η] * (P)] was measured as described below. Regarding shear viscosity (η) * The shear viscosity (η) at a measurement temperature of 200℃ was determined within the range of 0.01 ≤ ω ≤ 100. * The angular velocity distribution [ω (rad / s)] of the viscoelasticity was determined using a viscoelasticity measuring apparatus (e.g., the Anton Paar Physica MCR301 viscoelasticity measuring apparatus used in the embodiments described later). A parallel plate was used as the sample holder, and the sample thickness was set to approximately 2.0 mm. Five measurement points were set for each order of magnitude of ω. The strain was appropriately selected within the range of 3% to 10% to ensure that torque could be detected within the measurement range without becoming excessively large.

[0081] The samples used for shear viscosity determination were prepared as follows: using a molding machine (e.g., a pressure molding machine manufactured by Shinto Metal Industries in the examples described later), at a preheating temperature of 190°C, a preheating time of 5 minutes, a heating temperature of 190°C, a heating time of 2 minutes, and a heating pressure of 100 kgf / cm². 2 Cooling temperature 20℃, cooling time 5 minutes, cooling pressure 100 kgf / cm² 2 Under these conditions, the sample was pressurized and molded to a thickness of 2 mm.

[0082] (4) the zero shear viscosity at 2000C (η0(P)) and the weight average molecular weight (Mw) measured by the GPC-VISCO method satisfy the following relationship (Eq-1).

[0083] 0.01 x 10 -13 < Mw 3.4 ≤ η0≤ 3.5 x 10 -13 < Mw 3.4 (Eq-1)

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

[0085] 0.05 x 10 -13 < Mw 3.4 ≤ η0≤ 3.0 x 10 -13 < Mw 3.4 (Eq-1')

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

[0087] 0.1 x 10 -13 < Mw 3.4 ≤ η0≤ 2.5 x 10 -13 < Mw 3.4 (Eq-1")

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

[0089] When the zero shear viscosity at 2000C (η0(P)) is below the upper limit, the elongational viscosity of the ethylene-based polymer shows strain rate hardening, and thus drawing fluctuation does not occur. Also, the long chain branching is short, and the number of molecules connecting the crystalline layers with each other is large at the same molecular weight, and thus the mechanical strength (impact resistance) of the ethylene-based resin composition (Z) is excellent.

[0090] In addition, when the molten resin flows into the mold, extensional stress occurs due to extensional flow. Once the extensional stress exceeds a critical value, brittle fracture occurs, and unstable flow at the mold exit called melt fracture occurs, and minute unevenness is formed on the surface of the molded body (F. N. Cogswell, Polymer Melt Rheology, Wiley, 1981). When the zero shear viscosity [η0(P)] is within the above range, the extensional stress increases at the strain rate in ordinary molding processing, and melt fracture occurs moderately. The minute unevenness is formed moderately on the surface of the film due to the melt fracture, and thus the balance between the transparency and the blocking resistance of the film obtained from the ethylene-based resin composition (Z) is excellent.

[0091] It can be considered that the relationship between the zero shear viscosity [η0(P)] and the weight average molecular weight (Mw) depends on the content and the length of the long chain branch in the ethylene-based polymer, and it can be considered that the more the content of the long chain branch and the shorter the length of the long chain branch, the smaller value the zero shear viscosity [η0(P)] shows; the less the content of the long chain branch and the longer the length of the long chain branch, the larger value the zero shear viscosity [η0(P)] shows.

[0092] The zero shear viscosity [η0(P)] can be adjusted by the kind of the component (A) or the solid carrier (S) of the catalyst (X) for olefin polymerization described later. In addition, even in the case of using the same catalyst (X) for olefin polymerization, it can be adjusted by the polymerization conditions or the polymerization process, and for example, by increasing the ethylene partial pressure, the zero shear viscosity [η0(P)] can be increased. According to the manufacturing conditions of the manufacturing example 9 described later, the zero shear viscosity [η0(P)] near the lower limit can be obtained; according to the manufacturing conditions of the manufacturing example 6 described later, the zero shear viscosity [η0(P)] near the upper limit can be obtained.

[0093] The zero shear viscosity [η0(P)] at 200°C is measured as described below.

[0094] The angular velocity ω (rad / sec) distribution of the shear viscosity (η * ) is measured at 200°C as the measurement temperature, in the range of 0.01 ≤ ω ≤ 100. The measurement uses a viscoelasticity measuring device (for example, the viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used in the examples described later). A parallel plate of was used as a sample holder, and the sample thickness was set to about 2.0 mm. Five points were set for each order of magnitude of ω as the measurement point. The strain amount was appropriately selected in the range of 3 to 10% so that the torque could be detected in the measurement range, and the torque did not become too large.

[0095] The sample used for the shear viscosity measurement was prepared as follows: using a molding machine (for example, a press molding machine manufactured by JISICO, used in the examples described later), the sample was press-molded into a thickness of 2 mm under the conditions of a preheating temperature of 190°C, a preheating time of 5 minutes, a heating temperature of 190°C, a heating time of 2 minutes, a heating pressure of 100 kgf / cm 2 , a cooling temperature of 20°C, a cooling time of 5 minutes, and a cooling pressure of 100 kgf / cm 2 .

[0096] The zero shear viscosity (η0) was calculated by fitting the Carreau model of the following equation to the measured rheological curve (distribution of shear viscosity (η * ) versus angular velocity (ω)) using a non-linear least squares method.

[0097] η * = η0[1 + (λω) a ] (n-1) / a

[0098] (λ represents a parameter having a time dimension, a represents a fitting parameter, and n represents the power law index of the material.)

[0099] Here, the fitting of d in the following equation was performed in such a manner that d becomes the minimum using a non-linear least squares method.

[0100]

[0101] (ηexp(ω) represents the measured shear viscosity, and ηcalc(ω) represents the shear viscosity calculated by the Carreau model.)

[0102] The weight average molecular weight (Mw) and the like were measured using gel permeation chromatography (GPC) as follows.

[0103] The detector used a differential refractometer and a capillary viscometer, the column temperature was set to 145°C, o-dichlorobenzene was used as the mobile phase, the flow rate was set to 1.0 ml / min, the sample concentration was set to 0.1% by weight, and polystyrene was used as the standard polymer. In the examples described later, the GPC-Visco detector (GPC-VISCO) PL-GPC220 manufactured by Agilent was used as the measuring device, two Agilent PLgel Olexis were used as the analysis column, and the product manufactured by Tosoh Corporation was used as the standard polystyrene. Regarding the molecular weight calculation, the measured viscosity was calculated from the viscometer and the refractometer, and the number average molecular weight (Mn), the weight average molecular weight (Mw), the Z average molecular weight (Mz), and the molecular weight distribution (Mw / Mn, Mz / Mw) were calculated using the measured universal calibration.

[0104] The ethylene-α-olefin copolymer (A) preferably has the following characteristics shown in (5).

[0105] (5) The number average molecular weight (Mn), the weight average molecular weight (Mw), and the Z average molecular weight (Mz) measured by the GPC-Viscosity Detector method (GPC-VISCO) satisfy the following relational expression (Eq-2).

[0106] -7.0 ≤ Mz / Mw - Mw / Mn ≤ 2.0... (Eq-2)

[0107] The following relational expression (Eq-2') is preferably satisfied.

[0108] -6.0 ≤ Mz / Mw - Mw / Mn ≤ 1.0... (Eq-2')

[0109] The following relational expression (Eq-2") is more preferably satisfied.

[0110] -5.0 ≤ Mz / Mw - Mw / Mn ≤ 0.0... (Eq-2")

[0111] When Mz / Mw - Mw / Mn is large, the molecular weight distribution extends to the high molecular weight side, and when Mz / Mw - Mw / Mn is above the lower limit, the melt film stability of the ethylene-based resin composition (Z) is excellent, and when Mz / Mw - Mw / Mn is below the upper limit, the film formability of the ethylene-based resin composition (Z) is excellent.

[0112] Mz / Mw - Mw / Mn can be adjusted by the kind of the component (A) or the solid carrier (S) of the catalyst (X) for olefin polymerization described later, and even when the same catalyst (X) for olefin polymerization is used, it can be adjusted by the polymerization conditions or the polymerization process. The Mz / Mw - Mw / Mn near the lower limit can be obtained according to the production conditions of Production Example 9 described later, and the Mz / Mw - Mw / Mn near the upper limit can be obtained according to the polymerization conditions of Production Example 10 described later.

[0113] The number average molecular weight (Mn), the weight average molecular weight (Mw), and the Z average molecular weight (Mz) are measured according to the above method.

[0114] The ethylene-α-olefin copolymer (A) preferably has the following characteristics shown in (6).

[0115] (6) The ratio (Mz / Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw) measured by the GPC-Viscosity Detector method (GPC-VISCO) is in the range of 4.0 to 15.0, preferably 5.0 to 12.0, more preferably 6.0 to 10.0. The larger Mz / Mw is, the more the high molecular weight component is, and when Mz / Mw is above the lower limit, the blocking resistance is excellent, and when Mz / Mw is below the upper limit, the transparency is excellent.

[0116] Mz / Mw can be adjusted by the kind of the component (A) or the solid carrier (S) of the olefin polymerization catalyst (X) described later, and even in the case of using the same olefin polymerization catalyst (X), it can be adjusted by the polymerization conditions or polymerization process. According to the manufacturing conditions of Manufacturing Example 3 described later, Mz / Mw near the lower limit can be obtained; according to the polymerization conditions of Manufacturing Example 10 described later, Mz / Mw near the upper limit can be obtained.

[0117] The ethylene-a-olefin copolymer (A) preferably has the property shown in the following (7).

[0118] (7) The intrinsic viscosity [[η] (dl / g)] measured in decalin at 135°C and the weight average molecular weight (Mw) measured by the GPC-Viscosity Detector method (GPC-VISCO) satisfy the following relational expression (Eq-3).

[0119] 0.7 x 10 -4 x Mw 0.776 ≤ [η] ≤ 1.65 x 10 -4 x Mw 0.776 (Eq-3)

[0120] It is preferable to satisfy the following (Eq-3').

[0121] 0.7 x 10 -4 x Mw 0.776 ≤ [η] ≤ 1.40 x 10 -4 x Mw 0.776 (Eq-3')

[0122] It is more preferable to satisfy the following (Eq-3").

[0123] 0.8 x 10 -4 x Mw 0.776 ≤ [η] ≤ 1.20 x 10 -4 x Mw 0.776 (Eq-3")

[0124] It is known that when long-chain branches are introduced in an ethylene polymer, the intrinsic viscosity [[η] (dl / g)] decreases with respect to the molecular weight compared to a linear ethylene polymer without long-chain branches (for example, Walther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched Polymer II, p. 137 (1999)). Therefore, in the case where the intrinsic viscosity [[η] (dl / g)] is 1.65 x 10 -4 x Mw 0.776 The ethylene polymer has a plurality of long-chain branches, and the moldability and flowability are excellent.

[0125] The intrinsic viscosity [[η] (dl / g)] can be adjusted by the kind of the component (A) or the solid carrier (S) of the olefin polymerization catalyst (X) described later. Also, even in the case of using the same olefin polymerization catalyst (X), it can be adjusted by the polymerization conditions or polymerization process, for example, by increasing the ethylene partial pressure, the intrinsic viscosity [[η] (dl / g)] can be increased. In the production conditions of Production Example 9 described later, the intrinsic viscosity [[η] (dl / g)] near the lower limit can be obtained; according to the production conditions of Production Example 2 described later, the intrinsic viscosity [[η] (dl / g)] near the upper limit can be obtained.

[0126] The intrinsic viscosity [[η] (dl / g)] is measured as described below using decalin solvent. About 20 mg of the sample is dissolved in 15 ml of decalin, and the relative viscosity ηsp is measured in an oil bath at 135°C. After dilution by adding 5 ml of decalin solvent to this decalin solution, the relative viscosity ηsp is measured by the same procedure. This dilution procedure is repeated twice more, and the value of ηsp / C at the time when the concentration (C) is extrapolated to 0 is calculated as the intrinsic viscosity [η] (unit: dl / g) as shown in the following equation.

[0127] [η] = lim (ηsp / C) (C→0)

[0128] The weight average molecular weight (Mw) is measured by the above method.

[0129] The ethylene-α-olefin copolymer (A) preferably has the following characteristics (8).

[0130] (8) By 1 The number of vinyl groups, vinylidene groups, 2-substituted internal olefins, and 3-substituted internal olefins measured by H-NMR satisfies the following relational expression (Eq-3).

[0131] 0.1 ≤ vinyl + vinylidene + 2-substituted internal olefin + 3-substituted internal olefin ≤ 1.0 (Eq-3)

[0132] The following relational expression (Eq-3') is preferably satisfied.

[0133] 0.3 ≤ vinyl + vinylidene + 2-substituted internal olefin + 3-substituted internal olefin ≤ 0.9 (Eq-3')

[0134] The following relational expression (Eq-3") is more preferably satisfied.

