Propylene resin composition, film, and method for producing film

Abstract

Provided is a propylene resin composition containing (A) a propylene polymer having a melting point of 120°C or higher, (B) a propylene-alpha-olefin copolymer that satisfies a specific requirement, (C) a modified polyolefin having a constituent unit derived from an unsaturated carboxylic acid and / or a derivative thereof, and (D) an ethylene polymer. When the total content of (A), (B), (C), and (D) is taken to be 100 mass parts, the content of (A) is 45-79.9 mass parts, the content of (B) is 15-40 mass parts, the content of (C) is 0.1-10 mass parts, and the content of (D) is 5-30 mass parts.

Description

Propylene-based resin composition, film, and method for producing film

[0001] The present disclosure relates to a propylene-based resin composition, a film, and a method for producing the film.

[0002] Propylene-based polymers are used as thermoplastic molding materials with excellent rigidity, heat resistance, etc. Propylene-based polymers are nonpolar materials, and therefore have poor adhesion to polar materials, such as ethylene-vinyl alcohol copolymers. To improve adhesion, propylene-based resin compositions are known in which modified polyolefins, obtained by modifying polyolefins with unsaturated carboxylic acids and / or derivatives thereof, are blended with propylene-based polymers (e.g., Patent Documents 1 and 2).

[0003] JP-A-9-111069 JP-A-4-300933

[0004] Depending on the application, a layer or film formed from a propylene-based resin composition may be subjected to deformation processing such as drawing or bending. Specific applications requiring deformation processing include, for example, food packaging materials, construction materials, and packaging materials for lithium-ion batteries. However, layers or films formed from conventional propylene-based resin compositions tend to whiten due to deformation processing.

[0005] The present inventors have investigated blending a soft elastomer component with a propylene-based polymer in order to improve whitening resistance during deformation processing. The present inventors have found that although whitening resistance can be improved by increasing the content of the propylene-based elastomer component as the soft elastomer component in a propylene-based resin composition, mechanical strength in a high-temperature atmosphere may decrease. The present disclosure aims to provide a propylene-based resin composition capable of forming a layer or film that is excellent in whitening resistance during deformation processing and mechanical strength in a high-temperature atmosphere.

[0006] One aspect of the propylene-based resin composition of the present disclosure comprises: (A) a propylene-based polymer having a melting point (Tm) of 120°C or higher as measured by differential scanning calorimetry (DSC); (B) a propylene-α-olefin copolymer having a structural unit (i) derived from propylene and a structural unit (ii) derived from an α-olefin having 5 to 20 carbon atoms, and satisfying the following requirements (B1) to (B4); (C) a modified polyolefin having a structural unit derived from an unsaturated carboxylic acid and / or a derivative thereof; and (D) an ethylene-based polymer, wherein, when the total content of (A), (B), (C), and (D) is 100 parts by mass, the content of (A) is 45 to 79.9 parts by mass, the content of (B) is 15 to 40 parts by mass, the content of (C) is 0.1 to 10 parts by mass, and the content of (D) is 5 to 30 parts by mass. (B1) When the total content of the structural unit (i) and the structural unit (ii) is taken as 100 mol %, the content of the structural unit (i) is 75 to 93 mol %, and the content of the structural unit (ii) is 7 to 25 mol %; (B2) The density measured at 25°C in accordance with ASTM D1505 is 851 to 900 kg / m 3 (B3) The intrinsic viscosity [η] in decalin solvent at 135°C is 1.6 to 5.0 dl / g; (B4) The melting point (Tm) measured by differential scanning calorimetry (DSC) is less than 110°C or is not observed.

[0007] According to the present disclosure, it is possible to provide a propylene-based resin composition capable of forming a layer or film that is excellent in whitening resistance during deformation processing and mechanical strength in a high-temperature atmosphere.

[0008] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. A numerical range "A to B" indicates A or more and B or less. In this specification, when the units of the numerical values ​​written before and after "to" that indicate a numerical range are the same, the unit of the numerical value written before "to" may be omitted. For example, "851 kg / m 3 ~900 kg / m 3 " to "851 to 900 kg / m3 ". In this specification, when referring to the amount of each component in a composition, if the composition contains multiple substances corresponding to each component, it means the total amount of multiple substances present in the composition, unless otherwise specified. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, unless otherwise specified, each component in the composition or each structural unit in the polymer (resin) may be contained in one type or in two or more types. In this specification, room temperature means 23°C.

[0009] [Propylene-Based Resin Composition] The propylene-based resin composition of the present disclosure (hereinafter also referred to as "the composition") contains a propylene-based polymer (A), a propylene-α-olefin copolymer (B), a modified polyolefin (C) having structural units derived from an unsaturated carboxylic acid and / or a derivative thereof, and an ethylene-based polymer (D), each of which will be explained below.

[0010] <Propylene-Based Polymer (A)> The propylene-based polymer (A) may be, for example, a homopolymer of propylene (homopolypropylene), or a copolymer of propylene and an α-olefin other than propylene having 2 to 20 carbon atoms. The copolymer may be, for example, a random copolymer (random polypropylene) or a block copolymer. The propylene-based polymer (A) is preferably a homopolypropylene or a random copolymer of propylene and an α-olefin other than propylene having 2 to 20 carbon atoms.

[0011] The propylene polymer (A) may have at least one structural unit derived from a biomass-derived monomer. Examples of the biomass-derived monomer include biomass-derived propylene, biomass-derived ethylene, and biomass-derived α-olefins having 4 to 20 carbon atoms. The same type of monomer constituting the polymer may be only biomass-derived monomers, only fossil fuel-derived monomers, or both biomass-derived monomers and fossil fuel-derived monomers.

[0012] As the random copolymer, a copolymer of propylene and an α-olefin having 2 to 10 carbon atoms other than propylene is preferred, and specifically, a copolymer of propylene and ethylene, or a copolymer of propylene, ethylene and an α-olefin having 4 to 10 carbon atoms is preferred.

[0013] The content of structural units derived from propylene in the random copolymer is preferably 65 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, even more preferably 92 mol% or more, particularly preferably 92.5 mol% or more, and preferably 99.9 mol% or less, more preferably 99.8 mol% or less, based on 100 mol% of the total of structural units derived from propylene and structural units derived from α-olefins having 2 to 20 carbon atoms other than propylene. The content of structural units derived from α-olefins having 2 to 20 carbon atoms other than propylene in the random copolymer is preferably 35 mol% or less, more preferably 30 mol% or less, even more preferably 10 mol% or less, even more preferably 8 mol% or less, particularly preferably 7.5 mol% or less, and preferably 0.1 mol% or more, more preferably 0.2 mol% or more, based on 100 mol% of the total of structural units derived from propylene and structural units derived from α-olefins having 2 to 20 carbon atoms other than propylene. The content of the above structural units is 13 It can be measured by C-NMR.

[0014] Examples of the α-olefins having 2 to 20 carbon atoms other than propylene include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-nonadecene, and 1-eicosene. One or more of the α-olefins having 2 to 20 carbon atoms other than propylene may be used.

[0015] The melting point (Tm) of the propylene polymer (A) measured by a differential scanning calorimeter (DSC) is preferably 120° C. or higher, more preferably 125 to 170° C., still more preferably 130 to 168° C., and particularly preferably 135 to 165° C. A melting point within the above range is preferred because it provides a good balance between moldability and heat resistance and good properties as a crystalline polypropylene.

[0016] The melting point of the propylene polymer (A) is the melting point (the temperature at the apex of the melting peak) observed using a DSC when the polymer is heated from room temperature to 200°C at a heating rate of 10°C / min, held at 200°C for 10 minutes, cooled to -20°C at a heating rate of 10°C / min, held at -20°C for 1 minute, and then heated again to 200°C at a heating rate of 10°C / min. The heat of fusion (ΔH), which is the integrated value of the melting peak, is preferably 50 to 120 J / g. When two or more melting peaks are observed, the highest temperature among the apex temperatures of these peaks is taken as the melting point.

[0017] The melt flow rate (MFR) of the propylene polymer (A) is, for example, 0.1 to 500 g / 10 min, preferably 0.5 g / 10 min or more, more preferably 1 g / 10 min or more, and preferably 300 g / 10 min or less, more preferably 200 g / 10 min or less, even more preferably 100 g / 10 min or less, and particularly preferably 90 g / 10 min or less, 50 g / 10 min or less, 30 g / 10 min or less, or 10 g / 10 min or less. When the MFR is within the above range, a composition with excellent moldability can be easily obtained, and a composition or film with excellent dispersibility between the propylene polymer (A) and the propylene-α-olefin copolymer (B) described below and excellent mechanical strength such as tensile strength can be easily obtained. The MFR of the propylene polymer (A) is measured in accordance with ASTM D1238E under conditions of 230°C and a load of 2.16 kg.

[0018] The propylene polymer (A) may have either an isotactic structure or a syndiotactic structure, and either structure may be selected in consideration of the compatibility between the propylene polymer (A) and the propylene-α-olefin copolymer (B) described below.

[0019] The propylene polymer (A) contained in the present composition may be one type or two or more types. The propylene polymer (A) may be, for example, a homopolypropylene or a random polypropylene, or may be a mixture of a homopolypropylene and a random polypropylene from the viewpoint of a balance between adhesiveness, whitening resistance, and the like. When the present composition contains a homopolypropylene and a random polypropylene as the propylene polymer (A), the content of the random polypropylene is preferably 10 to 300 parts by mass, more preferably 50 to 250 parts by mass, and even more preferably 100 to 200 parts by mass, per 100 parts by mass of the homopolypropylene.

[0020] The propylene polymer (A) can be produced by various known methods using a catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.

[0021] <Propylene / α-olefin copolymer (B)> The propylene / α-olefin copolymer (B) (hereinafter also referred to as "copolymer (B)") has a structural unit (i) derived from propylene and a structural unit (ii) derived from an α-olefin having 5 to 20 carbon atoms.

[0022] Copolymer (B) satisfies the following requirements (B1) to (B4): (B1) When the total content of structural unit (i) and structural unit (ii) is taken as 100 mol %, the content of structural unit (i) is 75 to 93 mol %, and the content of structural unit (ii) is 7 to 25 mol %. (B2) The density, measured at 25°C in accordance with ASTM D1505, is 851 to 900 kg / m 3 (B3) The intrinsic viscosity [η] in decalin solvent at 135°C is 1.6 to 5.0 dl / g. (B4) The melting point (Tm) measured by differential scanning calorimetry (DSC) is less than 110°C or is not observed.

[0023] The copolymer (B) is a soft elastomer component having an excellent balance between flexibility and mechanical strength. The present composition containing the copolymer (B) together with the propylene-based polymer (A), the modified polyolefin (C), and the ethylene-based polymer (D) is, for example, an adhesive resin composition having an excellent balance between whitening resistance and mechanical strength.

[0024] The copolymer (B) is not particularly limited as long as it is a copolymer obtained by using at least propylene and one or more α-olefins having 5 to 20 carbon atoms. The copolymer (B) is preferably a random copolymer.

[0025] The content of the structural unit (i) is 75 to 93 mol%, preferably 80 to 93 mol%, more preferably 83 to 93 mol%, and even more preferably 83 to 89 mol%. The content of the structural unit (ii) is 7 to 25 mol%, preferably 7 to 20 mol%, more preferably 7 to 17 mol%, and even more preferably 11 to 17 mol%. A film formed from the present composition containing such a copolymer (B) has an excellent balance between whitening resistance and mechanical strength. The contents of the structural unit (i) and the structural unit (ii) are calculated based on the total content of the structural unit (i) and the structural unit (ii) taken as 100 mol%. The contents of the structural unit (i) and the structural unit (ii) are 13 It can be measured by C-NMR, specifically by the method described in the Examples section.

