Resin composition, and single-layer or multilayer film

Abstract

Provided is a resin composition which contains: an unmodified propylene polymer (A) that contains 60-100 mol% of a constituent unit derived from propylene and satisfies a specific requirement; an unmodified 1-butene-propylene-ethylene copolymer (B) that satisfies a specific requirement; a modified polyolefin (C) that contains a constituent unit derived from an unsaturated carboxylic acid and / or a derivative thereof; and an unmodified ethylene polymer (D) that contains 60-100 mol% of a constituent unit derived from ethylene. In this resin composition, the content of the 1-butene-propylene-ethylene copolymer (B) is 10.1-49.9% by mass (provided that the resin composition is taken as 100% by mass).

Description

Resin compositions, and single-layer or multi-layer films

[0001] The present invention relates to resin compositions, as well as single-layer or multi-layer films.

[0002] Polypropylene is widely used as a thermoplastic molding material with excellent rigidity, heat resistance, and transparency. Because polypropylene is a non-polar material, it has poor adhesion to polar materials such as ethylene-vinyl alcohol copolymers. Therefore, techniques for modifying polypropylene with unsaturated carboxylic acids or their derivatives to improve adhesion are widely known. Furthermore, because polypropylene lacks flexibility, when used as an adhesive, it is usually compounded with a soft rubber component.

[0003] By compounding polypropylene with a soft rubber component in this way, a polypropylene-based adhesive with improved adhesion can be obtained (for example, Patent Documents 1 and 2). On the other hand, the soft rubber component causes whitening during secondary processing such as deep drawing and bending, so there has also been a need for improved whitening resistance. Specific applications requiring deep drawing or bending include, for example, food packaging materials, building materials, and lithium-ion battery packaging materials.

[0004] Among these, the use of multilayer films as packaging materials for lithium-ion battery casings is expanding. Packaging materials made of multilayer films include at least a base layer, a metal foil layer, a heat-adhesive resin layer, and an adhesive layer that bonds two adjacent layers. Multilayer films offer a high degree of freedom in shape, making them easy to process when manufacturing casings. However, when a multilayer film is deformed, the deformed area may turn white. Whitening in the casing can cause cracks and short circuits, so there is a demand for materials with excellent resistance to whitening.

[0005] Patent Document 3 describes a battery packaging material in which a base layer, a metal foil layer having a chemical treatment layer on at least one side, an acid-modified polyolefin layer, and a heat-seal layer consisting of a high-melting-point polypropylene layer and an ethylene-propylene random copolymer layer are laminated in order, wherein the high-melting-point polypropylene layer is positioned on the metal foil layer side of the ethylene-propylene random copolymer layer and has a melting point of 150°C or higher. In this battery packaging material, by positioning the high-melting-point polypropylene layer, which has a melting point of 150°C or higher, on the metal foil layer side of the ethylene-propylene random copolymer layer, the high-melting-point polypropylene layer will not melt even if a temperature rise occurs inside the outer packaging material due to overcharging or the like, preventing contact between the metal terminals and the metal foil layer, and suppressing the occurrence of internal short circuits.

[0006] Patent Document 4 describes a polypropylene resin composition for battery packaging films, comprising a propylene-ethylene block copolymer (A) containing a propylene-ethylene random copolymer component (A2) and a propylene-ethylene polymer component (A1) that meets specific conditions such as ethylene content, obtained by multi-stage polymerization. It is stated that the film formed from this composition has excellent heat resistance, sealing properties, and moldability, high seal strength and impact resistance, and improved whitening resistance and cracking resistance during deformation processing in a well-balanced manner.

[0007] Japanese Patent Publication No. 9-111069, Japanese Patent Publication No. 4-300933, Japanese Patent Publication No. 2007-273398, Japanese Patent Publication No. 2015-230777

[0008] Single-layer or multi-layer films used in packaging materials for lithium-ion batteries and the like have room for improvement in terms of balancing whitening resistance and mechanical properties. Therefore, the present invention aims to provide a resin composition that has an excellent balance between whitening resistance and mechanical properties, and a single-layer or multi-layer film comprising a layer containing the resin composition.