[0135] 0.5 ≤ vinyl + vinylidene + 2-substituted internal olefin + 3-substituted internal olefin ≤ 0.8 (Eq-3")

[0136] The number of vinyl groups, vinylidene groups, 2-substituted internal olefins, and 3-substituted internal olefins in the polymer is measured by1 The number per 1000 carbon atoms contained in the polymer measured by H-NMR method. The generation amount ratio and the number of vinyl group, vinylidene group, 2-substituted internal olefin, 3-substituted internal olefin are known to increase or decrease depending on the transition metal compound used (H. SAIKI, S. MAKOTO, T. MASAO, S. MORIHIKO, Y. AKIHIRO, J. Polym. Sci., A: Polym. Chem., 38, 4641 (2000)). They can be adjusted by the kind of component (A) or solid support (S) of the olefin polymerization catalyst (X) described later. Also, even in the case of using the same olefin polymerization catalyst (X), it can be adjusted by the polymerization conditions or polymerization process, for example, by increasing or decreasing the ethylene partial pressure, and it can be increased or decreased.

[0137] When the number of vinyl group + vinylidene group + 2-substituted internal olefin + 3-substituted internal olefin is above the lower limit, long chain branching is easily generated, and the moldability is excellent; when the number of vinyl group + vinylidene group + 2-substituted internal olefin + 3-substituted internal olefin is below the upper limit, the melt film of the extrusion laminate is not easily oxidized, the heat sealability is excellent, and the transparency and mechanical strength of the molded body are excellent.

[0138] By 1 The number of vinyl group, vinylidene group, 2-substituted internal olefin, 3-substituted internal olefin measured by H-NMR (500 MHz) is determined as follows using a nuclear magnetic resonance device (for example, the AVANCE III (ultra-low temperature probe) type nuclear magnetic resonance device manufactured by Bruker used in the examples described later).

[0139] The measurement mode is set to single pulse, the pulse width is 45°. The number of points is set to 32k, the observation range is set to 20 ppm (-6 to 14 ppm), the repetition time is set to 7 seconds, and the number of accumulations is set to 64 times. After dissolving 20 mg of the sample in ortho-dichlorobenzene-d 40.6 ml, it is measured at 120°C.

[0140] In 1 In the H-NMR spectrum, the relative values of the number of double bonds calculated from the signal integral values from various double bonds (vinyl group, vinylidene group, internal olefin) and the total number of carbon atoms calculated from the total integral value of H signals in 4.5 ppm to 5.8 ppm are calculated, and the number of various double bonds per 1000 carbons in the polymer is calculated. 1 The number of various double bonds per 1000 carbons in the polymer is calculated.

[0141] The ethylene-α-olefin copolymer (A) preferably has the characteristics shown in (9) below.

[0142] (9) The melting curve obtained by differential scanning calorimetry (DSC) has multiple peaks.

[0143] In the case of having a plurality of peaks, the low-melting component is more, and heat sealability at low temperature is excellent.

[0144] Regarding differential scanning calorimetry (DSC), a differential scanning calorimeter (for example, Diamond DSC manufactured by PerkinElmer, Inc. was used in the examples described later) was used and measurement was performed as described below.

[0145] About 5 mg of a sample was charged into an aluminum pan, and temperature was increased to 200°C at a rate of 10°C / min, and after keeping at 200°C for 10 minutes, temperature was decreased to -30°C at a rate of 10°C / min, and then temperature was increased to 200°C at a rate of 10°C / min to obtain an endothermic curve at that time. The endothermic curve having two or more peaks means that the melting curve obtained by differential scanning calorimetry (DSC) has a plurality of peaks.

[0146] 〔Ethylene-α-olefin copolymer (B)〕

[0147] The ethylene-α-olefin copolymer (B) is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 6 to 10 carbon atoms. As the α-olefin having 4 to 10 carbon atoms to be copolymerized with ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and the like can be exemplified.

[0148] The ethylene-α-olefin copolymer (B) has the following properties (a) to (c).

[0149] (a) The density is 890 kg / m 3 930 kg / m 3 Preferably, 900 kg / m 3 925 kg / m 3 More preferably, 905 kg / m 3 920 kg / m 3 in the following range.

[0150] When the density is equal to or higher than the lower limit, the film surface formed from the ethylene-based resin composition (Z) has less tackiness; when the density is equal to or lower than the upper limit, the film formed from the ethylene-based resin composition (Z) has good impact strength, and good mechanical strength such as heat seal strength, bag breaking strength of a bag formed from the film.

[0151] (b) The melt flow rate (MFR) is in the range of 0.1 g / 10 minutes or more and 10 g / 10 minutes or less, preferably 0.5 g / 10 minutes or more and 5.0 g / 10 minutes or less, more preferably 0.8 g / 10 minutes or more and 3.0 g / 10 minutes or less.

[0152] When the melt flow rate (MFR) is above the lower limit, the film formed from the vinyl resin composition (Z) has fewer fisheyes and a better appearance. When the melt flow rate (MFR) is below the upper limit, the vinyl resin composition (Z) has high melt tension and good moldability, such as melt film stability.

[0153] (c) The intrinsic viscosity [η] (dl / g) measured in decahydronaphthalene at 135 °C and the weight-average molecular weight (Mw) measured by GPC-Viscosity Detector (GPC-VISCO) satisfy the following relationship (Eq-4).

[0154] 1.90×10 -4 ×Mw 0.776 ≤[η]≤2.80×10 -4 ×Mw 0.776 …(Eq-4)

[0155] Preferably, the following relation (Eq-4') is satisfied.

[0156] 2.20×10 -4 ×Mw 0.776 ≤[η]≤2.60×10 -4 ×Mw 0.776 …(Eq-4')

[0157] As described above, it is known that when there are no long branches in ethylene-based polymers, the intrinsic viscosity [[η](dl / g)] increases relative to molecular weight compared to ethylene-based polymers with long branches. Therefore, the ethylene-α-olefin copolymer (B) with [[η](dl / g)] above the lower limit is a linear ethylene-α-olefin copolymer that is substantially free of long branches. The ethylene-based resin composition (Z) of the present invention containing such an ethylene-α-olefin copolymer has high melt tension and excellent foam stability.

[0158] 〈Ethylene-based resin composition (Z)〉

[0159] The ethylene-based resin composition (Z) of the present invention contains the above-mentioned ethylene-α-olefin copolymer (A) and the above-mentioned ethylene-α-olefin copolymer (B).

[0160] The mass fraction (W) of the above ethylene-α-olefin copolymer (A) A The mass fraction (W) of the above-mentioned ethylene-α-olefin copolymer (B) and B The total is set at 100% by mass, in W A 1–50% by mass, W B At a concentration of 50–99% by mass, the vinyl resin composition (Z) exhibits excellent moldability and mechanical strength, and the film formed from the vinyl resin composition (Z) shows a particularly excellent balance between transparency and anti-blocking properties.

[0161] In W A more than 50 mass% and 99 mass% or less, W B In the case where it is 1 mass% or more and less than 50 mass%, the ethylene-based resin composition (Z) is excellent in moldability and mechanical strength, and in particular, can be molded at a lower resin pressure (or at a higher melt tension).

[0162] W A It is preferably 5 to 40 mass%, and more preferably 10 to 30 mass%. In this range, the ethylene-based resin composition (Z) is excellent in moldability and mechanical strength, and the balance between transparency and blocking resistance of a film molded from the ethylene-based resin composition (Z) is excellent.

[0163] In addition, the ethylene-based resin composition (Z) according to the present application can be composed of substantially only the above-described ethylene-a-olefin copolymer (A) and the above-described ethylene-a-olefin copolymer (B), but is not limited thereto, and can contain a thermoplastic resin other than the above-described ethylene-a-olefin copolymer (A) and the above-described ethylene-a-olefin copolymer (B) (hereinafter referred to as "other thermoplastic resin"). By blending the "other thermoplastic resin" to the above-described ethylene-a-olefin copolymer (A) and the above-described ethylene-a-olefin copolymer (B), the ethylene-based resin composition (Z) obtained as a thermoplastic resin composition is excellent in moldability and mechanical strength.

[0164] The blending ratio of the total of the above-described ethylene-a-olefin copolymer (A) and the above-described ethylene-a-olefin copolymer (B) to the "other thermoplastic resin" (total mass of ethylene-a-olefin copolymer (A) and ethylene-a-olefin copolymer (B) / mass of other thermoplastic resin) is usually 99.9 / 0.1 to 0.1 / 99.9, preferably 90 / 10 to 10 / 90, and more preferably 70 / 30 to 30 / 70.

[0165] (Other thermoplastic resins)

[0166] As the other thermoplastic resin, a crystalline thermoplastic resin such as polyolefin, polyamide, polyester, and polyacetal; a non-crystalline thermoplastic resin such as polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate, polyphenylene ether, and polyacrylate can be used. It is also preferable to use polyvinyl chloride.

[0167] As the above polyolefin, specifically, ethylene-based polymers, propylene-based polymers, butene-based polymers, 4-methyl-l-pentene-based polymers, 3-methyl-l-butene-based polymers, hexene-based polymers, and the like can be exemplified. Among them, ethylene-based polymers, propylene-based polymers, and 4-methyl-l-pentene-based polymers are preferred, and in the case of ethylene-based polymers, existing ethylene-based polymers can be used, and ethylene-polar group-containing vinyl copolymers can also be used, and more preferably, existing ethylene-based polymers are used. The ethylene-based polymers and propylene-based polymers can be ethylene-based polymers and propylene polymers, respectively, which contain monomers derived from biomass.

[0168] In the ethylene-based resin composition (Z) of the present application, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifog agent, a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an anti-aging agent, a hydrochloric acid absorber, an antioxidant, and the like can be added as an additive as needed without impairing the object of the present application.

[0169] The total amount of the additive is usually 10 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the total of the components other than the additive in the ethylene-based resin composition (Z).

[0170] 〈Method for producing ethylene-α-olefin copolymer〉

[0171] Next, the method for producing the ethylene-a-olefin copolymer (A) will be described.

[0172] The ethylene-a-olefin copolymer (A) can be efficiently produced by polymerizing ethylene and an a-olefin having 4 to 10 carbon atoms in the presence of an olefin polymerization catalyst (X) containing the following components (A) and a solid carrier (S).

[0173] [Olefin polymerization catalyst (X)]

[0174] The olefin polymerization catalyst (X) contains the following components (A) and a solid carrier (S).

[0175] <Components (A)>

[0176] The component (A) is a transition metal compound represented by the following formula (1) (hereinafter also referred to as "transition metal compound (1)"). The olefin polymerization catalyst (X) contains at least one kind of transition metal compound (1). That is, one kind of transition metal compound (1) can be used as the component (A), and a plurality of kinds of transition metal compounds (1) can also be used.

[0177]

[0178] In the above formula (1), M is a zirconium atom or a hafnium atom, and is preferably a zirconium atom.

[0179] In the above formula (1), n is an integer of 1 to 4 selected in such a manner that the transition metal compound (1) is electrically neutral, and is preferably 2.

[0180] In the above formula (1), X is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a conjugated diene derivative group, and is preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0181] As the above halogen atom, fluorine, chlorine, bromine, and iodine can be exemplified, and chlorine is particularly preferred.

[0182] As the above hydrocarbon group having 1 to 20 carbon atoms, for example, the following can be exemplified:

[0183] methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl (butane-2-yl), tert-butyl (2-methylpropane-2-yl), isobutyl (2-methylpropyl), pentane-2-yl, 2-methylbutyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), diisopentyl (1,2-dimethylpropyl), isohexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, texyl (2,3-dimethylbutane-2-yl), 4,4-dimethylpentyl, and the like, straight-chain or branched-chain alkyl groups;

[0184] vinyl, allyl, propenyl (prop-1-ene-1-yl), isopropenyl (prop-1-ene-2-yl), allenyl (prop-1,2-diene-1-yl), but-3-ene-1-yl, crotyl (but-2-ene-1-yl), but-3-ene-2-yl, methallyl (2-methylallyl), buta-1,3-dienyl, pent-4-ene-1-yl, pent-3-ene-1-yl, pent-2-ene-1-yl, isopentenyl (3-methylbut-3-ene-1-yl), 2-methylbut-3-ene-1-yl, pent-4-ene-2-yl, isoprene (3-methylbut-2-ene-1-yl), and the like, straight-chain or branched-chain alkenyl groups or groups containing unsaturated double bonds;

[0185] ethynyl, prop-2-yn-1-yl, propargyl (prop-1-yn-1-yl), and the like, straight-chain or branched-chain alkynyl groups or groups containing unsaturated triple bonds;

[0186] linear or branched alkyl groups containing aromatic groups such as benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl (4-isopropylbenzyl), 2,4,6-triisopropylbenzyl, 4-tert-butylbenzyl, 3,5-di-tert-butylbenzyl, 1-phenylethyl, benzhydryl (diphenylmethyl), and unsaturated double bond-containing groups;

[0187] cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, 1-adamantyl, 2-adamantyl, and the like;

[0188] cycloheptatrienyl, norbornenyl;

[0189] aromatic substituents such as phenyl, tolyl (methylphenyl), xylyl (dimethylphenyl), mesityl (2,4,6-trimethylphenyl), cuminyl (isopropylphenyl), mesityl (2,3,5,6-tetramethylphenyl), 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, naphthyl, biphenyl, terphenyl, binaphthyl, acenaphthyl, phenanthryl, anthryl, pyrenyl, ferrocenyl, and the like, preferably methyl, isobutyl, neopentyl, diisopentyl (Siamyl), benzyl, phenyl, tolyl, xylyl, mesityl, cuminyl.