[0026] Copolymer (B) having the content of the structural unit (i) and the structural unit (ii) within the above range tends to have a good balance of flexibility and mechanical strength, and in particular tends to have a good balance of flexibility and tensile strength.

[0027] Examples of α-olefins having 5 to 20 carbon atoms include 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-nonadecene, and 1-eicosene. Among these, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene are preferred because they can produce a crystalline structure with many tie molecules and result in a copolymer that is superior in balance between flexibility and tensile strength, and 4-methyl-1-pentene is more preferred because they can result in a copolymer that is superior in tensile strength.

[0028] In producing copolymer (B), at least one α-olefin having 5 to 20 carbon atoms is used, and two or more types may be used, but preferably one α-olefin is used. Copolymer (B) has at least one structural unit (ii) derived from an α-olefin having 5 to 20 carbon atoms, and may have two or more types, but preferably has one structural unit (ii).

[0029] The copolymer (B) may further contain other structural units in addition to the structural unit (i) and the structural unit (ii). Examples of polymerizable monomers that derive other structural units include ethylene, 1-butene, vinyl compounds, vinyl esters, conjugated dienes, and non-conjugated polyenes. The total content of the structural units (i) and (ii) in the copolymer (B) is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 98% by mass or more, based on the mass of the copolymer (B).

[0030] The copolymer (B) may have at least one structural unit derived from a biomass-derived monomer. Examples of the biomass-derived monomer include biomass-derived propylene and biomass-derived α-olefins having 5 to 20 carbon atoms. The same type of monomer constituting the copolymer may be only biomass-derived monomers, only fossil fuel-derived monomers, or both biomass-derived monomers and fossil fuel-derived monomers.

[0031] The density of the copolymer (B) is 851 to 900 kg / m 3 and preferably 851 to 890 kg / m 3 , more preferably 851 to 880 kg / m 3 , more preferably 855 to 875 kg / m 3 The copolymer (B) having a density within the above range has excellent flexibility. The density is measured at 25°C in accordance with ASTM D1505. The density of the copolymer (B) can be adjusted, for example, by the contents of the structural units (i) and (ii).

[0032] The intrinsic viscosity [η] of the copolymer (B) is 1.6 to 5.0 dl / g, preferably 1.6 to 4.0 dl / g, and more preferably 1.8 to 2.5 dl / g. The copolymer (B) having an intrinsic viscosity [η] within the above range exhibits excellent moldability, mechanical strength, and low stickiness. The intrinsic viscosity [η] is measured at 135°C in decalin solvent.

[0033] The melting point (Tm) of copolymer (B) is less than 110°C or is not observed. If a melting point is observed, the melting point is preferably 90°C or less, more preferably 85°C or less. The lower limit is not particularly limited, but it may be 50°C or more, or even 55°C or more. If a melting point is observed, the melting point is preferably 50°C or more but less than 110°C, more preferably 50 to 90°C, even more preferably 55 to 90°C, and particularly preferably 55 to 85°C. Copolymer (B) having a melting point within the above range or no observed melting point has excellent flexibility. The melting point (Tm) of copolymer (B) can be adjusted, for example, by the content of structural units (i) and (ii).

[0034] The melting point is measured by DSC, specifically by the method described in the Examples section. The melting point refers to the temperature at the apex of the melting peak. "No melting point observed in DSC measurement" means that no melting peak is observed in DSC measurement. "No melting peak observed" means that no crystalline melting peak with a heat of crystalline fusion (ΔH) of 1 J / g or more is observed in the range of -70 to 200°C. When two or more melting peaks are observed, the highest temperature among the apex temperatures of these peaks is the melting point.

[0035] When a melting peak is observed, the heat of fusion (ΔH), which is the integrated value of the melting peak, is preferably 1 to 50 J / g, more preferably 5 to 45 J / g, and even more preferably 10 to 40 J / g. A copolymer (B) having ΔH in the above range exhibits a good balance between flexibility and low stickiness.

[0036] The weight average molecular weight (Mw) of copolymer (B) is preferably 100,000 to 550,000, more preferably 200,000 to 525,000, and even more preferably 300,000 to 500,000. Copolymer (B) having an Mw within the above range exhibits excellent moldability, mechanical strength, and low stickiness. Mw is a value measured by gel permeation chromatography (GPC) and converted into polystyrene equivalent. Details of the measurement conditions are described in the Examples section.

[0037] The ratio (Mw / Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the copolymer (B) is preferably 1.0 to 3.5, more preferably 1.4 to 3.0, and even more preferably 1.7 to 2.5. Copolymer (B) with an Mw / Mn in the above range exhibits a good balance of mechanical strength, impact resistance, and low stickiness. Mw / Mn is an index indicating molecular weight distribution. Mw and Mn are values ​​measured by gel permeation chromatography (GPC) and converted into polystyrene equivalents. Details of the measurement conditions are described in the Examples section.

[0038] The MFR of copolymer (B) is preferably 0.1 to 30 g / 10 min, more preferably 0.2 to 15 g / 10 min, and even more preferably 1 to 10 g / 10 min. Copolymer (B) having an MFR in the above range exhibits a good balance of moldability, mechanical strength, and low stickiness. The MFR of copolymer (B) is measured in accordance with ASTM D1238E under conditions of 230°C and a load of 2.16 kg.

[0039] The glass transition temperature (Tg) of the copolymer (B) is preferably −20 to 5° C., more preferably −15 to 0° C., and even more preferably −12 to −3° C. The copolymer (B) having a Tg in the above range has excellent shape conformability. Tg is measured by DSC, specifically, by the method described in the Examples section.

[0040] The copolymer (B) has a breaking stress of preferably 10 to 40 MPa, more preferably 13 to 37 MPa, and even more preferably 15 to 35 MPa. The copolymer (B) has a tensile modulus of preferably 1 to 250 MPa, more preferably 3 to 230 MPa, and even more preferably 5 to 200 MPa.

[0041] The stress at break and tensile modulus of copolymer (B) are measured using dumbbell test pieces prepared as follows: Copolymer (B) is heated for 5 minutes using a hydraulic hot press set at 190°C, molded under a pressure of 7.5 MPa for 2 minutes, and then cooled at 20°C under a pressure of 7.5 MPa for 5 minutes to produce a 2 mm-thick sheet. After 7 days or more have passed at room temperature since molding, ASTM No. 4 dumbbells are prepared from the sheet in accordance with ASTM D638, and the tensile modulus and stress at break are measured for the dumbbells at 23°C and a pulling rate of 50 mm / min.

[0042] The Shore A hardness (instantaneous value) of the copolymer (B) is preferably 25 to 99, more preferably 28 to 98, even more preferably 50 to 98, and particularly preferably 55 to 97. When it is difficult to measure the Shore A hardness, a similar evaluation can be performed using the Shore D hardness instead, and the Shore D hardness (instantaneous value) of the copolymer (B) is preferably 12 to 62, and more preferably 16 to 60.

[0043] The Shore A hardness and Shore D hardness of copolymer (B) are values ​​measured on a test piece prepared as follows. Using a hydraulic hot press molding machine set at 190°C, copolymer (B) is heated for 5 minutes, molded under a pressure of 7.5 MPa for 2 minutes, and then cooled at 20°C under a pressure of 7.5 MPa for 5 minutes to prepare a sheet with a thickness of 2 mm. Three of these sheets are stacked to prepare a test piece. After 7 days or more have passed at room temperature since the molding, a durometer (type A or type D) is used in accordance with ASTM D2240, and the scale is read immediately after the indenter is brought into contact with the test piece. In this way, the Shore A hardness and Shore D hardness are obtained.

[0044] The copolymer (B) contained in the present composition may be one type or two or more types.

[0045] (Method for Producing Copolymer (B)) The copolymer (B) can be suitably produced by a method comprising a step of polymerizing propylene and at least one olefin selected from α-olefins having 5 to 20 carbon atoms in the presence of an olefin polymerization catalyst described below. By using such an olefin polymerization catalyst and appropriately setting the polymerization conditions within the ranges described below, the copolymer (B) satisfying the above-mentioned requirements can be easily produced.

[0046] The olefin polymerization catalyst is preferably a catalyst containing a bridged metallocene compound (a) and at least one compound (b) selected from the following (b-1) to (b-3): (b-1) an organoaluminum oxy compound, (b-2) an ionic compound that reacts with the bridged metallocene compound (a) to form an ion pair, and (b-3) an organoaluminum compound.

[0047] <Bridged Metallocene Compound (a)> The bridged metallocene compound (a) is preferably a bridged metallocene compound represented by the following formula [a1], and more preferably a bridged metallocene compound represented by the following formula [a2]. One or more bridged metallocene compounds (a) may be used.

[0048]

[0049] The meanings of the symbols in formula [a1] are as follows: M is a Group 4 transition metal, such as a titanium atom, a zirconium atom, or a hafnium atom; j is an integer of 1 to 4; Q is selected from a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair; when j is an integer of 2 to 4, multiple Qs may be the same or different; R A and R B may be the same or different and are mononuclear or polynuclear hydrocarbon residues capable of forming a sandwich structure with M. Y is a carbon atom or a silicon atom. R C and R D may be the same or different and are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group, and may be bonded to each other to form a ring.

[0050]

[0051] The meanings of the symbols in formula [a2] are as follows: 1 is a hydrocarbon group, a silicon-containing group, or a halogen-containing hydrocarbon group. 2 ~R 10 are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different, and the respective substituents may be bonded to each other to form a ring. M is a Group 4 transition metal. j is an integer of 1 to 4. Q is selected from a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair. When j is an integer of 2 to 4, multiple Qs may be the same or different.

[0052] Among the bridged metallocene compounds represented by formula [a2], a bridged metallocene compound represented by the following formula [a3] is particularly preferred in terms of polymerization properties, availability, and the ease with which a propylene / α-olefin copolymer satisfying the above requirements can be obtained.

[0053]

[0054] The meanings of the symbols in formula [a3] are as follows: 1b is a hydrocarbon group, a silicon-containing group, or a halogen-containing hydrocarbon group. 2b ~R 12b are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group, and may be the same or different, and the respective substituents may be bonded to each other to form a ring. M is a Group 4 transition metal. n is an integer of 1 to 3. j is an integer of 1 to 4. Q is selected from a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair. When j is an integer of 2 to 4, multiple Qs may be the same or different.

[0055] R 1 From R 10 and R 1b From R 12b Examples of the hydrocarbon group in include a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, and a group in which one or more hydrogen atoms of a saturated hydrocarbon group are substituted with a cyclic unsaturated hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10.

[0056] Examples of the linear hydrocarbon group include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decanyl group; and linear alkenyl groups such as an allyl group.

[0057] Examples of branched hydrocarbon groups include branched alkyl groups such as an isopropyl group, a tert-butyl group, a tert-amyl group, a 3-methylpentyl group, a 1,1-diethylpropyl group, a 1,1-dimethylbutyl group, a 1-methyl-1-propylbutyl group, a 1,1-propylbutyl group, a 1,1-dimethyl-2-methylpropyl group, and a 1-methyl-1-isopropyl-2-methylpropyl group.

[0058] Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a methylcyclohexyl group; and polycyclic groups such as a norbornyl group, an adamantyl group, and a methyladamantyl group.

[0059] Examples of the cyclic unsaturated hydrocarbon group include aryl groups such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group; cycloalkenyl groups such as a cyclohexenyl group; and polycyclic unsaturated alicyclic groups such as a 5-bicyclo[2.2.1]hept-2-enyl group.

[0060] Examples of the group in which one or more hydrogen atoms of a saturated hydrocarbon group are substituted with a cyclic unsaturated hydrocarbon group include groups in which one or more hydrogen atoms of an alkyl group are substituted with an aryl group, such as a benzyl group, a cumyl group, a 1,1-diphenylethyl group, and a triphenylmethyl group.