[0009] The present invention relates, for example, to the following [1] to

[11] . [1] A resin composition comprising: an unmodified propylene polymer (A) containing 60 to 100 mol% of constituent units derived from propylene and satisfying the following requirement (a); an unmodified 1-butene-propylene-ethylene copolymer (B) satisfying the following requirements (b-1) and (b-2); a modified polyolefin (C) containing constituent units derived from an unsaturated carboxylic acid and / or its derivative; and an unmodified ethylene polymer (D) containing 60 to 100 mol% of constituent units derived from ethylene, wherein the content of the 1-butene-propylene-ethylene copolymer (B) is 10.1 to 49.9% by mass (provided that the resin composition is 100% by mass). (a) The melting point observed by differential scanning calorimetry is 100°C or higher. (b-1) The content of constituent unit (i) derived from 1-butene is 50 to 96 mol%, the content of constituent unit (ii) derived from propylene is 1 to 40 mol%, and the content of constituent unit (iii) derived from ethylene is 3 to 20 mol% (provided that the total of constituent units (i), (ii), and (iii) is 100 mol%). (b-2) The ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene (Mw / Mn) is 3.0 or less.

[0010] [2] The resin composition according to [1], comprising: 45.0 to 84.8 parts by mass of the propylene polymer (A); 10.1 to 49.9 parts by mass of the 1-butene-propylene-ethylene copolymer (B); 0.1 to 10.0 parts by mass of the modified polyolefin (C); and 5.0 to 30.0 parts by mass of the ethylene polymer (D) (provided that the total of the propylene polymer (A), the 1-butene-propylene-ethylene copolymer (B), the modified polyolefin (C), and the ethylene polymer (D) is 100 parts by mass).

[0011] [3] The resin composition according to [1] or [2], wherein the modified polyolefin (C) contains 0.01 to 5% by mass of constituent units derived from an unsaturated carboxylic acid and / or its derivatives, converted to constituent units derived from maleic anhydride, and in the modified polyolefin (C), the content of constituent units derived from propylene in the constituent units excluding the constituent units derived from the unsaturated carboxylic acid and / or its derivatives is 90 to 100 mol%.

[0012] [4] The resin composition according to any one of [1] to [3], wherein the 1-butene-propylene-ethylene copolymer (B) satisfies at least one selected from the group consisting of the following requirements (b-3) and (b-4): (b-3) The melt flow rate (MFR) measured at 230°C and a 2.16 kg load in accordance with ASTM D1238 is 1 to 100 g / 10 min. (b-4) The molar ratio of the content of constituent unit (i) derived from 1-butene to the content of constituent unit (iii) derived from ethylene (content of constituent unit (i) / content of constituent unit (iii)) is 6 or more.

[0013] [5] A single-layer or multilayer film comprising at least one layer containing the resin composition described in any of [1] to [4].

[0014] [6] A multilayer film comprising at least one layer containing the resin composition described in any of [1] to [4], wherein both sides of the layer containing the resin composition are in contact with other layers.

[0015] [7] A multilayer film comprising at least one layer containing the resin composition described in any of [1] to [4], wherein one or both sides of the layer containing the resin composition are in contact with at least one layer selected from the group consisting of a metal-containing layer, a polyolefin layer, and a polar resin layer.

[0016] [8] A single-layer or multi-layer film according to any of [5] to [7], which is a film for food packaging.

[0017] [9] A single-layer or multi-layer film for use as a building material, as described in any of [5] to [7].

[0018]

[10] A single-layer or multi-layer film according to any one of [5] to [7], which is a film for packaging pouch-type batteries.