[0190] The above hydrocarbon group having 1 to 20 carbon atoms can be a halogenated hydrocarbon group in which part or all of the hydrogen atoms of the above hydrocarbon group having 1 to 20 carbon atoms are substituted with halogen atoms, and as examples thereof, fluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, pentafluorophenylmethyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, trifluoromethylphenyl, bistrifluoromethylphenyl, and the like can be listed, preferably pentafluorophenyl.

[0191] As the above silicon-containing group, for example, trimethylsilyl, triethylsilyl, triisopropylsilyl, diphenylmethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, triphenylsilyl, tris(trimethylsilyl)silyl, trimethylsilylmethyl, and the like can be listed, preferably trimethylsilylmethyl.

[0192] As the above-mentioned oxygen-containing group, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, allyloxy group, n-butoxy group, sec-butoxy group, isobutoxy group, t-butoxy group, benzyloxy group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-di-t- butylphenoxy group, 2,4,6-trimethylphenoxy group, 2,4,6-triisopropylphenoxy group, acetyloxy group, t-amyloyl group, benzoyloxy group, trifluoroacetyloxy group, perchloric acid anion, periodate anion, preferably methoxy group, ethoxy group, isopropoxy group, t-butoxy group can be exemplified.

[0193] As the above-mentioned nitrogen-containing group, for example, amino group, cyano group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, allylamino group, diallylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholinyl group, pyrrolyl group, bistrifurylimide group, and the like can be exemplified.

[0194] As the above-mentioned conjugated diene derivative group, for example, 1,3-butadienyl group, isoprenyl group (2-methyl-l,3-butadienyl group), metaprenyl group (1,3-pentadienyl group), 2,4-hexadienyl group, 1,4-diphenyl-l,3-pentadienyl group, cyclopentadienyl group, and the like can be exemplified, preferably 1,3-butadienyl group, 1,3-pentadienyl group.

[0195] In the above-mentioned formula (1), Q is a carbon atom or a silicon atom, preferably a silicon atom.

[0196] In the above-mentioned formula (1), R 1 ~R 14 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms.

[0197] As the hydrocarbon group having 1 to 20 carbon atoms of R 1 ~R 14 , a linear or branched alkyl group such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, isopropyl group, sec-butyl group (butane-2-yl group), t-butyl group (2-methylpropane-2-yl group), isobutyl group (2-methylpropyl group), pentane-2-yl group, 2-methylbutyl group, isopentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), diisopentyl group (1,2-dimethylpropyl group), isohexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, Thexyl group (2,3-dimethylbutane-2-yl group), 4,4-dimethylpentyl group, and the like can be exemplified.

[0198] linear or branched alkenyl group or unsaturated double bond-containing group such as vinyl, allyl, propenyl (prop-1-en-1-yl), isopropenyl (prop-1-en-2-yl), propadienyl (prop-1,2-dien-1-yl), but-3-en-1-yl, crotyl (but-2-en-1-yl), but-3-en-2-yl, methallyl (2-methylallyl), buta-1,3-dienyl, pent-4-en-1-yl, pent-3-en-1-yl, pent-2-en-1-yl, isopentenyl (3-methylbut-3-en-1-yl), 2-methylbut-3-en-1-yl, pent-4-en-2-yl, isoprene (3-methylbut-2-en-1-yl), and the like;

[0199] linear or branched alkynyl group or unsaturated triple bond-containing group such as ethynyl, prop-2-yn-1-yl, propargyl (prop-1-yn-1-yl), and the like;

[0200] aromatic-containing linear or branched alkyl group and unsaturated double bond-containing group such as benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl (4-isopropylbenzyl), 2,4,6-triisopropylbenzyl, 4-tert-butylbenzyl, 3,5-di-tert-butylbenzyl, 1-phenylethyl, benzhydryl (diphenylmethyl), pentafluorophenylmethyl, and the like;

[0201] cyclic saturated hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, 1-adamantyl, 2-adamantyl, and the like;

[0202] cycloheptatrienyl, norbornenyl;

[0203] aromatic substituent such as phenyl, tolyl (methylphenyl), xylyl (dimethylphenyl), mesityl (2,4,6-trimethylphenyl), cumyl (isopropylphenyl), mesityl (2,3,5,6-tetramethylphenyl), 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, naphthyl, biphenyl, terphenyl, binaphthyl, acenaphthyl, phenanthryl, anthryl, pyrenyl, ferrocenyl, and the like;

[0204] halogenated hydrocarbon group in which the above hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen atoms for some or all of the hydrogen atoms, such as fluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluorophenylmethyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, trifluoromethylphenyl, bistrifluoromethylphenyl, and the like,

[0205] Preferably, the following compounds are used: methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, neopentyl, tert-pentyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclooctenyl, norbornyl, bicyclo[2.2.2]octane-1-yl, 1-adamantyl, 2-adamantyl, benzyl, diphenylmethyl , cumyl, 1,1-diphenylethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, cinnamyl, phenyl, tolyl, xylyl, mesitylelel, cumenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 4-adamantylphenyl, naphthyl, biphenyl, terphenyl, binatyl, phenanthryl, anthracene, ferrocene, pentafluorophenyl.

[0206] As R 1 ~R 14 The silicon-containing group having 1 to 20 carbon atoms is preferably trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, triphenylsilyl, cyclopentadienyldimethylsilyl, cyclopentadienyldiphenylsilyl, indenedimethylsilyl, fluorenyldimethylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-triisopropylsilylphenyl, 3,5-bis(trimethylsilyl)phenyl, etc. Examples include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-triisopropylsilylphenyl, and 3,5-bis(trimethylsilyl)phenyl.

[0207] As R 1 ~R 14Oxide groups with 1 to 20 carbon atoms include, for example, methoxy, ethoxy, isopropoxy, allyloxy, n-butoxy, tert-butoxy, pentadienoxy, benzyloxy, phenoxy, naphthoxy, tolyloxy, isopropylphenoxy, allylphenoxy, tert-butylphenoxy, methoxyphenoxy, biphenoxy, binaphthoxy, allyloxymethyl, benzyloxymethyl, phenoxymethyl, methoxyethyl, methoxyallyl, benzyloxyallyl, phenoxyallyl, dimethoxymethyl, dioxopentyl, tetramethyldioxopentyl, dioxohexyl, dimethyldioxohexyl, methoxyphenyl, isopropoxyphenyl, and allyloxy The compounds include methylphenyl, phenoxyphenyl, methylenedioxyphenyl, 3,5-dimethyl-4-methoxyphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, furanyl, methylfuranyl, tetrahydropyranyl, furfuryl, benzofuranyl, dibenzofuranyl, etc., preferably methoxy, isopropoxy, tert-butoxy, allyloxy, phenoxy, dimethoxymethyl, dioxolanecycloyl, methoxyphenyl, isopropoxyphenyl, allyloxyphenyl, phenoxyphenyl, 3,5-dimethyl-4-methoxyphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, furanyl, methylfuranyl, benzofuranyl, dibenzofuranyl, etc.

[0208] As R 1 ~R 14 Nitrogen-containing groups with 1 to 20 carbon atoms include, for example, amino, dimethylamino, diethylamino, allylamino, benzylamino, dibenzylamino, pyrrolyl, piperidinyl, morpholinyl, dimethylaminomethyl, benzylaminomethyl, pyrrolylmethyl, dimethylaminoethyl, pyrrolylethyl, dimethylaminopropyl, pyrrolylpropyl, dimethylaminoallyl, pyrrolylallyl, aminophenyl, dimethylaminophenyl, 3,5-dimethyl-4-dimethylaminophenyl, 3,5-diisopropyl-4-dimethylaminophenyl, julolidinyl, tetramethyljulolidinyl, pyrrolylphenyl, and pyrrolylphenyl. Carbazolylphenyl, di-tert-butylcarbazolylphenyl, pyrrole, pyridinyl, quinolinyl, tetrahydroquinolinyl, isoquinolinyl, tetrahydroisoquinolinyl, indolyl, dihydroindolyl, carbazolyl, di-tert-butylcarbazolyl, imidazolyl, dimethylimidazolyl, benzimidazolyl, oxazolyl, oxazolyl, benzoxazolyl, etc., preferably amino, dimethylamino, diethylamino, pyrroleyl, dimethylaminophenyl, 3,5-dimethyl-4-dimethylaminophenyl, 3,5-diisopropyl-4-dimethylaminophenyl, juloridinyl, tetramethyljuloridinyl, pyrroleylphenyl, pyrrole, pyridinyl, carbazolyl, imidazolyl.

[0209] In the above equation (1), R 1 ~R 6 Adjacent substituents in the middle (e.g., R) 1 With R 2 R2 with R 3 , R 3 with R 4 , R 4 with R 5 , and R 5 with R 6 ) can be combined with each other to form a ring which can have a substituent. As the ring formed at this time, a 5- to 8-membered ring which can have a substituent, formed of a saturated hydrocarbon (hydrocarbon other than the indenyl ring portion described above) or an unsaturated hydrocarbon, which forms a fused ring with the indenyl ring portion, is preferred. Of these, in the case where a plurality of rings are present, they can be the same as or different from each other. The above-mentioned ring is more preferably a 5-membered ring or a 6-membered ring, without particular limitation as long as the effects of the present application can be achieved, and, at this time, as the structure in which the above-mentioned ring is combined with the indenyl ring portion of the parent nucleus, for example, a benzindenyl ring, a tetrahydrobenzoindenyl ring, a cyclopentanotetrahydronaphthalene ring can be exemplified, with a benzindenyl ring or a tetrahydrobenzoindenyl ring being preferred. These rings can have a substituent.

[0210] In the above formula (1), R 7 to R 12 adjacent to each other (for example, R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , and R 11 and R 12 ) can be combined with each other to form a ring which can have a substituent. As the ring formed at this time, a 5- to 8-membered ring which can have a substituent, formed of a saturated hydrocarbon (hydrocarbon other than the indenyl ring portion described above) or an unsaturated hydrocarbon, which forms a fused ring with the indenyl ring portion, is preferred. Of these, in the case where a plurality of rings are present, they can be the same as or different from each other. The above-mentioned ring is more preferably a 5-membered ring or a 6-membered ring, without particular limitation as long as the effects of the present application can be achieved, and, at this time, as the structure in which the above-mentioned ring is combined with the indenyl ring portion of the parent nucleus, for example, a benzindenyl ring, a tetrahydrobenzoindenyl ring, a cyclopentanotetrahydronaphthalene ring, a tetrahydrofluorene ring, a fluorene ring can be exemplified, with a benzindenyl ring or a tetrahydrobenzoindenyl ring being preferred. These rings can have a substituent.

[0211] In the above formula (1), R 13 and R 14These rings can also have substituents. The rings formed at this time are preferably 3 to 8-membered saturated or unsaturated rings which can have substituents. There is no particular limitation as long as the effects of the present application can be achieved, and a 4 to 6-membered ring is preferred, and in this case, as the structure combined with Q, for example, a cyclobutane ring, a cyclopentane ring, a fluorene ring, a silyl-cyclobutane (silyl-cyclobutane) ring, a silyl-cyclopentane (silyl-cyclopentane) ring, a silyl-cyclohexane (silyl-cyclohexane) ring, a silyl-fluorene ring are exemplified, and a cyclopentane ring, a silyl-cyclobutane ring, a silyl-cyclopentane ring are preferred. These rings can have substituents.

[0212] The following shows specific examples of the transition metal compound (1), but the scope of the present application is not particularly limited to these specific examples.

[0213] For convenience, the structure of the ligand other than the portion shown by the removal of MXn (metal portion) of the above-mentioned transition metal compound (1) is divided into 2-indenyl ring portion, 1-indenyl ring portion, indenyl ring portion R 1 , R 6 , and R 8 substituent, indenyl ring portion R 2 , R 5 , R 9 , and R 12 substituent, indenyl ring portion R 3 , R 4 , R 10 , and R 11 substituent, 1-indenyl ring portion R 7 substituent, structure of bridging portion. The abbreviation of the 2-indenyl ring portion is α, the abbreviation of the 1-indenyl ring portion is β, the abbreviation of the indenyl ring portion R 1 , R 6 , and R 8 substituent is γ, the abbreviation of the indenyl ring portion R 2 , R 5 , R 9 , and R 12 substituent is δ, the abbreviation of the indenyl ring portion R 3 , R 4 , R 10 , and R 11 substituent is ε, the abbreviation of the 1-indenyl ring portion R 7 substituent is ζ, and the abbreviation of the structure of bridging portion is η. The abbreviations of the respective substituents are shown in [Table 1] to [Table 7].