[0061] R 1 From R 10 and R 1b From R 12b Examples of the silicon-containing group in the formula include groups represented by the formula -SiR3 (wherein the multiple Rs are each independently an alkyl group or a phenyl group having 1 to 15 carbon atoms), such as a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group.

[0062] R 1 From R 10 and R 1b From R 12b Examples of the halogen-containing hydrocarbon group in the above formula include groups in which one or more hydrogen atoms of the hydrocarbon group are substituted with halogen atoms, such as a trifluoromethyl group.

[0063] R 2 From R 10 and R 2b From R 12b Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0064] R 2 From R 10 and R 2b From R 12b Among the substituents up to 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 8 and R 9 , R 9 and R 10 , R 2b and R 3b , R 3b and R 4b , R 5b and R 6b , R 6b and R 7b , R 8b and R 9b , R 9b and R 10b , R 10b and R 11b , R 11b and R 12b ) may be bonded to each other to form a ring, and the ring formation may occur at two or more positions in the molecule.

[0065] In this specification, examples of rings formed by bonding two substituents together (spiro rings, additional rings) include alicyclic rings and aromatic rings. Specific examples include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, and a cyclopentene ring, with a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring being preferred. Furthermore, such ring structures may further have a substituent such as an alkyl group on the ring.

[0066] R 1 and R 1bis preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, still more preferably not an aryl group, particularly preferably a linear hydrocarbon group, a branched hydrocarbon group, or a cyclic saturated hydrocarbon group, and particularly preferably a group in which the carbon having a free valence (the carbon bonded to the cyclopentadienyl ring) is a tertiary carbon.

[0067] R 1 and R 1b Specific examples of R include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group. 1 and R 1b is more preferably a substituent in which the carbon having a free valence is a tertiary carbon, such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, or a 1-adamantyl group, and particularly preferably a tert-butyl group or a 1-adamantyl group.

[0068] R 8 In one embodiment, R is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, and even more preferably an ethyl group. 8 is R 9 may be bonded to form a ring.

[0069] In the formula [a2] and the formula [a3], the fluorene ring portion is not particularly limited as long as it has a structure obtained from a known fluorene or fluorene derivative. 4 and R 5 is preferably a hydrogen atom from the viewpoint of stereoregularity and molecular weight. 4b and R 5b is preferably a hydrogen atom from the viewpoints of stereoregularity and molecular weight.

[0070] R 2 , R 3 , R 6 and R 7are preferably hydrogen atoms or hydrocarbon groups, more preferably at least two of them are hydrocarbon groups, and even more preferably at least two of them are hydrocarbon groups having 1 to 20 carbon atoms. 2 and R 3 are bonded to each other to form a ring, and R 6 and R 7 may be bonded to each other to form a ring. 2b , R 3b , R 6b and R 7b are preferably hydrogen atoms or hydrocarbon groups, more preferably at least two of them are hydrocarbon groups, and even more preferably at least two of them are hydrocarbon groups having 1 to 20 carbon atoms. 2b and R 3b are bonded to each other to form a ring, and R 6b and R 7b may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include a benzofluorenyl group, a dibenzofluorenyl group, an octahydrodibenzofluorenyl group, a 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group, a 1,1,3,3,6,6,8,8-octamethyl-2,3,6,7,8,10 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group, and 1',1',3',6',8',8'-hexamethyl-1'H,8'H-dicyclopenta[b,h]fluorenyl group are particularly preferred.

[0071] R 9 and R 10 In one embodiment, R is preferably a hydrocarbon group, and particularly preferably an aryl group. 9 is R 8 may be bonded to form a ring, in which case R 10 is preferably a hydrocarbon group, and particularly preferably an alkyl group.

[0072] R 8b is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and even more preferably a hydrogen atom or a methyl group.

[0073] R 9b is more preferably a hydrocarbon group, further preferably an alkyl group having one or more carbon atoms such as a linear alkyl group or a branched alkyl group, a cycloalkyl group or a cycloalkenyl group, and particularly preferably an alkyl group having one or more carbon atoms.

[0074] From a synthetic point of view, R 10b and R 11b is also preferably a hydrogen atom. Or, when n=1, R 9b and R 10b are more preferably bonded to each other to form a ring, and the ring is particularly preferably a six-membered ring such as a cyclohexane ring. 11b is preferably a hydrogen atom.

[0075] R 12b is preferably a hydrocarbon group, and particularly preferably an alkyl group.

[0076] M is a Group 4 transition metal, for example, Ti, Zr or Hf, preferably Zr or Hf, and particularly preferably Zr.

[0077] Q represents a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair.

[0078] Examples of halogen atoms in Q include fluorine, chlorine, bromine, and iodine.

[0079] The hydrocarbon group for Q is preferably an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 2-methylpropyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1,1-diethylpropyl group, a 1-ethyl-1-methylpropyl group, a 1,1,2,2-tetramethylpropyl group, a sec-butyl group, a tert-butyl group, a 1,1-dimethylbutyl group, a 1,1,3-trimethylbutyl group, and a neopentyl group. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclohexylmethyl group, a cyclohexyl group, and a 1-methyl-1-cyclohexyl group. It is more preferable that the hydrocarbon group have 5 or fewer carbon atoms.

[0080] Examples of neutral conjugated or non-conjugated dienes having 10 or less carbon atoms include s-cis- or s-trans-η 4 -1,3-butadiene, s-cis- or s-trans-η 4 -1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η 4 -3-methyl-1,3-pentadiene, s-cis- or s-trans-η 4 -1,4-dibenzyl-1,3-butadiene, s-cis- or s-trans-η 4 -2,4-hexadiene, s-cis- or s-trans-η 4 -1,3-pentadiene, s-cis- or s-trans-η 4 -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η 4 and 1,4-bis(trimethylsilyl)-1,3-butadiene.

[0081] Examples of anionic ligands include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; and sulfonate groups such as mesylate and tosylate.

[0082] Examples of neutral ligands capable of coordinating with lone electron pairs include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ethers such as tetrahydrofuran (THF), diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0083] A preferred embodiment of Q is a halogen atom or an alkyl group having 1 to 5 carbon atoms.

[0084] n is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. When n is within the above range, the propylene / α-olefin copolymer can be efficiently obtained, which is preferable.

[0085] j is an integer of 1 to 4, preferably 2.

[0086] The above describes the structure of the bridged metallocene compound represented by formula [a2] or formula [a3], i.e., R 1 ~R 10 , R 1b ~R 12b Preferred embodiments of M, n, Q, and j have been described above. Any combination of the preferred embodiments of the bridged metallocene compound (a) is also a preferred embodiment. Such a bridged metallocene compound can be suitably used to obtain the copolymer (B) having the above-described physical properties.

[0087] An example of the bridged metallocene compound represented by the formula [a2] is diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride.

[0088] Examples of the bridged metallocene compound represented by formula [a3] include (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride and catalyst (b) described in Japanese Patent No. 6568082. Here, the octamethylfluorene refers to 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorene.

[0089] Other examples of the bridged metallocene compound represented by the formula [a1] include R A and R B may be the same or different, are a substituted indenyl group, and Y is a silicon atom. Examples of the substituent in the substituted indenyl group include a halogen atom, a hydrocarbon group, a silicon-containing group, and a halogen-containing hydrocarbon group. Specific examples of these include R in the formula [a2] and formula [a3]. 1 and R 2 and the like. C , R D and MQ j The R moiety is as described in the formula [a2] and formula [a3] sections. 9 , R 10 and MQ j Examples of such bridged metallocene compounds include dimethylsilylene-bis{1-(2-n-propyl-4-phenanthryl indenyl)}zirconium dichloride and dimethylsilylene-bis{1-(2-n-propyl-4-phenanthryl indenyl)}hafnium dichloride.

[0090] <Compound (b)> The compound (b) is at least one compound selected from an organoaluminum oxy-compound (b-1), an ionic compound (b-2) that reacts with the bridged metallocene compound (a) to form an ion pair, and an organoaluminum compound (b-3).

[0091] (Organoaluminum oxy compound (b-1)) Examples of the organoaluminum oxy compound (b-1) include conventionally known aluminoxanes such as compounds represented by the following formula [b1] and compounds represented by the following formula [b2], modified methylaluminoxanes having a structure represented by the following formula [b3], and boron-containing organoaluminum oxy compounds represented by the following formula [b4]. One or more types of organoaluminum oxy compound (b-1) may be used.

[0092]

[0093] In formula [b1] and formula [b2], R is a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group, and multiple Rs may be the same or different, and n is an integer of 2 or greater, preferably 3 or greater, and more preferably 10 or greater. In formula [b1] and formula [b2], methylaluminoxane in which R is a methyl group is preferably used.

[0094]

[0095] In formula [b3], Me is a methyl group, R is a hydrocarbon group having 2 to 10 carbon atoms, and m and n are each independently an integer of 2 or greater. Multiple Rs may be the same or different. Modified methylaluminoxane [b3] can be prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such modified methylaluminoxane [b3] is generally called MMAO (modified methyl aluminoxane). MMAO can be prepared, for example, by the methods described in U.S. Pat. Nos. 4,960,878 and 5,041,584.

[0096] Modified methylaluminoxanes prepared using trimethylaluminum and triisobutylaluminum (i.e., R is an isobutyl group in formula [b3]) are commercially produced by Tosoh Finechem Corporation and other companies under the trade names MMAO and TMAO.

[0097] MMAO is an aluminoxane with improved solubility in various solvents and improved storage stability. Specifically, unlike compounds that are insoluble or poorly soluble in benzene, such as the compounds represented by formula [b1] or [b2], MMAO is soluble in aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and the like.

[0098]

[0099] In formula [b4], R c is a hydrocarbon group having 1 to 10 carbon atoms, and there are multiple R d are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms. In a production method using an olefin polymerization catalyst, a propylene-α-olefin copolymer can be produced even at high temperatures as described below. Therefore, organoaluminum oxy compounds that are insoluble or slightly soluble in benzene, such as those exemplified in JP-A No. 2-78687, can also be used. Organoaluminum oxy compounds described in JP-A No. 2-167305 and aluminoxanes having two or more alkyl groups, such as those described in JP-A No. 3-103407, can also be suitably used.

[0100] The "benzene-insoluble or sparingly soluble" organoaluminum oxy-compound refers to an organoaluminum oxy-compound that is insoluble or sparingly soluble in benzene, and in which the amount of the compound that dissolves in benzene at 60°C is usually 10% by mass or less, preferably 5% by mass or less, and particularly preferably 2% by mass or less, calculated as Al atoms.

[0101] (Ionic Compound (b-2)) Examples of the compound (b-2) (hereinafter also referred to as "ionic compound (b-2)") that reacts with the bridged metallocene compound (a) to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in, for example, JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, JP-A-2004-51676, and U.S. Pat. No. 5,321,106. Further examples of the ionic compound (b-2) include heteropoly compounds and isopoly compounds. Among these, compounds represented by the following formula [b5] are preferred. The ionic compound (b-2) may be used alone or in combination of two or more.

[0102]

[0103] In formula [b5], R e+ For example, H + , oxonium cation, carbenium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation with a transition metal. f , R g , R h and R i each independently represents an organic group, preferably an aryl group or a halogen-substituted aryl group.

[0104] Examples of carbenium cations include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation, and tris(dimethylphenyl)carbenium cation.

[0105] Examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N,2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.

[0106] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation, and tris(dimethylphenyl)phosphonium cation.

[0107] R e+ Among the above examples, carbenium cations and ammonium cations are preferred, and triphenylcarbenium cation, N,N-dimethylanilinium cation, and N,N-diethylanilinium cation are particularly preferred.

[0108] ・R e+ is a carbenium cation (carbenium salt): Examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(3,5-ditrifluoromethylphenyl)borate, tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate, and tris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl)borate.