[0019]

[11] A method for producing a single-layer or multilayer film, comprising the step of melt-extruding a resin composition according to any one of [1] to [4].

[0020] The resin composition and single-layer or multi-layer film of the present invention exhibit an excellent balance between whitening resistance and mechanical properties. The single-layer or multi-layer film is suitably used as a packaging material for food packaging, building materials, and outer casings for lithium-ion batteries.

[0021] [Resin Composition] The resin composition of the present invention contains a propylene polymer (A), a 1-butene-propylene-ethylene copolymer (B), a modified polyolefin (C) containing structural units derived from an unsaturated carboxylic acid and / or its derivatives, and an ethylene polymer (D).

[0022] <Propylene-based polymer (A)> Propylene-based polymer (A) contains 60 to 100 mol% of propylene-derived structural units out of 100 mol% of total structural units derived from polymerizable monomers. Propylene-based polymer (A) is a polymer different from the 1-butene-propylene-ethylene copolymer (B), modified polyolefin (C), and ethylene-based polymer (D) described later. Examples of propylene-based polymer (A) include propylene homopolymer and copolymers of propylene and α-olefins having 2 to 20 carbon atoms (excluding propylene). Examples of α-olefins having 2 to 20 carbon atoms (excluding propylene) include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. The α-olefin may be one type or two or more types.

[0023] The propylene polymer (A) is preferably at least one polymer selected from the group consisting of propylene homopolymers, propylene-ethylene copolymers, and copolymers of propylene and α-olefins having 4 to 10 carbon atoms, more preferably a propylene homopolymer and / or a propylene-ethylene copolymer, and even more preferably a propylene homopolymer and a propylene-ethylene copolymer.

[0024] The copolymer of propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) may be a random copolymer or a block copolymer. The content of structural units derived from α-olefin in the propylene-α-olefin copolymer is preferably 35 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less, out of 100 mol% of the total structural units derived from polymerizable monomer, for example, 0.1 mol% or more. The content of structural units derived from propylene in the copolymer is preferably 65 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, out of 100 mol% of the total structural units derived from polymerizable monomer, for example, 99.9 mol% or less. The content of the structural units can be measured by the method described in the examples.

[0025] The propylene polymer (A) satisfies the following requirement (a): (a) Its melting point, as observed by differential scanning calorimetry, is 100°C or higher. The melting point is preferably 100 to 170°C, more preferably 120 to 165°C, and even more preferably 130 to 165°C. When the melting point of the propylene polymer (A) is within the above range, a resin composition with excellent heat resistance and mechanical properties at high temperatures (e.g., about 80°C) can be easily obtained. The melting point can be measured by the method described in the examples.

[0026] The melt flow rate (MFR) of the propylene polymer (A), measured at 230°C and a load of 2.16 kg in accordance with ASTM D1238, is preferably 0.01 to 1000 g / 10 min, more preferably 0.05 to 100 g / 10 min, even more preferably 0.1 to 50 g / 10 min, even more preferably 0.5 to 30 g / 10 min, and particularly preferably 1 to 10 g / 10 min. When the MFR of the propylene polymer (A) is within the above range, the resin composition exhibits excellent fluidity when melt-extruded.

[0027] The density of the propylene polymer (A) is preferably 700 to 1100 kg / m³. 3 More preferably 750 to 1050 kg / m 3 More preferably 800 to 1000 kg / m 3 Particularly preferred is 850 to 950 kg / m 3 Therefore, when the density of the propylene polymer (A) is within the above range, a resin composition with a good balance of impact resistance, rigidity, and transparency can be easily obtained. The density can be measured by the method described in the examples.

[0028] The structure of the propylene polymer (A) may be either an isotactic or syndiotactic structure, and either structure can be selected considering its compatibility with the 1-butene-propylene-ethylene copolymer (B) described later. Examples of the propylene polymer (A) include an isotactic propylene polymer (A1) and a syndiotactic propylene polymer (A2).