[0214] [Table 1]

[0215] [Table 1]

[0216] 2-indenyl ring portion

[0217] [Table 2]

[0218] [Table 2]

[0219] 1-indenyl ring moiety

[0220]

[0221] wherein the above [Table 1] to [Table 2] wavy line indicates a binding site with a bridged moiety.

[0222] [Table 3]

[0223] [Table 3]

[0224] Indenyl ring R1, R6, R8 substituents

[0225] γ-1 hydrogen γ-2 methyl γ-3 ethyl γ-4 n-propyl γ-5 allyl γ-6 n-butyl γ-7 but-3-en-1-yl γ-8 benzyl γ-9 pentafluorophenylmethyl γ-10 phenyl γ-11 tolyl γ-12 naphthyl γ-13 4-t-butylphenyl γ-14 5-methyl-2-furyl γ-15 5-methyl-2-thienyl

[0226] R in the above [Table 3] 1 , R 6 and R 8 substituents can be the same or different from each other in their combinations.

[0227] [Table 4]

[0228] [Table 4]

[0229] Indenyl ring R2, R5, R9, R12 substituents

[0230]

[0231] R in the above [Table 4] 2 , R 5 , R 9 and R 12 substituents can be the same or different from each other in their combinations.

[0232] [Table 5]

[0233] [Table 5]

[0234] Indenyl ring R3, R4, R10, R11 substituents

[0235] ε-1 hydrogen ε-2 methyl ε-3 methoxy ε-4 ethyl ε-5 ethoxy ε-6 n-propyl ε-7 isopropyl ε-8 isopropoxy ε-9 n-butyl ε-10 isobutyl ε-11 sec-butyl ε-12 t-butyl ε-13 neopentyl ε-14 cyclopentyl ε-15 cyclohexyl ε-16 Thexyl group ε-17 t-octyl ε-18 phenoxy

[0236] R in the above [Table 5] 3 , R 4 , R 10 and R 11 substituents can be the same or different from each other in their combinations.

[0237] [Table 6]

[0238] [Table 6]

[0239] 1-indenyl ring R7substituent

[0240]

[0241] [Table 7]

[0242] [Table 7]

[0243] bridging moiety

[0244] η-1 methylene η-2 1,1-ethylene η-3 benzyl (phenylmethylene) η-4 dimethylmethylene (isopropylidene) η-5 methylethylmethylene (sec-butylidene) η-6 diethylmethylene (3-pentylidene) η-7 dipropylmethylene (4-heptylidene) η-8 dibutylmethylene (5-nonylidene) η-9 dibenzylmethylene η-10 (methyl)(phenyl)methylene (1-phenylethylidene) η-11 (methyl)(4-methylphenyl)methylene η-12 (methyl)(4-methoxyphenyl)methylene η-13 diphenylmethylene η-14 di(4-methylphenyl)methylene η-15 di(4-methoxyphenyl)methylene η-16 di(4-dimethylaminophenyl)methylene η-17 1,1-cyclobutylidene η-18 1,1-cyclopentylidene η-19 1,1-cyclohexylidene η-20 dimethylsilyl η-21 diethylsilyl η-22 divinylsilyl η-23 dipropylsilyl η-24 diisopropylsilyl η-25 diallylsilyl η-26 din-butylsilyl η-27 dit-butylsilyl η-28 di-n-hexylsilyl η-29 diphenylsilyl η-30 di(4-methylphenyl)silyl η-31 1,1-silylcyclobutyl (trimethylsilyl) η-32 1,1-silylcyclopentyl (tetramethylsilyl) η-33 1,1-silylcyclohexyl (pentamethylsilyl) η-34 (methyl)(ethyl)silyl η-35 (methyl)(vinyl)silyl η-36 (methyl)(allyl)silyl η-37 (methyl)(n-hexyl)silyl η-38 (methyl)(n-octyl)silyl η-39 (methyl)(n-decyl)silyl η-40 (methyl)(cyclohexyl)silyl η-41 (methyl)(phenyl)silyl

[0245] As specific examples of the metal moiety MXn, the following can be cited:

[0246] ZrF2, ZrCl2, ZrBr2, ZrI2, Zr(Me)2, Zr(Bn)2, Zr(allyl)2, Zr(CH2-tBu)2, Zr(1,3-pentadienyl), Zr(1,3-pentadienyl), Zr(2,4-hexadienyl), Zr(1,4-diphenyl-1,3-pentadienyl), Zr(CH2-Si(Me)3)2, Zr(OMe)2, Zr(OiPr)2, Zr(NMe2)2, Zr(OMs)2, Zr(OTs)2, Zr(OTf)2,

[0247] HfF2, HfCl2, HfBr2, HfI2, Hf(Me)2, Hf(Bn)2, Hf(allyl)2, Hf(CH2-tBu)2, Hf(1,3-pentadienyl), Hf(1,3-pentadienyl), Hf(2,4-hexadienyl), Hf(1,4-diphenyl-1,3-pentadienyl), Hf(CH2-Si(Me)3)2, Hf(OMe)2, Hf(OiPr)2, Hf(NMe2)2, Hf(OMs)2, Hf(OTs)2, Hf(OTf)2, and the like.

[0248] Me is methyl, Bn is benzyl, tBu is tert-butyl, Si(Me)3 is trimethylsilyl, OMe is methoxy, OiPr is isopropoxy, NMe2 is dimethylamino, OMs is methanesulfonate, OTs is p-toluenesulfonate, OTf is triflate.

[0249] According to the above, in the case where the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-5 in [Table 2], the indenyl ring moiety R 1 , R 6 and R 8 substituents are all γ-1 in [Table 3], the 2-indenyl ring moiety R 2 and R 5Substituents are each [Table 4] δ-1, 2-indenyl ring portion R 3 and R 4 Substituents are each [Table 5] ε-1, 1-indenyl ring portion R 7 Substituents are [Table 6] ζ-30, 1-indenyl ring portion R 9 Substituents are [Table 4] δ-38, 1-indenyl ring portion R 12 Substituents are [Table 4] δ-3, bridging portion is a combination of [Table 7] η-20, and the MXn of the metal portion is ZrCl2, a compound represented by the following formula [6] is exemplified.

[0250]

[0251] In addition, in a case where the 2-indenyl ring portion is [Table 1] α-1, the 1-indenyl ring portion is [Table 2] β-2, the indenyl ring portion R 1 , R 6 and R 8 Substituents are each [Table 3] γ-1, 2-indenyl ring portion R 2 and R 5 Substituents are each [Table 4] δ-2, 2-indenyl ring portion R 3 and R 4 Substituents are each [Table 5] ε-1, 1-indenyl ring portion R 7 Substituents are [Table 6] ζ-1, bridging portion is [Table 7] η-4, and the MXn of the metal portion is Zr(NMe2)2, a compound represented by the following formula [7] is exemplified.

[0252]

[0253] In addition, in a case where the 2-indenyl ring portion is [Table 1] α-3, the 1-indenyl ring portion is [Table 2] β-1, the indenyl ring portion R 1 and R 6 Substituents are each [Table 3] γ-2, indenyl ring portion R 2 , R 5 and R 12 Substituents are each [Table 4] δ-1, 1-indenyl ring portion R 7 Substituents are [Table 6] ζ-12, 1-indenyl ring portion R 8 Substituents are [Table 3] γ-1, 1-indenyl ring portion R 9 Substituents are [Table 4] δ-42, 1-indenyl ring portion R 10 Substituents are [Table 5] ε-3, 1-indenyl ring portion R 11The following compound is an example of a compound represented by formula [8] when the substituent is ε-12 in [Table 5], the bridging part is η-31 in [Table 7], and the metal part MXn is HfMe2.

[0254]

[0255] Additionally, in the 2-indenyl ring portion, the α-1 and 1-indenyl ring portions in [Table 1] are represented, and the β-1 and 2-indenyl ring portions in [Table 2] are represented. 1 and R 6 All substituents are γ-1,2-indenyl ring moieties R in [Table 3]. 2 The substituent is the δ-7,2-indenyl ring moiety R in [Table 4]. 3 R 4 R 10 and R 11 All substituents are ε-1, 2-indenyl ring moieties R in [Table 5] 5 The substituent is the δ-2,1-indenyl ring moiety R in [Table 4]. 7 The substituents are the ζ-1, 1-indenyl ring moiety R in [Table 6]. 8 The substituents are the γ-9, 1-indenyl ring moiety R in [Table 3]. 9 and R 12 The following compound is an example of a compound represented by formula [9], wherein all substituents are δ-1 in [Table 4], the bridging part is η-29 in [Table 7], and the metal part MXn is Zr(1,3-pentadienyl).

[0256]

[0257] The aforementioned transition metal compound (1) can be manufactured using existing known methods, and the manufacturing method is not particularly limited.

[0258] The substituted indene compound as a starting material can be produced using a publicly known method, and the production method is not particularly limited. As the publicly known production method, for example, the production methods disclosed in “Organometallics 1994, 13, 954.”, “Organometallics 2006, 25, 1217.”, Japanese Patent Application Laid-Open No. 2006-509059, “Bioorg. Med. Chem. 2008, 16, 7399.”, WO 2009 / 080216, “Organometallics 2011, 30, 5744.”, Japanese Patent Application Laid-Open No. 2011-500800, “Organometallics 2012, 31, 4962.”, “Chem. Eur. J. 2012, 18, 4174.”, Japanese Patent Application Laid-Open No. 2012-012307, Japanese Patent Application Laid-Open No. 2012-121882, Japanese Patent Application Laid-Open No. 2014-196319, Japanese Patent Application Laid-Open No. 2014-513735, Japanese Patent Application Laid-Open No. 2015-063495, Japanese Patent Application Laid-Open No. 2016-501952, Japanese Patent Application Laid-Open No. 2019-059933, and the like can be exemplified.

[0259] As the publicly known production method of the transition metal compound (1) and the precursor compound (ligand), for example, “Macromolecules 2001, 34, 2072.”, “Macromolecules 2003, 36, 9325.”, “Organometallics 2004, 23, 5332.”, “Eur. J. Inorg. Chem. 2005, 1003.”, “Eur. J. Inorg. Chem. 2009, 1759.”, and the like can be exemplified.

[0260] In addition, in the above-described transition metal compound (1), there are two directions (front face and back face) of the face of the indenyl ring portion sandwiching the bridging portion and binding to the central metal. Therefore, in the case where the 2-indenyl ring portion does not have a symmetrical face, for example, there are two structural isomers represented by the following general formulae [10a] or [10b].

[0261]

[0262] Also, in the case where the substituent R 13 is different from R 14 , for example, there are also two structural isomers represented by the following general formulae [11a] or [11b].

[0263]

[0264] The purification, fractionation or selective production of the structural isomer mixture can be performed using a known method, and the production method is not particularly limited. As the known production method, in addition to the methods listed as the production method of the above-mentioned transition metal compound (1), the production methods disclosed in Japanese Patent Application Laid-Open No. 10-109996, "Organometallics 1999, 18, 5347.", "Organometallics 2012, 31, 4340.", Japanese Patent Application Laid-Open No. 2011-502192, and the like can be listed.

[0265] Among the above-mentioned transition metal compounds (1), the transition metal compound can be used alone as one kind, or two or more kinds can be used in combination, a structural isomer mixture can be used, one kind of structural isomer can be used alone, or two or more kinds of structural isomer mixtures can be used. As described above, according to the present application, as the transition metal compound constituting the catalyst for olefin polymerization, the above-mentioned transition metal compound (1) can be used alone to produce an ethylene-based polymer into which a large amount of long chain branching is introduced with high catalytic activity, and within a range not impairing this effect, one or more kinds of transition metal compounds other than the above-mentioned transition metal compound (1) can be used as the above-mentioned transition metal compound. At this time, the transition metal compound (1) can be in any of the above-mentioned modes.

[0266] < Solid carrier (S) >

[0267] The solid carrier (S) contained in the catalyst for olefin polymerization (X) is an inorganic compound or an organic compound, and is a solid in a particulate or fine particulate form.

[0268] As the inorganic compound used as the above-mentioned solid carrier (S), a porous oxide, a solid aluminoxane compound, an inorganic chloride, clay, a clay mineral, or an ion-exchangeable layered compound can be listed.

[0269] As the above-mentioned porous oxide, SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, and ThO2, or a composite or mixture containing them, specifically, natural or synthetic zeolite, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, and SiO2-TiO2-MgO, and the like can be used. Among these, a substance in which SiO2 is the main component is preferred.