[0109] ・R e+When is an ammonium cation (ammonium salt): Examples of the ammonium salt include trialkylammonium salts, N,N-dialkylanilinium salts, and dialkylammonium salts.

[0110] Specific examples of the trialkylammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis(o-tolyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(4-trifluoromethylphenyl)borate, and tri(n- tri(n-butyl)ammonium tetrakis(o-tolyl)borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis(p-tolyl)borate, dioctadecylmethylammonium tetrakis(o-tolyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(4-trifluoromethylphenyl)borate, and dioctadecylmethylammonium tetrakis(3,5-ditrifluoromethylphenyl)borate.

[0111] Specific examples of N,N-dialkylanilinium salts include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N,2,4,6-pentamethylanilinium tetraphenylborate, and N,N,2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate.

[0112] Specific examples of dialkylammonium salts include diisopropylammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

[0113] (Organoaluminum Compound (b-3)) Examples of the organoaluminum compound (b-3) include an organoaluminum compound represented by the following formula [b6] and an alkylated complex of a metal of Group 1 of the periodic table with aluminum represented by the following formula [b7]. One or more types of organoaluminum compound (b-3) may be used.

[0114] R a m Al (OR b ) n H p X q ...[b6] In formula [b6], R a and R b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m is a number that satisfies 0<m≦3, n is a number that satisfies 0≦n<3, p is a number that satisfies 0≦p<3, q is a number that satisfies 0≦q<3, and m+n+p+q=3.

[0115] M 2 AlR a 4 ... [b7] In formula [b7], M 2is Li, Na or K, and there are multiple R a are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

[0116] Examples of the organoaluminum compound [b6] include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, and trioctylaluminum; tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritolylaluminum; and compounds of the formula (i-CH) x Al y (C5H 10 ) z (wherein x, y, and z are positive numbers, and z≦2x); alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; a 2.5 Al (OR b ) 0.5 (In the formula, R a and R b is R in formula [b6] a and R bpartially alkoxylated alkylaluminums having an average composition represented by the formula (I); alkylaluminum aryloxides such as diethylaluminum phenoxide and diethylaluminum (2,6-ditert-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; ethylaluminum dichloride; partially halogenated alkylaluminums such as alkylaluminum dihalides such as aluminum hydride; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, diisopropylaluminum hydride, and diisobutylaluminum hydride; partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; and partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

[0117] Examples of the alkylated complex [b7] include LiAl(C2H5)4 and LiAl(C7H 15 ) 4. Compounds similar to the alkylated complex [b7] can also be used, specifically organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms. Examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2.

[0118] As the organoaluminum compound (b-3), trimethylaluminum and triisobutylaluminum are preferred because they are readily available.

[0119] <<Carrier (c)>> A carrier (c) may be used as a component of the olefin polymerization catalyst. The carrier (c) is preferably an inorganic or organic compound that is a granular or particulate solid. One type of carrier (c) may be used, or two or more types may be used.

[0120] (Inorganic Compound) Examples of inorganic compounds include porous oxides, inorganic halides, clay minerals, clays (usually composed mainly of clay minerals), and ion-exchange layered compounds (most clay minerals are ion-exchange layered compounds).

[0121] Examples of porous oxides include SiO2, Al2O3, MgO, ZrO, TiO2, BO3, CaO, ZnO, BaO, and ThO2, as well as composites or mixtures containing these oxides. Examples of composites or mixtures include natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-VO5, SiO2-Cr2O3, and SiO2-TiO2-MgO. Among these, porous oxides containing either or both of SiO2 and Al2O3 as the main components are preferred.

[0122] The properties of the porous oxide vary depending on the type and manufacturing method, but the particle size is preferably in the range of 10 to 300 μm, more preferably 20 to 200 μm; the specific surface area is preferably 50 to 1000 m 2 / g, more preferably 100 to 700 m 2 / g; the pore volume is preferably in the range of 0.3 to 3.0 cm 3 Such porous oxides are calcined, if necessary, at a temperature of, for example, 100 to 1000°C, preferably 150 to 700°C before use.

[0123] Examples of inorganic halides include MgCl, MgBr, MnCl, and MnBr. The inorganic halides may be used as they are, or may be used after being pulverized using a ball mill, a vibration mill, or the like. It is also possible to dissolve the inorganic halide in a solvent such as alcohol, and then precipitate the resulting component in the form of fine particles using a precipitating agent.

[0124] Clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, but may also be synthetically produced. Note that ion-exchangeable layered compounds are compounds having a crystalline structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with weak bonding forces, and the ions contained therein are exchangeable.

[0125] Specific examples of clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, synthetic mica and other mica group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, hectorite, taeniolite, and halloysite.

[0126] It is also preferable to subject clay and clay minerals to chemical treatment. Examples of chemical treatments that can be used include surface treatments to remove impurities adhering to the surface and treatments that affect the crystalline structure of the clay. Examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment.

[0127] Examples of ion-exchangeable layered compounds include ionic crystalline compounds having a layered crystal structure such as hexagonal close-packed type, antimony type, CdCl2 type, CdI2 type, etc. Specific examples of ion-exchangeable layered compounds include crystalline acid salts of polyvalent metals such as α-Zr(HAsO4)2.H2O, α-Zr(HPO4), α-Zr(KPO4), 3H2O, α-Ti(HPO4), α-Ti(HAsO4)2.H2O, α-Sn(HPO4), H2O, γ-Zr(HPO4), γ-Ti(HPO4), and γ-Ti(NH4PO4)2.H2O.

[0128] Ion-exchangeable layered compounds may be converted into layered compounds with expanded interlayer spacing by utilizing their ion-exchange properties and exchanging the interlayer exchangeable ions with other large, bulky ions. Such bulky ions act as supports supporting the layered structure and are commonly called pillars. For example, oxide supports (pillars) can be formed between layers by intercalating the following metal hydroxide ions between the layers of a layered compound and then dehydrating them by heating. The introduction of another substance between the layers of a layered compound in this manner is called intercalation.

[0129] Examples of the guest compound to be intercalated include cationic inorganic compounds such as TiCl4 and ZrCl4; metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.); 13 O4 (OH) 24 ] 7+ , [Zr(OH) 14 ] 2+ , and [Fe3O(OCOCH3)] + These guest compounds may be used alone or in combination of two or more.

[0130] When intercalating a guest compound, a polymer obtained by hydrolysis and polycondensation of metal alkoxides (R is a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, or a colloidal inorganic compound such as SiO2 may also be present.

[0131] Among the inorganic compounds, clay minerals and clays are preferred, with the montmorillonite group, vermiculite, hectorite, taeniolite and synthetic mica being particularly preferred.

[0132] (Organic Compound) Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specific examples of the organic compound include polymers synthesized using ethylene and an α-olefin having 3 to 20 carbon atoms as the main components; polymers synthesized using vinylcyclohexane or styrene as the main component; and modified products of these polymers.

[0133] <Organic Compound Component (d)> An organic compound component (d) may be used as a component of the olefin polymerization catalyst. The organic compound component (d) is used, as necessary, for purposes such as improving the polymerization performance in the α-olefin polymerization reaction and the physical properties of the resulting copolymer. Examples of the organic compound component (d) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates. One type of organic compound component (d) may be used, or two or more types may be used.

[0134] <<Constitution of Olefin Polymerization Catalyst>> When polymerizing olefins using an olefin polymerization catalyst, the amounts of each component that can constitute the olefin polymerization catalyst are preferably as follows, or are preferably set as follows:

[0135] (1) When olefin polymerization is carried out using an olefin polymerization catalyst, the bridged metallocene compound (a) is used in an amount of usually 10 -9 ~10 -1 moles, preferably 10 -8 ~10 -2 It is used in molar amounts.

[0136] (2) When the organoaluminum oxy compound (b-1) is used as a component of the olefin polymerization catalyst, the compound (b-1) is used in such an amount that the molar ratio [Al / M] of the aluminum atom (Al) in the compound (b-1) to the total transition metal atoms (M) in the bridged metallocene compound (a) is preferably 0.01 to 5,000, more preferably 0.05 to 2,000.

[0137] (3) When the ionic compound (b-2) is used as a component of the olefin polymerization catalyst, the compound (b-2) is used in such an amount that the molar ratio of the compound (b-2) to the total transition metal atoms (M) in the bridged metallocene compound (a), [(b-2) / M], is preferably 1 to 10, more preferably 1 to 5.

[0138] (4) When the organoaluminum compound (b-3) is used as a component of the olefin polymerization catalyst, the compound (b-3) is used in such an amount that the molar ratio of the compound (b-3) to the total transition metal atoms (M) in the bridged metallocene compound (a), [(b-3) / M], is preferably 10 to 5,000, more preferably 20 to 2,000.

[0139] (5) When an organic compound component (d) is used as a component of an olefin polymerization catalyst, when compound (b) is an organoaluminum oxy compound (b-1), the organic compound component (d) is used in an amount such that the molar ratio of the organic compound component (d) to the compound (b-1) [(d) / (b-1)] is preferably 0.01 to 10, more preferably 0.1 to 5; when compound (b) is an ionic compound (b-2), the organic compound component (d) is used in an amount such that the molar ratio of the organic compound component (d) to the compound (b-2) [(d) / (b-2)] is preferably 0.01 to 10, more preferably 0.1 to 5; and when compound (b) is an organoaluminum compound (b-3), the organic compound component (d) is used in an amount such that the molar ratio of the organic compound component (d) to the compound (b-3) [(d) / (b-3)] is preferably 0.01 to 2, more preferably 0.005 to 1.

[0140] <Polymerization Method> In producing the copolymer (B), the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method.

[0141] In the liquid phase polymerization method, it is preferable to use an inert hydrocarbon medium. Examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. One or more inert hydrocarbon mediums may be used. A so-called bulk polymerization method can also be used, in which the liquefied olefin to be supplied to the polymerization itself is used as a solvent.

[0142] The polymerization temperature is preferably −50 to +200° C., more preferably 0 to +180° C. The polymerization pressure is preferably normal pressure to 10 MPa gauge pressure, more preferably normal pressure to 5 MPa gauge pressure.

[0143] The polymerization reaction can be carried out in any of batch, semi-continuous, and continuous modes. The polymerization can also be carried out in two or more stages with different reaction conditions. The molecular weight of the resulting copolymer (B) can be adjusted by adding hydrogen or the like to the polymerization system, changing the polymerization temperature, or by adjusting the amount of compound (b) used.

[0144] When producing the copolymer (B), it is possible to produce a copolymer (B) having high stereoregularity while maintaining high catalytic activity even under high-temperature conditions that are advantageous in industrial production. Such high-temperature conditions include a polymerization temperature of preferably 40°C or higher, more preferably 40 to 200°C, even more preferably 45 to 150°C, and particularly preferably 50 to 150°C (in other words, a temperature that can be industrially implemented is particularly preferred).

[0145] When producing the copolymer (B), the use of hydrogen in particular is preferable because it can improve the polymerization activity of the catalyst and increase or decrease the molecular weight of the resulting polymer. When hydrogen is added to the polymerization system, the amount of hydrogen is preferably about 0.00001 to 100 NL per mole of olefin. The hydrogen concentration in the polymerization system can be adjusted not only by adjusting the amount of hydrogen supplied, but also by carrying out a reaction that produces or consumes hydrogen within the polymerization system, by separating hydrogen using a membrane, or by releasing a portion of the hydrogen-containing gas outside the system.

[0146] When producing the copolymer (B), after synthesis by the above method, known post-treatment steps such as a catalyst deactivation step, a catalyst residue removal step, and a drying step may be carried out, if necessary.