[0029] Examples of isotactic propylene polymers (A1) include homopolypropylene with excellent heat resistance, block polypropylene with an excellent balance of heat resistance and flexibility, and random polypropylene with an excellent balance of flexibility and transparency. Examples of block polypropylene include known block polypropylene having preferably 3 to 30% by mass of n-decane eluting rubber component. Examples of random polypropylene include known random polypropylene having a melting peak measured by differential scanning calorimeter (DSC) preferably of 100°C or higher, more preferably in the range of 110°C to 150°C. The isotactic propylene polymer (A1) may be one type or two or more types.

[0030] Isotactic propylene polymers (A1) can be produced, for example, by polymerizing propylene or propylene with other α-olefins using a Ziegler catalyst system or a metallocene catalyst system. The Ziegler catalyst system includes, for example, a solid catalyst component containing magnesium, titanium, halogens, and electron donors as essential components, an organoaluminum compound, and an electron donor. The metallocene catalyst system uses, for example, a metallocene compound as one component of the catalyst.

[0031] The syndiotactic propylene polymer (A2) preferably contains 90 mol% or more of structural units derived from propylene and 10 mol% or less of structural units selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms, and more preferably contains 91 mol% or more of structural units derived from propylene and 9 mol% or less of structural units selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms (provided that the total content of structural units derived from propylene and structural units selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms is 100 mol%).

[0032] Examples of α-olefins having 4 to 20 carbon atoms include 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. The syndiotactic propylene polymer (A2) can be produced using a method such as that described in International Publication No. 2011 / 078054. The syndiotactic propylene polymer (A2) may consist of one type or two or more types.

[0033] The propylene polymer (A) is an unmodified polymer. Polymer modification means altering the chemical structure of the main chain or side chains of the polymer by chemical means. Modification methods include, for example, oxidation-reduction treatment, graft polymerization, and modification by other chemical reactions. The propylene polymer (A) does not contain, for example, structural units derived from unsaturated carboxylic acids and / or their derivatives. The propylene polymer (A) may be one type or two or more types.

[0034] <1-Butene-Propylene-Ethylene Copolymer (B)> 1-Butene-Propylene-Ethylene Copolymer (B) satisfies the following requirements (b-1) and (b-2). 1-Butene-Propylene-Ethylene Copolymer (B) is a polymer different from the modified polyolefin (C) and ethylene-based polymer (D) described later.

[0035] (b-1) The content of constituent unit (i) derived from 1-butene is 50 to 96 mol%, the content of constituent unit (ii) derived from propylene is 1 to 40 mol%, and the content of constituent unit (iii) derived from ethylene is 3 to 20 mol% (provided that the total of constituent units (i), (ii), and (iii) is 100 mol%).

[0036] The content of constituent unit (i) is preferably 55 to 91.5 mol%, more preferably 60 to 85 mol%, even more preferably 65 to 80 mol%, and particularly preferably 70 to 75 mol%. The content of constituent unit (ii) is preferably 5 to 40 mol%, more preferably 10 to 35 mol%, even more preferably 15 to 30.5 mol%, and particularly preferably 20 to 25 mol%. The content of constituent unit (iii) is preferably 3.5 to 17 mol%, more preferably 4.0 to 15 mol%, even more preferably 4.5 to 13 mol%, and particularly preferably 5.0 to 10 mol%. The content (mol%) of each constituent unit in copolymer (B) is determined by the method described in the examples. 13 The results are measured using 13C-NMR. Because the content of each constituent unit falls within the aforementioned range, copolymer (B) exhibits excellent compatibility with propylene polymer (A).

[0037] (b-2) The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) on a polystyrene basis (Mw / Mn) is 3.0 or less. The Mw / Mn is preferably 2.7 or less, more preferably 2.5 or less, even more preferably 2.3 or less, and particularly preferably 2.0 or less. The Mw / Mn is, for example, 1.0 or more. Mw, Mn, and Mw / Mn can be measured by the method described in the examples.