[0270] The above porous oxide can contain a small amount of carbonates, sulfates, nitrates, oxide components of Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, Li2O, and the like.

[0271] The properties of such porous oxides vary depending on the kind and the manufacturing method thereof, and the particle diameter of the solid carrier (S) is usually 0.2 to 300 μm, preferably 1 to 200 μm, the specific surface area is usually 50 to 1200 m 2 / g, preferably 100 to 1000 m 2 / g, and the pore volume is usually 0.3 to 30 cm 3 / g. Such a carrier can be used after being fired at, for example, 100 to 1000°C, preferably 150 to 700°C, as needed.

[0272] As the above solid aluminoxane compound, there can be mentioned an aluminoxane having a structure represented by the following general formula (S-a), an aluminoxane having a structure represented by the following general formula (S-b), and an aluminoxane having a structure in which a repeating unit represented by the following general formula (S-c) and a repeating unit represented by the following general formula (S-d) are present, and the like.

[0273]

[0274] In the above formulas (S-a) to (S-d), R e are each independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, isopropyl, isopropenyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclohexyl, cyclooctyl, phenyl, tolyl, ethylphenyl, and the like, and are preferably methyl, ethyl, isobutyl, and particularly preferably methyl. Also, a part of R e may be substituted with a halogen atom such as chlorine or bromine, and the halogen content can be 40% by weight or less based on R e . The straight line in the above formulas (S-c) and (S-d) not connected to an atom represents a bond to another atom not shown.

[0275] In the above formulas (S-a) and (S-b), r represents an integer of 2 to 500, preferably 6 to 300, and particularly preferably 10 to 100. In the above formulas (S-c) and (S-d), s and t each represent an integer of 1 or more. r, s, and t are selected so that the above aluminoxane can substantially maintain a solid state under the reaction environment employed.

[0276] The solid aluminoxane compound described above is different from the known carriers for olefin polymerization catalysts in that it does not contain inorganic solid components such as silica and alumina, and organic polymer components such as polyethylene and polystyrene, and is a solidified substance in which an aluminum alkyl compound is the main component. The "solid" means that the aluminoxane component substantially maintains a solid state under the reaction environment employed. More specifically, it means that the aluminoxane component substantially maintains a solid state when the above component (A) is brought into contact with the aluminoxane component to produce a catalyst for the polymerization of an olefin (e.g., a catalyst for the polymerization of ethylene), and when the polymerization of an olefin (e.g., ethylene) is carried out using the catalyst for the polymerization of an olefin thus produced (e.g., suspension polymerization).

[0277] Whether the aluminoxane component described above is in a solid state can be most easily confirmed by visual observation, but in many cases it is difficult to confirm by visual observation, for example, during polymerization. In this case, it can be judged, for example, from the properties of the polymer powder obtained after polymerization or the state of adhesion on the reactor, and the like. Conversely, if the properties of the polymer powder are good and the adhesion on the reactor is small, even if a small amount of the aluminoxane component described above dissolves out under the polymerization environment, it does not depart from the gist of the present application. As an index for judging the properties of the polymer powder, the bulk density, the particle shape, the surface shape, the degree of presence of amorphous polymer, and the like can be listed, and from a quantitative viewpoint, the bulk density of the polymer is preferred. The bulk density described above is usually in the range of 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

[0278] The solubility ratio of the solid aluminoxane compound described above in n-hexane maintained at a temperature of 25°C is usually in the range of 0 to 40 mol%, preferably 0 to 20 mol%, and particularly preferably 0 to 10 mol%.

[0279] As for the solubility ratio, it is determined by adding 2 g of the solid aluminoxane compound carrier to 50 ml of n-hexane maintained at 25°C, stirring for 2 hours, then separating the solution fraction using a G-4 glass filter, and measuring the aluminum concentration in the filtrate. Thus, the solubility ratio is determined as the ratio of the aluminum atoms present in the above filtrate to the amount of aluminum atoms corresponding to 2 g of the aluminoxane used.

[0280] As the solid aluminoxane compound described above, a publicly known solid aluminoxane can be used without any limitation, and a solid polyaluminoxane composition described in International Publication No. 2014 / 123212, for example, can also be used. As publicly known production methods, for example, production methods described in Japanese Patent No. 7-42301, Japanese Patent Laid-Open No. 6-220126, Japanese Patent Laid-Open No. 6-220128, Japanese Patent Laid-Open No. 11-140113, Japanese Patent Laid-Open No. 11-310607, Japanese Patent Laid-Open No. 2000-38410, Japanese Patent Laid-Open No. 2000-95810, International Publication No. 2010 / 55652, and the like can be exemplified.

[0281] The average particle diameter of the solid aluminoxane compound described above is usually in the range of 0.01 to 50,000 μm, preferably 0.1 to 1,000 μm, and particularly preferably 1 to 200 μm. The average particle diameter of the solid aluminoxane compound can be obtained by observing the particles with a scanning electron microscope, measuring the particle diameters of 100 or more particles, and performing weight averaging. First, with respect to the particle diameter d of each particle, the length is measured with two parallel lines sandwiching the particle image in the horizontal direction and the vertical direction, and is obtained using the following formula.

[0282] Particle diameter d = ((horizontal direction length) 2 + (vertical direction length) 2 ) 0.5

[0283] Next, with respect to the weight average particle diameter of the solid aluminoxane compound, the particle diameter d obtained above and the number of particles n are used to obtain the following formula.

[0284] Average particle diameter = ∑nd 4 / ∑nd 3

[0285] The specific surface area of the solid aluminoxane compound described above is preferably 50 to 1,000 m 2 / g, and more preferably 100 to 800 m 2 / g. The pore volume is preferably 0.1 to 2.5 cm 3 / g.

[0286] As the inorganic halide described above, for example, MgCl2, MgBr2, MnCl2, MnBr2, and the like can be exemplified. The inorganic halide can be used as it is, or can be pulverized using a ball mill or a vibration mill. Also, a substance in which the inorganic halide is precipitated in a fine particle form using a precipitant after being dissolved in a solvent such as alcohol can also be used.

[0287] Clay is typically composed primarily of clay minerals. Additionally, ion-exchangeable layered compounds are crystalline compounds with a parallel, stacked structure formed by ionic bonds and other weak bonding forces, in which ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. Furthermore, these clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products; synthetic compounds can also be used.

[0288] In addition, examples of clay, clay minerals, or ion-exchangeable layered compounds include clay, clay minerals, and ionic crystalline compounds with layered crystalline structures such as hexagonal close-packed type, antimony type, CdCl2 type, and CdI2 type.

[0289] Examples of such clays and clay minerals include kaolin, bentonite, wood-knot clay, frog-eye clay, diaspore, ferrosilicon, pyrophyllite, mica, montmorillonite, vermiculite, chlorite, palygorskite, kaolinite, perlite, dickite, halloysite, etc. Examples of ion-exchangeable layered compounds include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O.

[0290] Such clays, clay minerals, or ion-exchangeable layered compounds preferably have their radius measured using the mercury infiltration method. The above-mentioned materials have a pore volume of 0.1 cc / g or higher, with materials having a pore volume of 0.3 to 5 cc / g being particularly preferred. Here, regarding the pore volume, the mercury injection method using a mercury porosimeter is used to determine the pore radius. The range was measured. The radius was used. When using substances with a pore volume of less than 0.1 cc / g as carriers, there is a tendency to find it difficult to obtain high polymerization activity.

[0291] It is also preferable to perform chemical treatment on the clay and clay mineral. As the chemical treatment, surface treatment for removing impurities adhering to the surface, treatment for imparting an effect on the crystal structure of the clay, and the like can be used. As the chemical treatment, acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like can be specifically mentioned. In the acid treatment, in addition to being able to remove impurities from the surface, it is also possible to increase the surface area by dissolving cations such as Al, Fe, and Mg in the crystal structure. In the alkali treatment, the crystal structure of the clay is destroyed, and a change in the clay structure is imparted. In addition, in the salt treatment and the organic matter treatment, it is possible to form ion complexes, molecular complexes, organic derivatives, and the like, and change the surface area or the interlayer distance.

[0292] The ion-exchangeable layered compound can be a layered compound in a state in which the interlayer exchangeable ions are exchanged with other large ions by ion exchangeability, so that the interlayer is enlarged. Such a large ion assumes the role of a pillar supporting the layered structure, and is generally referred to as a pillar. In addition, the case in which such other substances are introduced into the interlayer of the layered compound is referred to as intercalation. As the guest compound for performing intercalation, cationic inorganic compounds such as TiCl4and ZrCl4, metal alkoxides (R is a hydrocarbon group or the like) such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3, metal hydroxide ions such as [Al 13 O4(OH) 24 ] 7+ , [Zr4(OH) 14 ] 2+ , [Fe3O(OCOCH3)6] + , and the like can be mentioned. These compounds can be used alone, or two or more thereof can be used in combination. In addition, when these compounds are intercalated, polymers obtained by hydrolysis of metal alkoxides (R is a hydrocarbon group or the like) such as Si(OR)4, Al(OR)3, and Ge(OR)4, colloidal inorganic compounds such as SiO2, and the like can also be present. In addition, as the pillar, oxides and the like obtained by heating and dehydrating the metal hydroxide ions intercalated in the interlayer can be mentioned.

[0293] The clay, the clay mineral, and the ion-exchangeable layered compound can be used as they are, or can be used after being subjected to treatment such as ball milling and sieving. In addition, they can also be used after being rehydrated and adsorbed, or after being subjected to heating and dehydration treatment. Furthermore, one kind can be used alone, or two or more thereof can be used in combination.

[0294] As the organic compound used as the above-mentioned solid carrier (S), for example, there can be mentioned a granular or particulate solid having a particle diameter in the range of 10 to 300 μm. As specific examples of the above-mentioned organic compound, for example, there can be mentioned a granular or particulate solid of a polymer produced mainly from an olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or the like, or a polymer or reactant produced mainly from vinylcyclohexane, styrene, divinylbenzene, or the like, and a modified body thereof.

[0295] As the above-mentioned solid carrier (S), from the viewpoint of preventing foreign matter at the time of molding, a porous oxide is preferred.

[0296] <Ingredient (C)>

[0297] The olefin polymerization catalyst (X) preferably further contains an ingredient (C) which is at least one compound selected from the group consisting of an organometallic compound (c-1), an organoaluminum oxy compound (c-2), and a compound (c-3) which forms an ion pair by reacting with the ingredient (A), represented by the following general formulas (3) to (5).

[0298] R a m Al(OR b ) n H p X q ... (3)

[0299] In formula (3), R a and R b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, X represents a halogen atom, m is a number satisfying 0 < m < 3, n is a number satisfying 0 < n < 3, p is a number satisfying 0 < p < 3, q is a number satisfying 0 < q < 3, and m + n + p + q = 3.

[0300] M a AlR a 4... (4)

[0301] In formula (4), M a represents Li, Na, or K, and R a represents a hydrocarbon group having 1 to 15 carbon atoms.

[0302] R a r M b R b s X t ... (5)

[0303] In formula (5), R a and R brespectively independently represent a hydrocarbon group having 1 or more and 15 or less carbon atoms, M b is selected from the group consisting of Mg, Zn and Cd, X represents a halogen atom, r is 0 < r < 2, s is 0 < s < 1, t is 0 < t < 1, and r + s + t = 2.

[0304] In the above organic metal compound (c-1), a compound represented by the above formula (3) is preferable, and specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, and the like can be exemplified.

[0305] dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, and the like;

[0306] alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, and the like;

[0307] alkylaluminum dihalides such as methyldichloroaluminum, ethyldichloroaluminum, isopropylaluminum dichloride, ethyldibromoaluminum, and the like;

[0308] hydrogenated alkylaluminum such as dihydrogenated methylaluminum, dihydrogenated ethylaluminum, dihydrogenated isopropylaluminum, dihydrogenated n-butylaluminum, dihydrogenated isobutylaluminum, dihydrogenated isohexylaluminum, dihydrogenated phenylaluminum, dihydrogenated cyclohexylaluminum, dihydrogenated sec-heptylaluminum, dihydrogenated sec-nonylaluminum, and the like;

[0309] alkoxydialkylaluminum such as ethoxydimethylaluminum, ethoxydiethylaluminum, methoxydiisopropylaluminum, ethoxydiisobutylaluminum, and the like.

[0310] As examples of the above formula (4), lithium aluminum hydride and the like can be exemplified. As examples of the above formula (5), dialkylzinc compounds described in Japanese Patent Application Publication No. 2003-171412 and the like can be exemplified, and the use in combination with a phenol compound and the like is also possible.

[0311] As the above organoaluminum oxy compound (c-2), an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and aluminoxane prepared from trimethylaluminum or triisobutylaluminum, for example, methylaluminoxane is particularly preferable. Such organoaluminum oxy compounds can be used alone as one kind or in combination of two or more kinds.