[0147] <Modified Polyolefin (C)> The modified polyolefin (C) has a main skeleton composed of a polyolefin and has structural units derived from an unsaturated carboxylic acid and / or a derivative thereof. The modified polyolefin (C) is, for example, a polyolefin modified (preferably a graft-modified) with an unsaturated carboxylic acid and / or a derivative thereof. The modified polyolefin (C) can be obtained, for example, by modifying (preferably graft-modifying) a polyolefin with an unsaturated carboxylic acid and / or a derivative thereof.

[0148] Examples of polyolefins to be modified include polypropylene (c1) and ethylene-α-olefin copolymer (c2). The modified polyolefin (C) may be one type or a mixture of two or more types. The modified polyolefin (C) may be, for example, either one type of modified polypropylene (c1) or a modified ethylene-α-olefin copolymer (c2), or a mixture of two or more types selected from these modified products.

[0149] The polyolefin may have at least one constituent unit derived from a biomass-derived monomer. Examples of biomass-derived monomers include biomass-derived propylene, biomass-derived ethylene, and biomass-derived α-olefins having 4 to 20 carbon atoms. The same type of monomer constituting the polyolefin may be only biomass-derived monomers, only fossil fuel-derived monomers, or both biomass-derived monomers and fossil fuel-derived monomers.

[0150] Examples of polypropylene (c1) include propylene homopolymers and propylene-α-olefin copolymers. The α-olefin is an α-olefin other than propylene. Examples of the α-olefin include ethylene and α-olefins having 4 to 20 carbon atoms, with ethylene and α-olefins having 4 to 10 carbon atoms being preferred, and ethylene and α-olefins having 4 to 8 carbon atoms being more preferred. The α-olefin may be one type or two or more types. The copolymer may be, for example, a random copolymer or a block copolymer.

[0151] In one embodiment, the content of structural units derived from propylene in the propylene-α-olefin copolymer is preferably 50 mol% or more and less than 100 mol%, more preferably 70 mol% or more, even more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 95 mol% or more, and the content of structural units derived from α-olefins other than propylene is preferably more than 0 mol% and 50 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, still more preferably 10 mol% or less, and particularly preferably 5 mol% or less, provided that the total of the structural units derived from propylene and the structural units derived from α-olefins other than propylene is 100 mol%.

[0152] The propylene-α-olefin copolymer may be, for example, a propylene-ethylene-α-olefin copolymer. Examples of the α-olefin include α-olefins having 4 to 20 carbon atoms, and α-olefins having 4 to 10 carbon atoms are preferred. The α-olefin may be one type or two or more types. The copolymer may be, for example, a random copolymer or a block copolymer.

[0153] In the propylene-ethylene-α-olefin copolymer, the content of structural units derived from propylene is preferably 45 to 90 mol%, the content of structural units derived from ethylene is preferably 10 to 25 mol%, and the content of structural units derived from an α-olefin having 4 to 20 carbon atoms is preferably 1 to 30 mol%. In the propylene-ethylene-α-olefin copolymer, the content of structural units derived from propylene is preferably 50 to 85 mol%, the content of structural units derived from ethylene is preferably 10 to 22 mol%, and the content of structural units derived from an α-olefin having 4 to 20 carbon atoms is more preferably 5 to 28 mol%. In the propylene-ethylene-α-olefin copolymer, the content of structural units derived from propylene is preferably 55 to 80 mol%, the content of structural units derived from ethylene is preferably 10 to 20 mol%, and the content of structural units derived from an α-olefin having 4 to 20 carbon atoms is more preferably 10 to 28 mol%. However, the total of the structural units derived from propylene, the structural units derived from ethylene, and the structural units derived from an α-olefin having 4 to 20 carbon atoms is 100 mol %.

[0154] The polypropylene (c1) is preferably a crystalline polymer.

[0155] In the ethylene / α-olefin copolymer (c2), the α-olefin is an α-olefin other than ethylene, and examples of the α-olefin include α-olefins having 3 to 20 carbon atoms, preferably α-olefins having 3 to 10 carbon atoms. The α-olefin may be one type or two or more types. The copolymer may be, for example, a random copolymer or a block copolymer.

[0156] In the ethylene / α-olefin copolymer (c2), the content of structural units derived from ethylene is preferably 50 to 99 mol%, more preferably 55 to 98 mol%, and even more preferably 60 to 95 mol%, and the content of structural units derived from an α-olefin other than ethylene is preferably 1 to 50 mol%, more preferably 2 to 45 mol%, and even more preferably 5 to 40 mol%, provided that the total of the structural units derived from ethylene and the structural units derived from an α-olefin other than ethylene is 100 mol%.

[0157] The content of the above structural units is 13 It can be measured by C-NMR. Examples of α-olefins other than ethylene and propylene include 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-nonadecene, and 1-eicosene.

[0158] As the polyolefin to be modified, polypropylene (c1) is preferred from the viewpoint of being able to obtain a resin composition having excellent heat resistance, and polypropylene (c1) in which the content of structural units derived from propylene is 90 mol % or more of the total amount (100 mol %) of structural units derived from polymerizable monomers constituting said polypropylene is more preferred, polypropylene (c1) in which the content of structural units derived from propylene is 95 mol % or more is even more preferred, and a propylene homopolymer is particularly preferred.

[0159] Polyolefins such as polypropylene (c1) and ethylene-α-olefin copolymer (c2) can be produced by known methods using known catalysts such as Ziegler-Natta catalysts and metallocene catalysts.

[0160] Examples of unsaturated carboxylic acids and / or derivatives thereof that modify polyolefins include unsaturated compounds and / or derivatives thereof that have one or more carboxylic acid groups. Examples of unsaturated groups that the unsaturated compounds have include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups. One or more unsaturated carboxylic acids and / or derivatives thereof may be used.

[0161] Examples of unsaturated carboxylic acids include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (a registered trademark of endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid), acrylic acid, and methacrylic acid. Examples of derivatives of unsaturated carboxylic acids include acid anhydrides, imides, amides, and esters of unsaturated carboxylic acids, specifically maleic anhydride, citraconic anhydride, maleimide, monomethyl maleate, and glycidyl maleate. Among these, unsaturated carboxylic acids and their acid anhydrides are preferred, unsaturated dicarboxylic acids and their acid anhydrides are more preferred, and maleic acid, nadic acid, and their acid anhydrides are even more preferred.

[0162] The content (graft modification amount) of structural units derived from unsaturated carboxylic acids and / or derivatives thereof in the modified polyolefin (C) is preferably 0.01 to 10 mass%, more preferably 0.1 to 7 mass%, and even more preferably 1 to 5 mass%. Compositions containing such modified polyolefin (C) tend to have an excellent balance of moldability and adhesiveness. The content is measured by infrared spectroscopy if the structural unit has a functional group detectable by infrared spectroscopy, or by nuclear magnetic resonance spectroscopy if not.

[0163] Methods for grafting an unsaturated carboxylic acid and / or its derivative to a polyolefin include conventionally known graft polymerization methods such as a melt-kneading method and a solution method, etc. Examples include a method in which an unsaturated carboxylic acid and / or its derivative, and optionally a radical initiator such as an organic peroxide, are added to a molten polyolefin to cause a graft reaction, or a method in which an unsaturated carboxylic acid and / or its derivative, and optionally a radical initiator such as an organic peroxide, are added to a solution in which a polyolefin is dissolved in a solvent to cause a graft reaction.

[0164] As the radical initiator, for example, organic peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred.

[0165] The intrinsic viscosity [η] of the modified polyolefin (C) in decalin solvent at 135°C is preferably 0.1 to 10 dl / g, more preferably 0.2 to 5 dl / g, and even more preferably 0.3 to 3 dl / g, from the viewpoints of flexibility, adhesiveness, and mechanical strength.

[0166] <Ethylene-Based Polymer (D)> The ethylene-based polymer (D) is a polymer having preferably 60 to 100 mol % of structural units derived from ethylene, relative to 100 mol % of the total amount of structural units derived from polymerizable monomers.

[0167] The ethylene polymer (D) may have at least one structural unit derived from a biomass-derived monomer. Examples of the biomass-derived monomer include biomass-derived ethylene and biomass-derived α-olefins having 3 to 20 carbon atoms. The same type of monomer constituting the copolymer may be only biomass-derived monomers, only fossil fuel-derived monomers, or both biomass-derived monomers and fossil fuel-derived monomers.

[0168] The melt flow rate (MFR) of the ethylene polymer (D) is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, even more preferably 0.5 g / 10 min or more, and is preferably 10 g / 10 min or less, more preferably 9 g / 10 min or less, even more preferably 8 g / 10 min or less, for example, 0.1 to 10 g / 10 min. An ethylene polymer (D) having an MFR in the above range has, for example, excellent moldability and heat resistance. The MFR of the ethylene polymer (D) is measured in accordance with ASTM D1238E under conditions of 190°C and a load of 2.16 kg.

[0169] Examples of the ethylene polymer (D) include a homopolymer of ethylene and a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Specific examples of the ethylene polymer (D) include high-pressure low-density polyethylene (d1) and an ethylene / α-olefin copolymer (d2). These polymers will be described below.

[0170] <High-Pressure Low-Density Polyethylene (d1)> Any known high-pressure low-density polyethylene can be used as the high-pressure low-density polyethylene (d1) without any restrictions. High-pressure low-density polyethylene is generally polyethylene obtained by radical polymerization of ethylene under high temperature and high pressure. The method for producing high-pressure low-density polyethylene is not particularly limited, but examples thereof include a radical polymerization method in which ethylene is radically polymerized under conditions of 500 to 2000 atmospheres and 150 to 300°C. Examples of the polymerization initiator include organic peroxides.

[0171] The density of the high-pressure low-density polyethylene (d1) is preferably 900 to 925 kg / m 3 and more preferably 910 to 925 kg / m 3 The high-pressure low-density polyethylene (d1) having a density in the above range has, for example, excellent flexibility. The density is measured at 25°C in accordance with ASTM D1505.

[0172] The melting point (Tm) of the high-pressure low-density polyethylene (d1) measured by DSC is preferably 104 to 130° C., more preferably 105 to 125° C., and even more preferably 106 to 120° C. The high-pressure low-density polyethylene (d1) having a melting point within the above range is excellent in, for example, heat resistance and flexibility.

[0173] The melting point of the high-pressure low-density polyethylene (d1) is the melting point (the temperature at the apex of the melting peak) observed using a DSC when the sample is heated from room temperature to 200°C at a heating rate of 10°C / min, held at 200°C for 10 minutes, cooled to -20°C at a heating rate of 10°C / min, held at -20°C for 1 minute, and then heated again to 200°C at a heating rate of 10°C / min. When two or more melting peaks are observed, the highest temperature among the temperatures at the apex of these peaks is taken as the melting point.

[0174] The high-pressure low-density polyethylene (d1) is preferably a polymer having 100 mol % of structural units derived from ethylene, relative to a total of 100 mol % of structural units derived from polymerizable monomers.

[0175] <Ethylene / α-olefin copolymer (d2)> The ethylene / α-olefin copolymer (d2) has at least a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms.

[0176] The content of structural units derived from ethylene in the ethylene / α-olefin copolymer (d2) is preferably 60 to 99 mol%, more preferably 65 to 99 mol%, even more preferably 70 to 99 mol%, and particularly preferably 80 to 99 mol%. Ethylene / α-olefin copolymer (d2) having a content of structural units derived from ethylene within the above range has, for example, excellent heat resistance and flexibility.

[0177] The ethylene / α-olefin copolymer (d2) is characterized by having fewer long-chain branched structures than the high-pressure low-density polyethylene (d1), and is generally sometimes referred to as linear low-density polyethylene (LLDPE).

[0178] The content of structural units derived from an α-olefin having 3 to 20 carbon atoms in the ethylene / α-olefin copolymer (d2) is preferably 1 to 40 mol%, more preferably 1 to 35 mol%, even more preferably 1 to 30 mol%, and particularly preferably 1 to 20 mol%. Ethylene / α-olefin copolymer (d2) having a content of structural units derived from an α-olefin having 3 to 20 carbon atoms in the above range exhibits, for example, excellent heat resistance and flexibility.