[0038] Copolymer (B) that satisfies requirements (b-1) and (b-2) exhibits excellent compatibility with propylene polymer (A), and therefore, in the resin composition, whitening resistance can be efficiently improved while suppressing a decrease in mechanical properties. For this reason, the resin composition containing copolymer (B), in particular a resin composition containing 10.1 to 49.9% by mass of 1-butene-propylene-ethylene copolymer (B) per 100% by mass of the resin composition, exhibits an excellent balance between whitening resistance and mechanical properties. The resin composition exhibits an excellent balance between whitening resistance and mechanical properties at high temperatures (e.g., about 80°C).

[0039] The copolymer (B) preferably satisfies at least one selected from the group consisting of the following requirements (b-3) and (b-4), and more preferably satisfies the following requirements (b-3) and (b-4).

[0040] (b-3) The melt flow rate (MFR) measured at 230°C and a 2.16 kg load in accordance with ASTM D1238 is 1 to 100 g / 10 min. Preferably, the MFR is 2 to 90 g / 10 min, more preferably 3 to 85 g / 10 min, and even more preferably 3.2 to 80 g / 10 min. When the MFR of copolymer (B) is within the above range, it has good fluidity and the resulting molded article, such as a film, has good mechanical properties. When the MFR is above the lower limit, copolymer (B) has fluidity and the resin composition containing copolymer (B) is suitable for high-speed molding. When the MFR is below the upper limit, the resin composition containing copolymer (B) has excellent mechanical properties, adhesive strength, and durability.

[0041] (b-4) The molar ratio of the content of constituent unit (i) derived from 1-butene to the content of constituent unit (iii) derived from ethylene (content of constituent unit (i) / content of constituent unit (iii)) is 6 or more. The molar ratio is preferably 7 or more, more preferably 8 or more, even more preferably 9 or more, and particularly preferably 10 or more, for example, 20 or less. When the ratio is within the above range, copolymer (B) has excellent compatibility with propylene polymer (A).

[0042] 1-Butene-propylene-ethylene copolymer (B) is an unmodified polymer. 1-Butene-propylene-ethylene copolymer (B) does not contain constituent units derived from, for example, unsaturated carboxylic acids and / or their derivatives. 1-Butene-propylene-ethylene copolymer (B) may be used individually or in combination of two or more types.

[0043] <Preparation Method of 1-butene-propylene-ethylene Copolymer (B)> As a preparation method of 1-butene-propylene-ethylene copolymer (B), for example, there may be mentioned a method of polymerizing monomers by a known polymerization method such as a gas phase method, a bulk method or a slurry method in the presence of a catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. 1-butene-propylene-ethylene copolymer (B) has narrow molecular weight distribution and composition distribution, which not only enables the design of a molded article excellent in the balance between mechanical strength and flexibility, but also can achieve good compatibility especially when combined with a propylene-based polymer (A), and can delay the crystallization rate. Therefore, it is preferable to use an olefin polymerization catalyst containing a metallocene catalyst that can uniformly control the reaction, and it is particularly preferable to use an olefin polymerization catalyst containing a metallocene compound represented by the following general formula (1) or (2).

[0044]

[0045]

[0046] In the general formulas (1) and (2), R 1 to R 2 and R 5 to R 12 are each selected from the group consisting of a hydrogen atom, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different. The hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms. The hydrocarbon group may optionally contain one or more ring structures. Examples of the hydrocarbon group 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 and a tert-butyl group.

[0047] The silicon-containing hydrocarbon group is preferably an alkylsilyl group or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms. Examples of silicon-containing hydrocarbon groups include the trimethylsilyl group, the tert-butyldimethylsilyl group, and the triphenylsilyl group.