[0312] As the compound (c-3) which forms an ion pair with the above-mentioned component (A), a Lewis acid, an ionic compound, a borane compound, a carborane compound, a heteropoly compound, and a homopoly compound, and the like described in Japanese Patent Laid-Open No. 501950 / 1995, Japanese Patent Laid-Open No. 502036 / 1995, Japanese Patent Laid-Open No. 3-179005, Japanese Patent Laid-Open No. 3-179006, Japanese Patent Laid-Open No. 3-207703, Japanese Patent Laid-Open No. 3-207704, and US 5321106, and the like can be used.

[0313] The catalyst (X) for the polymerization of an olefin compound is not only very high in polymerization activity for an olefin compound when an organoaluminum compound such as methylaluminoxane is used as a cocatalyst component, but also reacts with active hydrogen in a solid carrier to easily produce a solid carrier component containing the cocatalyst component, and therefore it is preferred that the component (C) contains at least the organoaluminum compound (c-2).

[0314] <Method of using each component and order of adding>

[0315] The catalyst (X) for the polymerization of an olefin compound can be produced by mixing and contacting the component (A) and the component (S), and optionally the component (C) in an unreactive hydrocarbon.

[0316] As the method of contacting each component, in view of the order of contacting, for example, the following can be listed:

[0317] (i) a method of contacting the component (S) with the component (A);

[0318] (ii) a method of contacting the component (S) with the component (C), and then contacting the component (A);

[0319] (iii) a method of contacting the component (A) with the component (C), and then contacting the component (S);

[0320] (iv) a method of contacting the component (S) with the component (C), and then contacting a mixture of the component (A) and the component (C);

[0321] (v) a method of contacting the component (S) with the component (C), and then contacting a mixture of the component (A) and the component (C), and the like.

[0322] In the case where a plurality of components (C) are used, the components (C) can be the same as or different from each other. Among the above-mentioned methods, (i), (ii), and (iii) are preferred.

[0323] In each of the above methods showing the contact sequence, in the process including the contact of the component (S) with the component (C) and the process including the contact of the component (S) with the component (A), by allowing the component (G) to coexist, the fouling in the polymerization reaction is suppressed or the particle properties of the resulting polymer are improved. As the component (G), a compound having a polar functional group can be used, preferably a non-ion surfactant, more preferably a polyoxyalkylene block, a higher aliphatic amide, a polyoxyalkylene, a polyoxyalkylene alkyl ether, an alkyl diethanol amine, a polyoxyalkylene alkyl amine, a glycerin fatty acid ester, an N-acyl amino acid. One kind thereof can be used, or two or more kinds thereof can be used in combination.

[0324] As the solvent used in the preparation of the catalyst (X) for the polymerization of an olefin, an inert hydrocarbon solvent can be exemplified, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as chloroethylene, chlorobenzene, dichloromethane, or a mixture thereof, or the like.

[0325] When the component (C) is contacted with the component (S), chemical bonding occurs by the reaction of the reaction site in the component (C) with the reaction site in the component (S), and the contact of the component (C) with the component (S) is formed. The contact time of the component (C) with the component (S) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is usually -50 to 200°C, preferably -20 to 120°C. In the case where the initial contact of the component (C) with the component (S) is performed drastically, in most cases, the component (S) is disintegrated due to the reaction heat or the reaction energy, and the form of the resulting solid catalyst component is deteriorated, and when it is used for polymerization, continuous operation becomes difficult due to the poor form of the polymer. Therefore, at the initial stage of the contact of the component (C) with the component (S), in order to suppress the reaction heat, it is preferable to contact at a lower temperature, or to control the reaction heat so that the reaction can be performed at a rate at which the initial contact temperature can be maintained. The same applies to the case where the component (C) is contacted with the component (S) and then the component (C) is re-contacted. The contact weight ratio of the component (C) to the component (S) [weight of the component (C) / weight of the component (S)] can be arbitrarily selected, and when the contact weight ratio is high, more component (A) can be contacted, and the catalytic activity per unit weight of the solid catalyst component can be improved.

[0326] The contact weight ratio of the component (C) to the component (S) [weight of the component (C) / weight of the component (S)] is preferably 0.05 to 3.0, particularly preferably 0.1 to 2.0.

[0327] The contact time when the contact of component (C) and component (S) with component (A) is usually 1 minute to 20 hours, preferably 1 minute to 10 hours, and the contact temperature is usually in the range of -50 to 200°C, preferably -50 to 100°C.

[0328] Component (C-1) is usually used in an amount such that the molar ratio [(C-1) / M] of component (C-1) to the total transition metal atoms (M) in component (A) becomes 0.01 to 100,000, preferably 0.05 to 50,000.

[0329] Component (C-2) is usually used in an amount such that the molar ratio [(C-2) / M] of component (C-2) (aluminum atom conversion) to the total transition metal atoms (M) in component (A) becomes 10 to 500,000, preferably 20 to 100,000.

[0330] Component (C-3) is usually used in an amount such that the molar ratio [(C-3) / M] of component (C-3) to the total transition metal atoms (M) in component (A) becomes 1 to 10, preferably 1 to 5.

[0331] The ratio of component (C) to the total transition metal atoms (M) in component (A) can be determined by inductively coupled plasma emission spectrometry (ICP analysis). In the polymerization of ethylene, the olefin polymerization catalyst (X) can be used directly, or the olefin polymerization catalyst can be used after being pre-polymerized with an olefin to form a pre-polymerized catalyst (XP).

[0332] The pre-polymerized catalyst (XP) can be produced by pre-polymerizing ethylene or the like in the presence of the olefin polymerization catalyst (X) in an inert hydrocarbon solvent, and can be performed in any method of batch, semi-continuous, or continuous, and can be performed under reduced pressure, normal pressure, or elevated pressure. Also, it is desirable to produce the pre-polymerized catalyst (XP) in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g, per 1 g of the solid catalyst component.

[0333] After the pre-polymerized catalyst (XP) produced in the inert hydrocarbon solvent is separated from the suspension, it is resuspended in the inert hydrocarbon, ethylene can be introduced into the resulting suspension, and ethylene can also be introduced after drying.

[0334] The pre-polymerization temperature is -20 to 80°C, preferably 0 to 60°C, and the pre-polymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours. The pre-polymerization preferably uses an olefin in which ethylene is the main component.

[0335] As the form of the solid catalyst component used as the prepolymerization, the forms described above can be used without any limitation. Also, component (C) is used as needed, and the organometallic compound (c-1) represented by the above formula (3) is preferably used. When component (C) is used, component (C) is used in an amount such that the molar ratio of aluminum atoms (Al) in component (C) to transition metal atoms (M) in component (A) (Al / M) is 0.1 to 10,000, preferably 0.5 to 5,000.

[0336] As to the concentration of the catalyst (X) for olefin polymerization in the prepolymerization system, it is usually 1 to 1,000 g / L, more desirably 10 to 500 g / L, in terms of the catalyst for olefin polymerization / polymerization volume ratio. In the prepolymerization, the above component (G) can be allowed to coexist in order to suppress fouling or improve the particle properties.

[0337] In addition, in order to improve the fluidity of the prepolymerization catalyst (XP), suppress the generation of hot spots, lumps or polymer blocks during polymerization, component (G) can be brought into contact with the prepolymerization catalyst (XP) temporarily produced by the prepolymerization.

[0338] The temperature at the time of contact of the above component (G) is usually -50 to 50°C, preferably -20 to 50°C, and the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 10 hours.

[0339] At the time of contact of the catalyst (X) for olefin polymerization with component (G), component (G) is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, more desirably 0.4 to 5 parts by weight, relative to 100 parts by weight of the catalyst (X) for olefin polymerization.

[0340] The mixing contact of the catalyst (X) for olefin polymerization with component (G) can be carried out in an inert hydrocarbon solvent, and the same solvents as described above can be used as the inert hydrocarbon solvent.

[0341] In the method for producing an ethylene-based polymer according to the present application, as the catalyst (X) for olefin polymerization, a catalyst obtained by drying the prepolymerization catalyst (XP) (hereinafter also referred to as "dried prepolymerization catalyst") can be used. The drying of the prepolymerization catalyst (XP) is usually carried out after removing the hydrocarbon as the dispersion medium from the obtained suspension of the prepolymerization catalyst by filtration or the like.

[0342] The drying of the prepolymerization catalyst (XP) is performed by keeping the prepolymerization catalyst (XP) at a temperature of 70°C or lower, preferably in the range of 20 to 50°C, under the flow of an inert gas. The volatile component content of the resulting dried prepolymerization catalyst is desirably 2.0% by weight or less, preferably 1.0% by weight or less. The less the volatile component content of the dried prepolymerization catalyst, the better, and there is no particular lower limit, but in practice, it is 0.001% by weight. The drying time also depends on the drying temperature, and is usually 1 to 48 hours.

[0343] The dried prepolymerization catalyst described above has excellent fluidity, and thus can be stably supplied to a polymerization reactor. Also, when the dried prepolymerization catalyst described above is used, since a solvent for suspension can not be involved in the gas phase polymerization system, the polymerization can be stably performed.

[0344] [Method for producing ethylene-based polymer]

[0345] Next, a method for producing an ethylene-based polymer according to the present application will be described. An ethylene-based polymer is obtained by polymerizing (homopolymerizing or copolymerizing) ethylene in the presence of the above-described catalyst for olefin polymerization (X). By using the catalyst for olefin polymerization (X), an ethylene-based copolymer having high polymerization activity, excellent molding processability and mechanical strength, and a large amount of long-chain branches at a low density can be efficiently produced. The ethylene-based polymer of the present application refers to a polymer having an ethylene content of 10 mol% or more in the polymer.

[0346] In the present application, the polymerization can be performed by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method, but it is preferable to use the above-described prepolymerization catalyst (XP) in the suspension polymerization method and the gas phase polymerization method.

[0347] As specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chlorinated ethylene and chlorobenzene; dichloromethane; and mixtures thereof can be given. In addition, in the liquid phase polymerization method, the olefin itself can be used as a solvent.

[0348] When the polymerization of ethylene is performed using the above-described catalyst for olefin polymerization, it is generally used in an amount such that the component (A) becomes 1 x 10 -12 to 1 x 10 -1 mole per 1 liter of the reaction volume, preferably 1 x 10 -8 to 1 x 10 -2 mole. Also, it is preferable to use the component (C), particularly the organoaluminum compound represented by formula (3) in (c-1).

[0349] Further, the polymerization temperature of ethylene using the above-described prepolymerization catalyst (XP) is usually in the range of -50 to +200°C, preferably 0 to 170°C, and particularly preferably 60 to 170°C. The polymerization reaction can be carried out in any method of batch, semi-continuous, or continuous under the conditions of a polymerization pressure of usually normal pressure to 100 kgf / cm 2 , preferably normal pressure to 50 kgf / cm 2 . Also, the polymerization can be carried out in 2 or more stages with different reaction conditions.

[0350] The molecular weight of the obtained polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Generally, the more the low molecular weight component, the more the adhesion to the wall of the polymerization reactor and the stirring blade, and the more the burden on the cleaning process, and sometimes the production rate is reduced. In the polymerization, in order to suppress fouling or improve the particle properties, the component (G) can be co-presented.

[0351] Further, in the present application, the monomer supplied together with ethylene to the copolymerization reaction is one or more monomers selected from α-olefins having 4 to 10 carbon atoms, preferably α-olefins having 6 to 10 carbon atoms. As specific examples of the α-olefins having 4 to 10 carbon atoms, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene can be given. Also, within the range not impairing the effects of the present application, monomers other than ethylene and the α-olefins having 4 to 10 carbon atoms can be supplied, or can not be supplied.

[0352] 〈Method for producing ethylene-α-olefin copolymer (B)〉

[0353] The ethylene-α-olefin copolymer (B) can be obtained by polymerizing ethylene with an α-olefin having 4 to 10 carbon atoms, and the polymerization catalyst and the polymerization conditions used are not particularly limited as long as a polymer satisfying the above-described conditions can be obtained. As the ethylene-α-olefin copolymer (B), for example, commercially available products such as linear low density polyethylene, ethylene-α-olefin copolymer, high density polyethylene, etc. can be used. In the case of using commercially available products, for example, products satisfying the conditions (a) to (c) can be selected from LLDPE Evolue (registered trademark), ULTZEX (registered trademark), etc. manufactured by Prime Polymer Co., Ltd.

[0354] 〈Method for producing ethylene-based resin composition (Z)〉

[0355] The ethylene-based resin composition (Z) can be produced by melt-kneading the above-described ethylene-α-olefin copolymer (A) and the above-described ethylene-α-olefin copolymer (B), or can also be produced by dry blending the pellets of the ethylene-α-olefin copolymer (A) and the pellets of the ethylene-α-olefin copolymer (B). In the case of production by melt-kneading, a continuous extruder or a closed kneader can be used. For example, a single-screw extruder, a twin-screw extruder, a mixing roll, a Banbury mixer, a kneader, and the like can be cited. Among these, from the viewpoints of economy, processing efficiency, and the like, a single-screw extruder and / or a twin-screw extruder is preferably used.