[0179] In the ethylene / α-olefin copolymer (d2), the content of each of the structural units is the amount relative to 100 mol % of the total of the structural units derived from ethylene and the structural units derived from an α-olefin having 3 to 20 carbon atoms. When the content of each of the structural units is within the above range, it is possible to easily obtain, for example, a resin composition that is excellent in balance between impact resistance and flexibility.

[0180] Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-nonadecene, and 1-eicosene. Among these, α-olefins having 3 to 10 carbon atoms are preferred, α-olefins having 3 to 8 carbon atoms are more preferred, propylene, 1-butene, and 1-octene are even more preferred, and propylene is particularly preferred.

[0181] In producing the ethylene / α-olefin copolymer (d2), one type or two or more types of α-olefins having 3 to 20 carbon atoms may be used. The ethylene / α-olefin copolymer (d2) has at least one type of structural unit derived from an α-olefin having 3 to 20 carbon atoms, and may have two or more types.

[0182] In addition to the above structural units, the ethylene / α-olefin copolymer (d2) may contain one or more structural units derived from other polymerizable monomers, provided that the objectives of the present disclosure are not impaired. Examples of such other polymerizable monomers include vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids or derivatives thereof such as maleic anhydride; and non-conjugated polyenes such as dicyclopentadiene, cyclohexadiene, and 5-ethylidene-2-norbornene.

[0183] Examples of the ethylene-α-olefin copolymer (d2) include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-propylene-1-butene copolymer, an ethylene-propylene-ethylidenenorbornene copolymer, an ethylene-1-butene-1-octene copolymer, an ethylene-4-methyl-1-pentene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer. Among these, for example, an ethylene-propylene copolymer and an ethylene-1-butene copolymer are preferred.

[0184] The density of the ethylene / α-olefin copolymer (d2) is preferably 840 kg / m 3 More preferably, 850 kg / m 3 More preferably, 855 kg / m 3 or more, preferably 940 kg / m 3 Below, 930kg / m 3 Below, 920kg / m 3 or less than 910 kg / m 3 or less, more preferably 899 kg / m 3 More preferably, 890 kg / m or less 3 Particularly preferably 885 kg / m or less 3 or less, for example, 840 to 940 kg / m 3 A resin composition containing the copolymer (d2) having a density within the above range has, for example, a well-balanced and excellent impact resistance and rigidity. The density is measured at 25°C in accordance with ASTM D1505.

[0185] The ethylene / α-olefin copolymer (d2) had an MFR measured under conditions of 190°C and a load of 10 kg in accordance with ASTM D1238E. 10 and the ratio of MFR2 measured under the conditions of 190°C and a load of 2.16 kg (MFR 10 / MFR2) is preferably 4.0 or more, more preferably 5.0 or more, and is preferably 8.0 or less, more preferably 7.0 or less, for example, 4.0 to 8.0. 10 A resin composition containing the copolymer (d2) having a / MFR2 in the above range has, for example, excellent impact resistance.

[0186] The melting point (Tm) of the ethylene / α-olefin copolymer (d2) measured by DSC is preferably 30 to 100° C., more preferably 31 to 90° C., and even more preferably 32 to 80° C. A resin composition containing the copolymer (d2) having a melting point within the above range has, for example, excellent impact resistance.

[0187] The ethylene / α-olefin copolymer (d2) can be produced by a conventional method using, for example, a vanadium catalyst, a titanium catalyst, or a metallocene catalyst. Preferably, a metallocene catalyst is used to obtain an ethylene / α-olefin copolymer (d2) having a narrow molecular weight distribution and composition distribution. Such a copolymer (d2) is more suitable, for example, in terms of mechanical properties and impact resistance.

[0188] The ethylene polymer (D) contained in the composition may be one type or two or more types. The ethylene polymer (D) may be, for example, a high-pressure low-density polyethylene (d1), an ethylene-α-olefin copolymer (d2), or a mixture of the high-pressure low-density polyethylene (d1) and the ethylene-α-olefin copolymer (d2). When the composition contains the high-pressure low-density polyethylene (d1) and the ethylene-α-olefin copolymer (d2) as the ethylene polymer (D), the content of the high-pressure low-density polyethylene (d1) is preferably 5 to 300 parts by mass, more preferably 20 to 200 parts by mass, and even more preferably 50 to 100 parts by mass, per 100 parts by mass of the ethylene-α-olefin copolymer (d2), from the viewpoint of heat resistance or mechanical properties.

[0189] <Other Components> The composition may further contain polymers other than the above-mentioned (A) to (D). The composition may further contain additives. Examples of additives include weather resistance stabilizers, heat resistance stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, nucleating agents (crystal nucleating agents), lubricants, pigments, dyes, plasticizers, antioxidants, hydrochloric acid absorbers, and antioxidants. The composition may contain one or more additives.

[0190] <Content of Each Component> The preferred content of each component in the present composition is as follows. The contents in the following description are based on 100 parts by mass of the total content of the propylene polymer (A), copolymer (B), modified polyolefin (C), and ethylene polymer (D). The content of the propylene polymer (A) is usually 45 to 79.9 parts by mass, preferably 45 to 70 parts by mass, and more preferably 45 to 60 parts by mass. Films obtained from the present composition having a propylene polymer (A) content within the above range tend to have excellent mechanical strength and heat resistance. The content of the copolymer (B) is usually 15 to 40 parts by mass, preferably 17 to 35 parts by mass, more preferably 20 to 30 parts by mass, and particularly preferably 23 to 30 parts by mass. The higher the content of the copolymer (B), the better the film obtained from the present composition tends to have whitening resistance during deformation processing. Note that whitening during deformation processing is more likely to occur if fine cracks are present. When fine cracks occur in the film, the insulating properties of the film deteriorate when used as a battery packaging film. Furthermore, moisture penetrates into the exterior packaging material, which is thought to cause gas generation when the contents come into contact with moisture. The content of the modified polyolefin (C) is typically 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass, and more preferably 2 to 6 parts by mass. The higher the content of the modified polyolefin (C), the more likely the composition will have excellent adhesion to polar materials. The content of the ethylene polymer (D) is typically 5 to 30 parts by mass, preferably 5 to 25 parts by mass, and more preferably 5 to 20 parts by mass. When the content of the ethylene polymer (D) is within the above range, the composition tends to have excellent heat resistance and impact resistance.

[0191] The present composition, in which the content of the above components in the present composition is within the above range, has excellent adhesion to polar and non-polar materials, and the layer or film obtained from the composition has excellent whitening resistance during deformation processing and mechanical strength in a high-temperature atmosphere. Even when the content of copolymer (B) in the present composition is high, a layer or film having excellent mechanical strength in a high-temperature atmosphere can be formed.

[0192] The total content of the propylene polymer (A), copolymer (B), modified polyolefin (C), and ethylene polymer (D) in the composition can be appropriately set depending on the application and is not particularly limited. The total content of the propylene polymer (A), copolymer (B), modified polyolefin (C), and ethylene polymer (D) in the composition may be, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, based on the mass of the composition.

[0193] The melt flow rate (MFR) of the composition is preferably 0.1 to 25 g / 10 min, more preferably 0.5 to 15 g / 10 min, even more preferably 1 to 10 g / 10 min, and particularly preferably 3 to 8 g / 10 min. When the MFR is within the above range, whitening during deformation processing of the film can be effectively suppressed. The MFR of the composition is measured at 230°C under a load of 2.16 kg in accordance with ASTM D1238E.

[0194] <Method for Producing Resin Composition> The present composition can be produced using a conventionally known method. The present composition can be prepared by mixing the components to be blended in the composition using various known methods, such as a Henschel mixer, V-blender, ribbon blender, tumbler blender, kneader-ruder, or the like, or by melt-kneading using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, or the like. Furthermore, granulation or pulverization may be performed as necessary. During mixing or kneading, the components to be blended may be added all at once or in stages.

[0195] [Film] The film of the present disclosure has at least one layer (hereinafter also referred to as "layer (1)") formed from the propylene-based resin composition of the present disclosure. The film of the present disclosure may be a monolayer film consisting of layer (1). The film of the present disclosure may be a multilayer film having two or more layers (1), or may be a multilayer film having layer (1) and a layer other than layer (1). The thickness of layer (1) is preferably 10 to 150 μm, more preferably 20 to 100 μm. When the film has two or more layers (1), it is preferable that the thickness of each layer (1) is within the range.

[0196] The film of the present disclosure has excellent whitening resistance during deformation processing and mechanical strength in a high-temperature atmosphere. Therefore, when the film of the present disclosure is used as a food packaging material, a construction material, or a battery packaging material (e.g., a packaging material for a lithium-ion battery), whitening is unlikely to occur during secondary processing of the film, such as drawing or folding. Therefore, the film of the present disclosure can be suitably used as a food packaging film, a construction material film, or a battery packaging film (e.g., a packaging material film for a lithium-ion battery).

[0197] Among batteries, lithium ion batteries have been increasingly used in portable electronic devices, automobiles, and the like in recent years. For lithium ion batteries, pouch-type or embossed exterior packaging materials using multilayer films as packaging materials have been increasingly used to accommodate the demand for shape flexibility and miniaturization. Because multilayer films have a high degree of shape flexibility, they are easy to process when manufacturing pouch-type or embossed exterior packaging materials. However, when a multilayer film is deformed, the deformed areas may whiten. Since whitened areas in the exterior packaging material can cause short circuits, a material with excellent whitening resistance is desired. As described above, the film of the present disclosure has excellent whitening resistance during deformation processing. Therefore, the film of the present disclosure is particularly suitable for use as a packaging material constituting the exterior packaging material of a lithium ion battery.

[0198] In recent years, with the increase in the size of batteries, there is a demand for battery packaging films with even greater heat resistance. With the present composition, even when the content of copolymer (B) is high, a film with excellent mechanical strength in a high-temperature atmosphere can be formed.

[0199] A lithium-ion battery typically includes a positive electrode, a negative electrode, a separator between the positive and negative electrodes, and a nonaqueous electrolyte. The positive electrode typically includes a positive electrode current collector made of a metal or carbon material, and a positive electrode active material capable of absorbing and releasing lithium, such as a composite oxide of lithium and a transition metal. The negative electrode typically includes a negative electrode current collector made of a carbon material, and a negative electrode active material capable of absorbing and releasing lithium ions, such as metallic lithium, a lithium-containing alloy, or a metal or alloy capable of alloying with lithium. The nonaqueous electrolyte includes a lithium salt as an electrolyte and a nonaqueous solvent. In a lithium-ion battery, the positive electrode, negative electrode, and separator are impregnated with the nonaqueous electrolyte.

[0200] Lithium-ion batteries often have packaging material (lithium-ion battery packaging material) around their periphery. A positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte are enclosed inside the packaging material. Typically, a positive electrode terminal and a negative electrode terminal are connected to the positive electrode and the negative electrode, respectively. A portion of the positive electrode terminal and a portion of the negative electrode terminal are exposed to the exterior of the packaging material.

[0201] The case where the film of the present disclosure is used as a packaging material is described below: A lithium-ion battery is obtained by sandwiching a positive electrode, a negative electrode, etc. between a pair of films and heat-sealing the peripheral edges of the pair of films in a manner such that a portion of the positive electrode terminal and a portion of the negative electrode terminal are exposed to the outside of the pair of films.

[0202] Lithium ion batteries using the packaging material for lithium ion batteries can be used in, for example, portable electronic devices, personal computers, robots, drones, automobiles, aircraft, wearable devices, and energy storage systems (ESS) for home use or renewable energy power generation.