[0048] R 2 The hydrocarbon group is preferably a sterically bulky hydrocarbon group or a silicon-containing hydrocarbon group, i.e., a secondary or tertiary hydrocarbon group or a silicon-containing hydrocarbon group, and more preferably a hydrocarbon group or a silicon-containing hydrocarbon group having 4 or more carbon atoms. Examples of the hydrocarbon group include isopropyl group, 1,1-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, and 1,1-dimethylbutyl group. The hydrocarbon group is preferably a tert-butyl group. Examples of silicon-containing hydrocarbon groups include substituents in which some or all of the carbon atoms of the hydrocarbon group are substituted with silicon atoms.

[0049] R on the fluorene ring 5 ~R 12 Adjacent substituents may bond to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl and dibenzofluorenyl groups.

[0050] R on the fluorene ring 5 ~R 12 From the viewpoint of ease of synthesis of the metallocene compound, it is preferably symmetrical, i.e., R 5 = R 12 , R 6 = R 11 , R 7 = R 10 and R 8 = R 9 That is. R 5 ~R 12The fluorenyl group to which is bonded is preferably a group derived from unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene, or 2,3,6,7-tetrasubstituted fluorene. The 3, 6, 2, and 7 positions on the fluorene ring are R 7 , R 10 , R 6 and R 11 This corresponds to R. 5 ~R 12 Preferably all hydrogen atoms, R 5 ~R 6 , R 8 ~R 9 and R 11 ~R 12 is a hydrogen atom, R 7 and R 10 is a hydrocarbon group or a silicon-containing hydrocarbon group, R 5 , R 7 ~R 10 and R 12 is a hydrogen atom, R 6 and R 11 is a hydrocarbon group or a silicon-containing hydrocarbon group, or R 5 , R 8 ~R 9 and R 12 is a hydrogen atom, R 6 ~R 7 and R 10 ~R 11 This is a hydrocarbon group or a silicon-containing hydrocarbon group. 5 ~R 12 More preferably, all of them are hydrogen atoms.

[0051] R in general formula (1) 3 and R 4The hydrocarbon group is selected from the group consisting of hydrogen atoms and hydrocarbon groups, and may be the same or different. The hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms. Examples of the hydrocarbon group 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, and a tert-butyl group.

[0052] In general formulas (1) and (2), Y is a carbon atom or a silicon atom. In general formula (1), R 3 and R 4 Y is bonded to Y, forming a crosslinking portion consisting of a methylene group, a substituted methylene group, a silylene group, or a substituted silylene group. Examples of substituted methylene groups include dimethylmethylene, diisopropylmethylene, methyltert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, and diphenylmethylene. Examples of substituted silylene groups include dimethylsilylene and diisopropylsilylene. Y is preferably a carbon atom.

[0053] R in general formula (1) or (2) 2 If R is a tert-butyl group, 1 R is preferably a methyl group or an ethyl group, and more preferably a methyl group. 2 If is a tert-butyl group, then R in general formula (1) 3 and R 4 R is preferably a methyl group or a phenyl group, and more preferably a methyl group. 3 and R 4 These are preferably the same as each other. R in formula (1) 2 is a tert-butyl group, R 1If R is a methyl group, 5 ~R 12 R is preferably a hydrogen atom. 2 is a tert-butyl group, R 1 If R is an ethyl group, 5 , R 7 , R 8 , R 9 , R 10 , and R 12 is preferably a hydrogen atom, R 6 and R 11 Preferably, it is a tert-butyl group.

[0054] In formula (2), A is a divalent hydrocarbon group having 2 to 20 carbon atoms. A may contain an unsaturated bond and / or an aromatic ring. In formula (2), Y is bonded to A to form a cycloalkylidene group or a cyclomethylenesilylene group, etc. Examples of cycloalkylidene groups include cyclopropylidene, cyclobutylidene, cyclopentylidene, and cyclohexylidene.