[0356] In the case of performing the above-described melt-kneading and dry blending, the above-described "other thermoplastic resin" can be blended in addition to the above-described ethylene-α-olefin copolymer (A) and the above-described ethylene-α-olefin copolymer (B). Furthermore, the above-described "additive" can be further compounded in addition to the "other thermoplastic resin", or the above-described "additive" can be further compounded instead of the "other thermoplastic resin".

[0357] The order of addition of the above-described "other thermoplastic resin" and the above-described "additive" is not particularly limited. For example, the above-described "other thermoplastic resin" and the above-described "additive" can be blended at the same time as one or both of the above-described ethylene-α-olefin copolymer (A) and the above-described ethylene-α-olefin copolymer (B), or can also be added after the above-described ethylene-α-olefin copolymer (A) and the above-described ethylene-α-olefin copolymer (B) are kneaded.

[0358] The above-described ethylene-α-olefin copolymer (A) and the above-described ethylene-α-olefin copolymer (B) can each contain at least one or more structural units derived from ethylene or α-olefin from biomass. The same kind of monomer constituting the polymer can be only a monomer from biomass, can be only a monomer from fossil fuel, or can contain both a monomer from biomass and a monomer from fossil fuel. The monomer from biomass is a monomer formed using, as a raw material, all of natural raw materials and their residues which are regeneratable, of plant origin or animal origin, and the like, including fungi, yeast, algae, and bacteria, and the like, and contains 14C isotope in a proportion of about 1 x 10 -12 about 1 x 10-12 or less of the carbon. The biomass carbon concentration (pMC) measured in accordance with ASTM D6866 is about 100 (pMC). Ethylene and α-olefin from biomass can be obtained, for example, by a method known at present. From the viewpoint of reduction of environmental load, it is preferable that the above-described ethylene-α-olefin copolymer (A) and / or the above-described ethylene-α-olefin copolymer (B) contain a structural unit derived from a monomer from biomass.

[0359] 〔Molded body, film, multilayer film〕

[0360] By processing the ethylene-based resin composition (Z) according to the present application, a molded body, preferably a film or a multilayer film, having excellent moldability, mechanical strength such as impact strength, and high transparency and rigidity can be obtained. Here, the multilayer film has at least one layer comprising the ethylene-based resin composition (Z) described above, and preferably, in the multilayer film, at least one surface layer is a layer comprising the ethylene-based resin composition (Z) described above. The base material constituting the multilayer film can comprise the ethylene-based resin composition (Z), or can comprise a material other than the ethylene-based resin composition (Z).

[0361] The ethylene-based resin composition (Z) according to the present application can be processed by general film molding or sheet molding, blow molding, injection molding, and extrusion molding, and the like. In film molding, extrusion lamination molding, T-film molding, inflation molding (air cooling, water cooling, multi-stage cooling, high-speed processing), and the like can be exemplified. The obtained film can be used as a single layer, but by making it a multilayer, various functions can be further imparted. As the molding method employed at this time, co-extrusion methods can be exemplified. On the other hand, by a lamination molding method such as extrusion lamination molding or dry lamination, a paper or a barrier film (aluminum foil, vapor deposition film, coated film, and the like) that is difficult to co-extrude can be laminated. In any case, when a multilayer film in which at least one surface layer is formed of a layer comprising the ethylene-based resin composition (Z) described above is obtained, as a means for laminating a layer comprising the ethylene-based resin composition (Z) described above on a base material, such a method can be employed.

[0362] For the production of a high-functional product by multilayerization by a co-extrusion method in blow molding or injection molding, extrusion molding, the same as in film molding can be employed.

[0363] As the molded body obtained by processing the ethylene-based resin composition (Z) according to the present application, a film, a sheet, a blow-molded infusion bag, a blow-molded bottle, a gasoline tank, a tube obtained by extrusion molding, a pipe, a wire sheath, a tear-off cap, an injection-molded article of a daily necessity, a fiber, a large molded product obtained by rotational molding, and the like can be exemplified.

[0364] Further, a film obtained by processing the ethylene-based resin composition (Z) of the present application is suitable for various packaging films, protective films, infusion bags, agricultural materials, bag-in-boxes, semiconductor materials, pharmaceuticals, foodstuffs, and the like used in the packaging of water-containing products, liquid soup packaging bags, liquid paper containers, laminated original films, special-shaped liquid packaging bags (stand-up pouches and the like), standard bags, overwrap bags, envelope films, sugar bags, oil-containing product packaging bags, and the like. At this time, the film can be used as a film having one or more layers containing the ethylene-based resin composition (Z), or as a multilayer film having a layer containing the ethylene-based resin composition (Z) laminated on a substrate formed of nylon, polyester, polyolefin film, or the like.

[0365] The raw material of the substrate of the multilayer film can also contain an ethylene-based polymer, a propylene-based polymer, or the like containing a monomer derived from biomass.

[0366] Examples

[0367] The present application will be described more specifically below by way of examples. However, the present application is not limited to the descriptions of the following examples.

[0368] [Measurement and Evaluation Methods]

[0369] In the following examples and the like, various physical properties of the ethylene-α-olefin copolymer and the like were measured according to the methods described in the [Detailed Description of the Invention], and as an evaluation method not described in the [Detailed Description of the Invention], the following methods were used.

[0370] Blow molding evaluation:

[0371] Use An extruder and a blow molding machine with a die diameter of 100 mm (manufactured by Sumitomo Heavy Industries, Ltd.) were used, and a film with a thickness of 40 μm was obtained from an ethylene-based polymer under conditions of a die temperature of 190°C, an extrusion amount of 29 kg / hr, and a tube width of 320 mm. The obtained film was measured for the following items.

[0372] [Haze]

[0373] The total haze of the obtained film was measured according to JIS 7136.

[0374] [Internal haze]

[0375] The obtained film was placed in a sample cell filled with cyclohexanol, and measurement was performed according to JIS 7136.

[0376] [Glossiness 20°]

[0377] The glossiness of the obtained film was measured according to JIS Z8741 at an incident angle of 20°.

[0378] [Tensile elastic modulus]

[0379] The MD direction and the TD direction of the obtained film were measured in accordance with JIS K6781 at a test speed of 200 mm / min.

[0380] [Drop dart impact]

[0381] The obtained film was clamped by a pneumatic clamp in accordance with ASTM D1709 A method, and a hemispherical dart was dropped from a certain height, and the load at which the film was broken by 50% was read from a chart.

[0382] [Blocking force]

[0383] Two inner surfaces of the obtained tubular film were overlapped with each other to obtain a test piece, and the test piece was aged for 3 days under application of a load of 10 kg at 50°C. Thereafter, the test piece was cut to a width of 200 mm, and the force required to pull apart at 23°C at a speed of 200 mm / min was measured as the blocking force.

[0384] [Melt tension of composition]

[0385] A film obtained by blow molding was measured using a capillary rheometer: CAPILOGRAPH ID manufactured by Toyo Seiki Jiki K.K.. The conditions were set to a resin temperature of 190°C, a melt time of 6 minutes, a tube diameter of 1 mm, an extrusion speed of 15 mm / min, a take-up speed of 24 m / min (in the case where the melt filament was broken, the take-up speed was lowered by 5 m / min at a time), a nozzle diameter of 2 mm, and a nozzle length of 8 mm.

[0386] [Resin pressure]

[0387] The resin pressure at the time of film molding under the above conditions was recorded.

[0388] [Melt film stability]

[0389] The melt film (bubble) stability at the time of film molding under the above conditions was visually confirmed. The meanings of the symbols (evaluation results) in Table 12 are as follows.

[0390] O: The melt film (bubble) was stable, and the shaking was little

[0391] Δ: The stability of the melt film (bubble) was slightly poor, and the shaking was visible

[0392] X: The stability of the melt film (bubble) was poor, and the shaking was violent

[0393] [Raw material for use]

[0394] The transition metal compound and the component (G) used in the Examples and the like are as follows. ​​

[0395] Transition metal compound (A-1): dimethylsilylene(2-indenyl)(4-(3,5-di-t-butyl-4- methoxyphenyl)-7-methoxy-l-indenyl)zirconium dichloride [synthesized according to the method described in Japanese Patent Application Publication No. 2019-059933.]

[0396] Transition metal compound (B-1): dimethylsilylene(3-n-propylcyclopentadienyl)(cyclopentadienyl)zirconium dichloride [synthesized according to the method described in Japanese Patent No. 5455354.]

[0397] Transition metal compound (B-2): isopropylidene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride [synthesized according to the method described in Japanese Patent Application Publication No. Hei 4-69394.]

[0398] Component (G-1): lauryl diethanolamine (manufactured by Kao Corporation)

[0399] Component (G-2): EMULGEN (registered trademark) 108 (manufactured by Kao Corporation)

[0400] <Synthesis of prepolymer catalyst (XP-1)>

[0401] In a reactor with a stirrer having a content volume of 270 L, 10 kg of silica (average particle diameter: 70 μm, specific surface area: 340 m 2 / g, pore volume: 1.3 cm 3 / g, calcination at 250°C) as a solid support (S) manufactured by Fuji Silysia was suspended in 77 L of toluene, and then cooled to 0-5°C. To this suspension, 20.4 L of a toluene solution of methylaluminoxane as component (C) (3.5 mol / L in terms of Al atoms) was added dropwise over 30 minutes. At this time, the temperature in the system was maintained at 0-5°C. After the reaction was continued at 0-5°C for 30 minutes, the temperature was raised to 95-100°C over about 1.5 hours, and the reaction was continued at 95-100°C for 4 hours. After that, the temperature was lowered to room temperature, the supernatant was removed by decantation, and then washed twice with toluene, to thereby prepare a toluene slurry having a total amount of 58.0 L. A part of the obtained slurry component was sampled to investigate the concentration, and the slurry concentration was 248.0 g / L and the Al concentration was 1.21 mol / L.

[0402] Subsequently, the obtained toluene slurry 6.1 L and toluene 21.9 L were charged into the reactor with an agitator having an inner volume of 114 L after sufficient nitrogen substitution, and a 8 mM toluene solution of the transition metal compound (A-1) 5.4 L was added, and after contact at a system temperature of 20 to 25 °C for 1 hour, the supernatant was removed by decantation, and after washing twice with hexane, a slurry having a total amount of 30.9 L was prepared. While the obtained slurry was adjusted to 10 to 15 °C, a 0.92 M hexane solution of diisobutylaluminum hydride 3.1 L was added, and ethylene gas was supplied at a flow rate of 0.74 kg / hr, and after the addition of 1-hexene 34.3 mL, the system temperature was adjusted to 32 to 38 °C while adding 1-hexene 34.3 mL every 1 hour for a total of 5 times, and ethylene supply was started 6 hours later, and ethylene supply was stopped when the ethylene supply amount reached 4.5 kg. Thereafter, the system was sufficiently substituted with nitrogen, the supernatant was removed by decantation, and after washing four times with hexane, a slurry having a total amount of 21.9 L was prepared. While the obtained slurry was maintained at 35 to 40 °C, a 10 g / L hexane solution of component (G-1) 6.1 L was added, and contact was performed for 2 hours. After the entire amount of the obtained slurry was charged into an evaporative drier with an agitator having an inner volume of 43 L under a nitrogen atmosphere, the drier was depressurized to -68 kPaG over about 60 minutes, and after reaching -68 kPaG, vacuum drying was performed for about 4.3 hours, and hexane and volatile components in the prepolymer catalyst component were removed. Further depressurization was performed to -100 kPaG, and after reaching -100 kPaG, vacuum drying was performed for 8 hours, and a prepolymer catalyst (XP-1) 6.2 kg was obtained. A part of the obtained prepolymer catalyst (XP-1) was taken to investigate the composition, and 0.56 mg of Zr atoms was contained per 1 g of the prepolymer catalyst component.

[0403] < Synthesis of prepolymer catalyst (XP-2) >

[0404] A prepolymer catalyst (XP-2) 6.1 kg was obtained according to the production method of the prepolymer catalyst component (XP-1) described in Japanese Patent No. 5943941.

[0405] < Production of ethylene-based polymer >

[0406] [Production Example 1]

[0407] (Production of ethylene-α-olefin copolymer (A-1))

[0408] Ethylene-based polymers were produced by a gas phase polymerization process using a fluidized bed type gas phase polymerization reactor. 24 kg of spherical ethylene polymer particles having an average particle diameter of 900 μm were introduced into the reactor in advance, nitrogen was supplied, and after a fluidized bed was formed, ethylene, hydrogen, 1-hexene, a prepolymerization catalyst, and Electrostripper (registered trademark) EA were continuously supplied under the polymerization conditions shown in Table 8 to reach a steady state. The polymerization reaction product was continuously removed from the reactor, dried using a drying device, and powders of ethylene-α-olefin copolymer (A-1) were obtained.