[0203] In one embodiment, the film of the present disclosure has a layer (1) and a layer other than the layer (1) that is in contact with the layer (1). In one embodiment, one or both sides of the layer (1) are in contact with a layer other than the layer (1). Examples of the layer other than the layer (1) include a metal-containing layer, a polyolefin layer, and a polar resin layer.

[0204] In one embodiment, the film of the present disclosure has, in this order in the lamination direction, a first layer other than layer (1), layer (1), and a second layer other than layer (1). In the above film, the first layer is in contact with layer (1), and the second layer is in contact with layer (1). That is, when one surface of layer (1) is described as the first surface and the other surface is described as the second surface, the first layer is in contact with the first surface of layer (1), and the second layer is in contact with the second surface of layer (1). The first layer and the second layer may be the same or different.

[0205] The first layer and the second layer may each independently be, for example, a metal-containing layer, a polyolefin layer, or a polar resin layer. Layer (1) has excellent adhesion to both the metal-containing layer and the polar resin layer, and to the polyolefin layer. The thickness of each of the first layer and the second layer is preferably 10 to 300 μm, more preferably 20 to 200 μm.

[0206] In one embodiment, the film of the present disclosure has a layer (1) and a layer selected from a metal-containing layer, a polyolefin layer, and a polar resin layer (hereinafter also referred to as "layer (2)"). In the above film, layer (2) is in contact with layer (1). In one embodiment, the film of the present disclosure has layer (2), layer (1), and layer (2) in this order in the stacking direction.

[0207] Examples of metal-containing layers include aluminum layers, copper layers, and stainless steel layers. The thickness of the metal-containing layer is, for example, 10 to 300 μm. Examples of polyolefin layers include polypropylene layers, poly-4-methylpentene layers, and polyethylene layers. Examples of polar resin layers include polyester layers such as polyethylene terephthalate (PET) layers and polybutylene terephthalate (PBT) layers, polyamide layers, and ethylene-vinyl alcohol copolymer (EVOH) layers. The thickness of the polyolefin layer and the polar resin layer is, independently, for example, 10 to 100 μm.

[0208] The shape, size, thickness, etc. of the film of the present disclosure may be appropriately selected depending on the desired application. The film may be a stretched film or a non-stretched film. The film may be a single-layer film or a multilayer film. When the film is a multilayer film, at least one layer therein may be layer (1).

[0209] The thickness of the film of the present disclosure (the total thickness of each layer in the case of a multilayer film) is preferably 10 to 600 μm, more preferably 30 to 500 μm.

[0210] The film of the present disclosure can be produced, for example, by a production method including a step of melt-extrusion molding the propylene-based resin composition of the present disclosure to form layer 1. The film of the present disclosure can be produced, for example, by a method generally used industrially, such as a casting method, an inflation method, or an extrusion lamination method.

[0211] [Examples of Aspects] The present disclosure relates to, for example, the following [1] to

[12] . [1] A propylene-based resin composition comprising: (A) a propylene-based polymer having a melting point (Tm) of 120°C or higher as measured by a differential scanning calorimeter (DSC); (B) a propylene-α-olefin copolymer having a structural unit (i) derived from propylene and a structural unit (ii) derived from an α-olefin having 5 to 20 carbon atoms, and satisfying the following requirements (B1) to (B4); (C) a modified polyolefin having a structural unit derived from an unsaturated carboxylic acid and / or a derivative thereof; and (D) an ethylene-based polymer, wherein, when the total content of (A), (B), (C), and (D) is 100 parts by mass, the content of (A) is 45 to 79.9 parts by mass, the content of (B) is 15 to 40 parts by mass, the content of (C) is 0.1 to 10 parts by mass, and the content of (D) is 5 to 30 parts by mass. A propylene-based resin composition, (B1) in which, when the total content of the structural unit (i) and the structural unit (ii) is taken as 100 mol %, the content of the structural unit (i) is 75 to 93 mol % and the content of the structural unit (ii) is 7 to 25 mol %; (B2) in which the density measured at 25°C in accordance with ASTM D1505 is 851 to 900 kg / m 3(B3) the intrinsic viscosity [η] in decalin solvent at 135°C is 1.6 to 5.0 dl / g; (B4) the melting point (Tm) measured by differential scanning calorimetry (DSC) is less than 110°C or is not observed. [2] The propylene-based resin composition according to the above item [1], wherein the α-olefin in the propylene-α-olefin copolymer (B) is 4-methyl-1-pentene. [3] The propylene-based resin composition according to any one of [1] to [2], wherein the modified polyolefin (C) is a polyolefin modified with an unsaturated carboxylic acid and / or a derivative thereof, the polyolefin is a polypropylene (c1) in which a content of structural units derived from propylene is 90 mol % or more based on 100 mol % of all structural units derived from polymerizable monomers, and the content of structural units derived from unsaturated carboxylic acid and / or a derivative thereof in the modified polyolefin (C) is 0.01 to 10 mass %. [4] The propylene-based resin composition according to any one of [1] to [3], wherein the ethylene polymer (D) has a melt flow rate of 0.1 to 10 g / 10 min, as measured at 190°C under a load of 2.16 kg in accordance with ASTM D1238E. [5] The propylene-based resin composition according to any one of [1] to [4], wherein the resin composition has a melt flow rate of 0.1 to 25 g / 10 min, as measured in accordance with ASTM D1238E at 230°C under a load of 2.16 kg. [6] A film having at least one layer (1) formed from the propylene-based resin composition according to any one of [1] to [5]. [7] The film according to [6], wherein the film has, in this order in the lamination direction, a first layer other than the layer (1), the layer (1), and a second layer other than the layer (1), wherein the first layer is in contact with the layer (1), and the second layer is in contact with the layer (1). [8] The film according to [6], wherein the film has the layer (1) and a layer (2) selected from a metal-containing layer, a polyolefin layer, and a polar resin layer, and the layer (2) is in contact with the layer (1).[9] The film according to [6] above, which is a food packaging film, a building material film, or a battery packaging film.

[10] The film according to [7] above, which is a food packaging film, a building material film, or a battery packaging film.

[11] The film according to [8] above, which is a food packaging film, a building material film, or a battery packaging film.

[12] A method for producing a film having at least one layer (1) formed from a propylene-based resin composition, the method comprising the step of melt-extruding the propylene-based resin composition according to any one of [1] to [5] above.

[0212] The propylene-based resin composition of the present disclosure will be described below with reference to examples, but the propylene-based resin composition is not limited to these examples in any way.

[0213] [Various Measurement Methods] In the present examples, measurements were carried out according to the following methods.

[0214] <Propylene Content and α-Olefin Content> The propylene content and comonomer (α-olefin) content in the propylene-α-olefin copolymer (B) were determined under the following conditions: 13 C-NMR measurement was performed, and the obtained 13 It was calculated by analyzing the C-NMR spectrum. In this specification, the content of structural units derived from propylene is also referred to as "propylene content", and the content of structural units derived from the comonomer α-olefin (other than propylene) is also referred to as "comonomer content". For polymers other than copolymer (B), the content of each structural unit was calculated in accordance with the above measurement method. Apparatus: AVANCE III Cryo-500 Nuclear Magnetic Resonance Apparatus manufactured by Bruker Biospin Measurement Nuclei: 13C (125 MHz) Measurement mode: Single pulse proton broadband decoupling Pulse width: 45° (5.00 μsec) Number of points: 64k Measurement range: 250 ppm (-55 to 195 ppm) Repetition time: 5.5 seconds Number of accumulations: 128 Measurement solvent: orthodichlorobenzene / benzene-d6 (4 / 1 [v / v]) Sample concentration: ca. 60 mg / 0.6 mL Measurement temperature: 120°C Window function: exponential (BF: 1.0 Hz) Chemical shift reference: benzene-d6: 128 ppm

[0215] <Density> The density of the polymers such as the propylene polymer (A), the propylene-α-olefin copolymer (B) and the ethylene polymer (D) was measured at 25° C. in accordance with ASTM D1505.

[0216] <Intrinsic Viscosity [η]> The intrinsic viscosity [η] of polymers such as the propylene-α-olefin copolymer (B) and the modified polyolefin (C) was measured in decalin solvent at 135°C using an Ubbelohde viscometer. Approximately 20 mg of the polymer was dissolved in 15 mL of decalin, and the specific viscosity ηsp was measured in an oil bath heated to 135°C. After diluting this decalin solution with an additional 5 mL of decalin solvent, the specific viscosity ηsp was measured in the same manner. This dilution procedure was repeated two more times, and the value of ηsp / C when the concentration (C) was extrapolated to zero was calculated as the intrinsic viscosity [η] (see the formula below). [η] = lim(ηsp / C) (C → 0)

[0217] <Melting point (Tm), heat of fusion (ΔH), and glass transition temperature (Tg)> Using a hydraulic hot press molding machine set at 190 ° C, propylene-α-olefin copolymer (B) was heated for 5 minutes, molded under a pressure of 7.5 MPa for 2 minutes, and then cooled at 20 ° C and a pressure of 7.5 MPa for 5 minutes to produce a 500 μm thick sheet. After 7 days or more at room temperature from molding, a test piece of approximately 10 mg was punched out from the sheet and cooled from room temperature to -40 ° C at a temperature decrease rate of 10 ° C / min in a nitrogen atmosphere and held at that temperature for 5 minutes. Next, the temperature was increased to 200 ° C at a temperature increase rate of 10 ° C / min and held at that temperature for 10 minutes. Next, the temperature was decreased to -70 ° C at a temperature decrease rate of 10 ° C / min and held at that temperature for 1 minute. Next, the temperature was increased to 200 ° C at a temperature increase rate of 10 ° C / min. The heat of fusion (ΔH) was calculated from the integrated value of the crystalline melting peak when the temperature was raised for the second time. The melting point (Tm) was taken as the temperature at the peak apex of the crystalline melting peak when the temperature was raised for the second time. The glass transition temperature (Tg) was taken as the temperature at which the baseline shift occurred when the temperature was raised for the second time. When two or more melting peaks were observed, the highest temperature among the peak apex temperatures of these peaks was taken as the melting point. When the heat of fusion (ΔH) and the melting point (Tm) were not observed, it was indicated as "ND".

[0218] <Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)> A GPC apparatus, GPC-IR6_MCT gel permeation chromatograph manufactured by Polymer Characterization, Inc., was used to measure Mw and Mn in terms of polystyrene under the following conditions, and Mw / Mn was calculated. Separation columns: two TSKgel GNH6-HT columns manufactured by Tosoh Corporation, and two TSKgel GNH6-HTL columns manufactured by Tosoh Corporation (both column sizes: diameter 7.5 mm, length 300 mm) Column temperature: 140°C Mobile phase: o-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) containing 0.025 wt% BHT (manufactured by Takeda Pharmaceutical Co., Ltd.) as an antioxidant Movement speed: 1.0 mL / min Sample concentration: 10 mg / 10 mL Sample injection volume: 400 μL Detector: IR6 type MCT infrared detector Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation) Molecular weight conversion: polystyrene conversion / standard calibration method

[0219] <MFR> The MFR of the propylene polymer (A) and the propylene-α-olefin copolymer (B) was measured at 230°C under a load of 2.16 kg in accordance with ASTM D1238E. The MFR of the ethylene polymer (D) was measured at 190°C under a load of 2.16 kg in accordance with ASTM D1238E.

[0220] <Tensile Modulus and Stress at Break> Using a hydraulic hot press molding machine set at 190°C, propylene / α-olefin copolymer (B) was heated for 5 minutes, molded under a pressure of 7.5 MPa for 2 minutes, and then cooled at 20°C under a pressure of 7.5 MPa for 5 minutes to produce a sheet (test piece) with a thickness of 2 mm. After 7 days or more had passed at room temperature after molding, ASTM No. 4 dumbbells were produced from the sheet in accordance with ASTM D638, and the tensile modulus and stress at break of the dumbbells were measured under conditions of 23°C and a pulling rate of 50 mm / min.