[0409] [Production Examples 2 to 6, 9 to 10]

[0410] (Production of ethylene-α-olefin copolymers (A-2) to (A-6), (A-9), (A-10))

[0411] The same operation as in Production Example 1 was performed except that the polymerization conditions were changed as described in Table 8, and powders of ethylene-α-olefin copolymers (A-2) to (A-6), (A-9), (A-10) were obtained. In Table 8, CHEMISTAT (registered trademark) 2500 (manufactured by Sanyo Chemical Industries, Co., Ltd.) was described as a component not used in Production Example 1.

[0412] [Production Example 7]

[0413] (Production of ethylene-α-olefin copolymer (a-7))

[0414] Using the prepolymerization catalyst component (XP-2), powders of ethylene-α-olefin copolymer (a-7) were obtained according to the production method of ethylene-based polymer (α-1) described in Japanese Patent No. 5943941.

[0415] <Measurement of properties of polymers>

[0416] [Ethylene-α-olefin copolymer (A-1)]

[0417] Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.) as a heat-resistant stabilizer and calcium stearate (manufactured by Nitto Chemical Industry Co., Ltd.) at 850 ppm and 210 ppm, respectively, were added to the powders of ethylene-α-olefin copolymer (A-1) obtained in Production Example 1, and the mixture was melt-kneaded using a twin-screw co-rotating extruder manufactured by Ito Kogyo Co., Ltd. at a set temperature of 200°C and a screw rotation speed of 300 rpm, and then extruded into a strand shape and cut to obtain pellets. The obtained pellets were used as a test sample for measurement of properties. The results of the measurement are shown in Table 9.

[0418] [Ethylene-α-olefin copolymers (A-2) to (a-7), (A-9), (A-10)]​

[0419] Except for changing the ethylene-α-olefin copolymer (A-1) to any one of the ethylene-α-olefin copolymers (A-2) to (A-7), (A-9), and (A-10) obtained in Production Examples 2 to 7, respectively, the physical property measurement of the ethylene-α-olefin copolymer (A-1) was performed, the pellets were produced, and the physical property measurement was performed. The measurement results are shown in Table 9.

[0420] [Ethylene-based polymer (a-8)]

[0421] For the high-pressure method low-density polyethylene SUNTEC-LD M2504 (density: 927 kg / m 3 , MFR: 0.4 g / 10 minutes) manufactured by Asahi Kasei Corporation, the physical property measurement was performed in the same manner as the ethylene-α-olefin copolymer (A-1) in Production Example 1. The measurement results are shown in Table 9.

[0422] [Ethylene-α-olefin copolymer (B-1)]

[0423] For Evolue SP1510 manufactured by Prime Polymer Co., Ltd., the physical property measurement was performed in the same manner as the ethylene-α-olefin copolymer (A-1) in Production Example 1. The measurement results are shown in Table 10.

[0424] [Ethylene-α-olefin copolymer (B-2)]

[0425] For Evolue SP2120 manufactured by Prime Polymer Co., Ltd., the physical property measurement was performed in the same manner as the ethylene-α-olefin copolymer (A-1) in Production Example 1. The measurement results are shown in Table 10.

[0426] [Ethylene-α-olefin copolymer (B-3)]

[0427] For Evolue SP1520 manufactured by Prime Polymer Co., Ltd., the physical property measurement was performed in the same manner as the ethylene-α-olefin copolymer (A-1) in Production Example 1. The measurement results are shown in Table 10.

[0428] [Ethylene-α-olefin copolymer (B-4)]

[0429] For Evolue SP1540 manufactured by Prime Polymer Co., Ltd., the physical property measurement was performed in the same manner as the ethylene-α-olefin copolymer (A-1) in Production Example 1. The measurement results are shown in Table 10.

[0430] <Production of ethylene-based resin composition>

[0431] [Example 1]

[0432] The pellets of the obtained ethylene-α-olefin copolymer (A-1) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0433] [Example 2]

[0434] The pellets of the obtained ethylene-α-olefin copolymer (A-1) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-2) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0435] [Example 3]

[0436] The pellets of the obtained ethylene-α-olefin copolymer (A-2) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-2) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0437] [Example 4]

[0438] The pellets of the obtained ethylene-α-olefin copolymer (A-3) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0439] [Example 5]

[0440] The pellets of the obtained ethylene-α-olefin copolymer (A-3) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-2) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0441] [Example 6]

[0442] The pellets of the obtained ethylene-α-olefin copolymer (A-4) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0443] [Example 7]

[0444] The pellets of the obtained ethylene-α-olefin copolymer (A-4) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-2) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0445] [Example 8]

[0446] The pellets of the obtained ethylene-α-olefin copolymer (A-5) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0447] [Example 9]

[0448] The pellets of the obtained ethylene-α-olefin copolymer (A-5) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-2) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0449] [Example 10]

[0450] The pellets of the obtained ethylene-α-olefin copolymer (A-6) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0451] [Example 11]

[0452] The pellets of the obtained ethylene-α-olefin copolymer (A-2) 40% by weight and the pellets of the ethylene-α-olefin copolymer (B-3) 60% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0453] [Example 12]

[0454] The pellets of the obtained ethylene-α-olefin copolymer (A-3) 8% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 92% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0455] [Example 13]

[0456] The pellets of the obtained ethylene-α-olefin copolymer (A-9) 75% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 25% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 12.

[0457] [Example 14]

[0458] The pellets of the obtained ethylene-α-olefin copolymer (A-9) 75% by weight and the pellets of the ethylene-α-olefin copolymer (B-4) 25% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 12.

[0459] [Example 15]

[0460] The pellets of the obtained ethylene-α-olefin copolymer (A-10) 60% by weight and the pellets of the ethylene-α-olefin copolymer (B-4) 40% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 12.

[0461] [Example 16]

[0462] The pellets of the obtained ethylene-α-olefin copolymer (A-10) 90% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 10% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 12.

[0463] [Comparative Example 1]

[0464] The pellets of the obtained ethylene-α-olefin copolymer (a-7) 40% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 60% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0465] [Comparative Example 2]

[0466] The pellets of the obtained ethylene-α-olefin copolymer (a-7) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0467] [Comparative Example 3]

[0468] The pellets of the obtained ethylene-α-olefin copolymer (a-7) 80% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 20% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0469] [Comparative Example 4]

[0470] The pellets of the ethylene-based polymer (a-8) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-1) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11. With respect to the melt tension of the composition, the molten resin broke when stretched, and it was not possible to measure.

[0471] [Comparative Example 5]

[0472] The pellets of the ethylene-based polymer (a-8) 20% by weight and the pellets of the ethylene-α-olefin copolymer (B-2) 80% by weight were dry blended, and inflation molding evaluation was performed. The evaluation results are shown in Table 11.

[0473] [Comparative Example 6]

[0474] The obtained pellets of ethylene-α-olefin copolymer (a-7) 80% by weight and pellets of ethylene-α-olefin copolymer (B-1) 20% by weight were dry blended and subjected to inflation molding evaluation. The evaluation results are shown in Table 12.

[0475] [Comparative Example 7]

[0476] Ethylene-α-olefin copolymer (B-4) was used for inflation molding evaluation. The melt film stability was poor and no stable film could be collected.

[0477] [Comparative Example 8]

[0478] Ethylene-α-olefin copolymer (B-1) was used for inflation molding evaluation. The evaluation results are shown in Table 12. The resin pressure at the time of molding was high and the bubble stability was slightly poor and instability was observed.

[0479] [Table 8]

[0480]

[0481] [Table 9]

[0482]

[0483] [Table 10]

[0484] Table 10

[0485]

[0486] [Table 11]

[0487]

[0488] [Table 12]

[0489]

[0490] From Table 11, it is known that the transparency of the film of the examples is excellent compared to Comparative Examples 1 to 3; the blocking resistance of the film of the examples is excellent compared to Comparative Example 4; and the mechanical strength (diametral impact) of the film of the examples is excellent compared to Comparative Example 5.

Claims

1. A vinyl resin composition (Z), characterized in that it contains: Ethylene-α-olefin copolymer (A), which is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, satisfies the following conditions (1) to (4) and (9); and Ethylene-α-olefin copolymer (B), which is a copolymer of ethylene and an α-olefin with 4 to 10 carbon atoms, satisfies the following conditions (a) to (c). (1) Density is 890 kg / m³ 3 Above 935kg / m 3 Within the following range; (2) The melt flow rate (MFR) at 190℃ and 2.16kg load is in the range of 0.1g / 10min or more and less than 3.0g / 10min; (3) Melt tension at 190°C [MT(g)] and shear viscosity at 200°C and angular velocity of 1.0 rad / s [η] * The ratio of (P) to [MT / η] * (g / P)〕 at 1.20×10 -4 Above 2.90×10 -4 Within the following range; (4) The zero-shear viscosity [η0(P)] at 200℃ and the weight-average molecular weight (Mw) measured by the GPC-VISCO method satisfy the following relationship (Eq-1); (9) The melting curve obtained by differential scanning calorimetry (DSC) has multiple peaks, 0.01×10 -13 ×Mw 3.4 ≤η0≤3.5×10 -13 ×Mw 3.4 (Eq-1); (a) Density is 890 kg / m³ 3 Above 930kg / m 3 Within the following range; (b) The melt flow rate (MFR) at 190°C and 2.16 kg load is in the range of 0.1 g / 10 min to 10 g / 10 min; (c) The intrinsic viscosity [η] (dl / g) measured in decahydronaphthalene at 135 °C and the weight-average molecular weight (Mw) measured by GPC-VISCO satisfy the following relationship (Eq-4). 1.90×10 -4 ×Mw 0.776 ≤[η]≤2.80×10 -4 ×Mw 0.776 (Eq-4)。 2. The ethylene-based resin composition (Z) according to claim 1, characterized in that: The mass fraction (W) of the above ethylene-α-olefin copolymer (A) A The mass fraction (W) of the above ethylene-α-olefin copolymer (B) is more than 1% by mass and less than 50% by mass. B ) is 50% or more of 99% by mass, of which W A With W B The total is set to 100% of the mass.

3. The ethylene-based resin composition (Z) according to claim 1, characterized in that: The mass fraction (W) of the above ethylene-α-olefin copolymer (A) A The mass fraction (W) of the above ethylene-α-olefin copolymer (B) exceeding 50% by mass and below 99% by mass B The content is 1% or more but less than 50% by mass, of which W A With W B The total is set to 100% of the mass.

4. The ethylene-based resin composition (Z) according to any one of claims 1 to 3, characterized in that: The above-mentioned ethylene-α-olefin copolymer (A) satisfies the following condition (5), (5) The number-average molecular weight (Mn), weight-average molecular weight (Mw), and Z-average molecular weight (Mz) measured by the GPC-VISCO method satisfy the following relationship (Eq-2). -7.0≤Mz / Mw-Mw / Mn≤2.0 (Eq-2).

5. The ethylene-based resin composition (Z) according to any one of claims 1 to 3, characterized in that: The ethylene-α-olefin copolymer (A) also satisfies the following condition (6), (6) The ratio of Z-average molecular weight (Mz) to weight-average molecular weight (Mw) measured by GPC-VISCO is in the range of 4.0 to 15.

0.

6. The ethylene-based resin composition (Z) according to any one of claims 1 to 3, characterized in that: The ethylene-α-olefin copolymer (A) also satisfies the following condition (7), (7) The intrinsic viscosity [η] (dl / g) measured in decahydronaphthalene at 135℃ and the weight-average molecular weight (Mw) measured by GPC-VISCO satisfy the following relationship (Eq-3). 0.7×10 -4 ×Mw 0.776 ≤[η]≤1.65×10 -4 ×Mw 0.776 (Eq-3)。 7. The ethylene-based resin composition (Z) according to any one of claims 1 to 3, characterized in that: The above-mentioned ethylene-α-olefin copolymer (A) satisfies the following condition (8), (8) Through 1 The total number of vinyl, ethylene ide, disubstituted internal olefins, and trisubstituted internal olefins per 1000 carbon atoms, as measured by H-NMR, is in the range of 0.1 to 1.0 relative to 1000 carbon atoms.

8. The ethylene-based resin composition (Z) according to any one of claims 1 to 3, characterized in that: It also contains thermoplastic resins, but does not include the ethylene-α-olefin copolymer (A) and ethylene-α-olefin copolymer (B) mentioned above.

9. A molded body, characterized in that, The ethylene-based resin composition (Z) comprising any one of claims 1 to 8.

10. A membrane, characterized in that, The ethylene-based resin composition (Z) comprising any one of claims 1 to 8.

11. A multilayer film, characterized in that, It comprises a layer formed from the ethylene-based resin composition (Z) according to any one of claims 1 to 8.

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