[0221] <Shore D Hardness (Instantaneous Value)> Using a hydraulic hot press molding machine set at 190°C, propylene-α-olefin copolymer (B) was heated for 5 minutes, molded under a pressure of 7.5 MPa for 2 minutes, and then cooled at 20°C under a pressure of 7.5 MPa for 5 minutes to produce a sheet with a thickness of 2 mm. Three sheets were stacked to produce a test piece. After 7 days or more had passed at room temperature after molding, a durometer hardness tester (D type) was used, and the indenter was brought into contact with the test piece, and the scale was read immediately (in accordance with ASTM D2240).

[0222] <Shore A hardness (instantaneous value)> Using a hydraulic hot press molding machine set at 190°C, propylene-α-olefin copolymer (B) was heated for 5 minutes, molded under a pressure of 7.5 MPa for 2 minutes, and then cooled at 20°C under a pressure of 7.5 MPa for 5 minutes to produce a sheet with a thickness of 2 mm. Three sheets were stacked to produce a test piece. After 7 days or more had passed at room temperature after molding, a durometer hardness tester (Type A) was used, and the scale was read immediately after the indenter was brought into contact with the test piece (in accordance with ASTM D2240).

[0223] <Graft Modification Amount> The content ratio (graft modification amount) of the structural unit derived from an unsaturated carboxylic acid and / or a derivative thereof in the modified polyolefin (C) can be determined by measuring the peak attributable to the structural unit (1,790 cm when maleic anhydride is used) using an infrared absorption analyzer. -1 The intensity of the chromatogram was measured and quantified using a calibration curve prepared in advance.

[0224] [Polymers Used] The polymers used in the Examples and Comparative Examples are shown below. Unless otherwise specified, all polymers were prepared by polymerization according to conventional methods.

[0225] <Propylene-based polymer (A)> PP-1: homopolypropylene (MFR = 3.0 g / 10 min, melting point = 163°C, density = 910 kg / m 3 ) PP-2: Random polypropylene (propylene content = 96 mol%, ethylene content = 4 mol%, MFR = 7.0 g / 10 min, melting point = 138 ° C, density = 900 kg / m 3 )

[0226] <Propylene / α-olefin copolymer (B)> C3EL-1: To a 300-liter continuous polymerization reactor, n-hexane was continuously supplied from one supply port at a rate of 20.9 L / h, and from another supply port, a mixed hexane solution of diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride (catalyst type a), modified methylaluminoxane, and triisobutylaluminum (zirconium-equivalent concentration 0.6 mmol / L, modified methylaluminoxane aluminum-equivalent concentration 154 mmol / L, triisobutylaluminum aluminum-equivalent concentration 62 mmol / L) was continuously supplied at a rate of 0.057 L / h. Simultaneously, propylene was continuously fed to the continuous polymerization reactor through a separate feed port at a rate of 8.8 kg / h, 4-methyl-1-pentene (4MP-1) at a rate of 3.5 kg / h, and hydrogen at a rate of 0.2 NL / h. Continuous solution polymerization was carried out under conditions of a polymerization temperature of 60°C, a polymerization pressure of 1.0 MPaG, and a residence time of 1.5 hours, to obtain a propylene-4-methyl-1-pentene copolymer (B-1). C3EL-2: A propylene-4-methyl-1-pentene copolymer (B-2) was produced in the same manner as in the production method for C3EL-1, except that propylene was continuously fed at a rate of 16 kg / h, 4-methyl-1-pentene at a rate of 10 kg / h, and hydrogen at a rate of 2 NL / h. C3EL-3: Propylene / 4-methyl-1-pentene copolymer (4-methyl-1-pentene content = 27.5 mol%, MFR = 11 g / 10 min, density = 840 kg / m 3 ) C3EL-4: Propylene-ethylene copolymer (MFR = 8.0 g / 10 min, density = 879 kg / m 3 )

[0227]

[0228] <Modified Polyolefin (C)> MAH-PP-1: Modified homopolypropylene (maleic anhydride graft amount = 3.0 mass%, intrinsic viscosity [η] = 0.4 dl / g)

[0229] <Ethylene-based polymer (D)> EPR-1: ethylene-propylene copolymer (MFR = 0.6 g / 10 min, density = 870 kg / m 3 ) PE-1: Low-density polyethylene (MFR = 7.0 g / 10 min, density = 917 kg / m 3 )

[0230] Example 1 A resin composition was prepared by melt-kneading 20 parts by mass of PP-1, 38 parts by mass of PP-2, 20 parts by mass of C3EL-1, 5 parts by mass of MAH-PP-1, 10 parts by mass of EPR-1, and 7 parts by mass of PE-1 at 230°C using a single-screw extruder.

[0231] Commercially available polypropylene (F329RA, manufactured by Prime Polymer Co., Ltd., MFR: 24 g / 10 min) and the above resin composition were co-extruded at 290°C using a screw with a diameter of 50 mm and an effective length (L / D) of 28. The extruded polypropylene and the above resin composition were laminated in a feed block, with the polypropylene forming the outer layer and the resin composition forming the inner layer. In this manner, a film-like laminate with a thickness of approximately 40 μm, with both the outer and inner layers being 20 μm thick, was produced. The die temperature was 290°C. The molten laminate was brought into contact with the surface of aluminum foil (thickness: 20 μm) and then cooled with a chill roll equipped with a pinch roll while being taken up at a speed of 50 m / min to obtain a multilayer film for evaluating whitening resistance, which had a polypropylene layer, a resin composition layer, and an aluminum layer in this order in the lamination direction.

[0232] A 100 μm thick film was molded from the resin composition using an extruder equipped with a T-die. The resulting film was sandwiched between two 200 μm thick sheets of aluminum foil and heat-sealed for 10 seconds using a heat sealer at 180° C. and 0.1 MPa to obtain a multilayer film for adhesive strength measurement having an aluminum layer, a resin composition layer, and an aluminum layer in this order in the lamination direction.

[0233] [Examples 2 to 4 and Comparative Examples 1 to 4] In Examples 2 to 4 and Comparative Examples 1 to 4, resin compositions were produced in the same manner as in Example 1 according to the formulations shown in Table 2. Using the resin compositions, multilayer films for evaluating whitening resistance and multilayer films for measuring adhesive strength were produced in the same manner as in Example 1.

[0234] [Evaluation] The MFR, strength at break, and tensile fracture energy of the resin compositions obtained in the Examples or Comparative Examples were measured by the methods described below. The multilayer films for evaluating whitening resistance obtained in the Examples or Comparative Examples were used to evaluate whitening resistance according to the methods described below. The multilayer films for measuring adhesion obtained in the Examples or Comparative Examples were used to measure AL adhesion according to the methods described below.

[0235] <MFR> The MFR of the resin compositions obtained in the examples and comparative examples was measured in accordance with ASTM D1238E under conditions of 230°C and a load of 2.16 kg.

[0236] <Break Strength and Tensile Fracture Energy> Using a hydraulic hot press molding machine set at 210°C, the resin compositions obtained in the Examples or Comparative Examples were heated for 8 minutes, molded under a pressure of 10 MPa for 4 minutes, and then cooled at 20°C under a pressure of 10 MPa for 4 minutes to produce sheets (test specimens) with a thickness of 2 mm. After 7 days or more had passed at room temperature after molding, No. 5A dumbbells were produced from the sheets in accordance with JIS K7161-2, and the break strength and tensile fracture energy of the dumbbells were measured under conditions of 23°C (room temperature) and 80°C (high temperature) at a tensile speed of 500 mm / min.

[0237] <Evaluation of Whitening Resistance After Drawing> The multilayer films for evaluating whitening resistance obtained in the Examples or Comparative Examples were drawn at a speed of 200 mm / min using a die with a meshing depth of 5 mm. The degree of whitening on the wall surface of the obtained molded body was visually evaluated according to the following criteria: A: No whitening observed. B: Slight whitening observed. C: Significant whitening observed.

[0238] <Evaluation of AL Adhesion Strength> The multilayer films for adhesion strength measurement obtained in the Examples or Comparative Examples were cut into 20 mm widths, and the adhesion strength (unit: N / 20 mm) between the aluminum layer and the resin composition layer was measured using a tensile tester by the 180° peel method at room temperature of 23° C. The crosshead speed was 200 mm / min.

[0239]

Claims

1. A propylene-based resin composition comprising: (A) a propylene-based polymer having a melting point (Tm) of 120°C or higher as measured by differential scanning calorimetry (DSC); (B) a propylene-α-olefin copolymer having a structural unit (i) derived from propylene and a structural unit (ii) derived from an α-olefin having 5 to 20 carbon atoms, and satisfying the following requirements (B1) to (B4); (C) a modified polyolefin having a structural unit derived from an unsaturated carboxylic acid and / or a derivative thereof; and (D) an ethylene-based polymer; wherein, when the total content of (A), (B), (C), and (D) is 100 parts by mass, the content of (A) is 45 to 79.9 parts by mass, the content of (B) is 15 to 40 parts by mass, the content of (C) is 0.1 to 10 parts by mass, and the content of (D) is 5 to 30 parts by mass. (B1) When the total content of the structural unit (i) and the structural unit (ii) is taken as 100 mol%, the content of the structural unit (i) is 75 to 93 mol%, and the content of the structural unit (ii) is 7 to 25 mol%; (B2) The density measured at 25°C in accordance with ASTM D1505 is 851 to 900 kg / m 3 (B3) The intrinsic viscosity [η] in decalin solvent at 135°C is 1.6 to 5.0 dl / g; (B4) The melting point (Tm) measured by differential scanning calorimetry (DSC) is less than 110°C or is not observed.

2. The propylene-based resin composition according to claim 1, wherein the α-olefin in the propylene / α-olefin copolymer (B) is 4-methyl-1-pentene.

3. The propylene-based resin composition according to claim 1, wherein the modified polyolefin (C) is a polyolefin modified with an unsaturated carboxylic acid and / or a derivative thereof, the polyolefin is a polypropylene (c1) in which the content of structural units derived from propylene is 90 mol % or more of 100 mol % of the total amount of structural units derived from polymerizable monomers, and the content of structural units derived from unsaturated carboxylic acid and / or a derivative thereof in the modified polyolefin (C) is 0.01 to 10 mass %.

4. The propylene-based resin composition according to claim 1, wherein the ethylene-based polymer (D) has a melt flow rate of 0.1 to 10 g / 10 min, as measured at 190°C under a load of 2.16 kg in accordance with ASTM D1238E.

5. The propylene-based resin composition according to claim 1, wherein the melt flow rate of the resin composition measured in accordance with ASTM D1238E at 230°C under a load of 2.16 kg is 0.1 to 25 g / 10 min.

6. A film having at least one layer (1) formed from the propylene-based resin composition according to any one of claims 1 to 5.

7. The film according to claim 6, wherein the film has, in the stacking direction, a first layer other than the layer (1), the layer (1), and a second layer other than the layer (1), in that order, the first layer being in contact with the layer (1), and the second layer being in contact with the layer (1).

8. The film according to claim 6, wherein the film comprises the layer (1) and a layer (2) selected from a metal-containing layer, a polyolefin layer, and a polar resin layer, and the layer (2) is in contact with the layer (1).

9. The film according to claim 6, which is a food packaging film, a building material film, or a battery packaging film.

10. The film according to claim 7, which is a food packaging film, a building material film, or a battery packaging film.

11. The film according to claim 8, which is a food packaging film, a building material film, or a battery packaging film.

12. A method for producing a film having at least one layer (1) formed from a propylene-based resin composition, comprising a step of melt-extrusion molding the propylene-based resin composition according to any one of claims 1 to 5.

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