[0055] In general formulas (1) and (2), M is a metal atom selected from Group 4 of the periodic table. Examples of the metal atom include titanium, zirconium, and hafnium. The metal atom is preferably a zirconium atom.

[0056] In general formulas (1) and (2), j is an integer from 1 to 4 representing the number of Qs, which will be described later. j is preferably 2. In general formulas (1) and (2), Q is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand that can coordinate with a lone pair of electrons.

[0057] Examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of the hydrocarbon group include R 1 ~R 2 and R 5 ~R 12Examples of substituents similar to those exemplified for hydrocarbon groups include anionic ligands such as alkoxy groups such as methoxy, tert-butoxy, and phenoxy groups, carboxylate groups such as acetate and benzoate groups, and sulfonate groups such as mesylate and tosylate groups. Examples of neutral ligands that can coordinate with a lone pair of electrons include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, and ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0058] When j is 2 to 4, the multiple Qs may be the same or different from each other. When j is 2 to 4, preferably at least one Q is a halogen atom or an alkyl group, more preferably at least one Q is a halogen atom, and even more preferably all Qs are halogen atoms.

[0059] The olefin polymerization catalyst contains, in addition to a metallocene compound represented by formula (1) or formula (2), at least one compound (Y) selected from the group consisting of an organoaluminum oxy compound (Y-1), a compound that reacts with the metallocene compound to form an ion pair (Y-2), and an organoaluminum compound (Y-3). The olefin polymerization catalyst may also contain a particulate support.

[0060] Examples of organoaluminum oxy compounds (Y-1) include conventionally known aluminoxanes and modified aluminoxanes. Examples of compounds that react with metallocene compounds to form ion pairs (Y-2) (hereinafter sometimes abbreviated as "ionic compounds") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950 and Japanese Patent Publication No. 2004-51676, etc. Furthermore, heteropoly compounds and isopoly compounds are also included.

[0061] Examples of the ionic compound include triphenylboron, tris(o-tolyl)boron, tris(p-tolyl)boron, tris(3,5-dimethylphenyl)boron, trimethylboron, triisobutylboron; compounds having a halogen-containing aryl group such as compounds having a fluorine-containing aryl group including tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron; and trifluoroboron.

[0062] Examples of the organoaluminum compound (Y-3) include organoaluminum compounds represented by the following general formula (3). R a m Al(OR b ) n H p X q ...(3) (In the formula, R a and R b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is a number satisfying 0 < m ≤ 3, n is a number satisfying 0 ≤ n < 3, p is a number satisfying 0 ≤ p < 3, q is a number satisfying 0 ≤ q < 3, and m + n + p + q = 3.)

[0063] Examples of the organoaluminum compound represented by general formula (3) include dialkylaluminum hydrides such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, diisopropylaluminum hydride, and diisobutylaluminum hydride; and alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide.

[0064] The organoaluminum compound (Y-3) is preferably tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, and trioctylaluminum, or tri-branched-chain alkylaluminum such as triisobutylaluminum, and more preferably trimethylaluminum or triisobutylaluminum.

[0065] Polymerization using the olefin polymerization catalyst can be carried out by either liquid-phase polymerization methods such as dissolution polymerization and suspension polymerization, or by gas-phase polymerization methods. In liquid-phase polymerization, an inert hydrocarbon solvent may be used. Examples of inert hydrocarbon solvents include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, and decane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene, or mixtures thereof. Bulk polymerization can also be carried out using olefins containing 1-butene as the solvent.

[0066] The metallocene compound is present in an amount equivalent to, for example, 1 × 10⁶ metal atoms per liter of reaction volume. -8 ~1 x 10 -2 Moles, preferably 1 × 10 -7 ~1 x 10 -3 The amounts used are such that they are molars. The organoaluminum oxy compound (Y-1) is used in an amount such that the molar ratio [(Y-1) / M] of the transition metal atom (M) in the metallocene compound to the organoaluminum oxy compound (Y-1) is, for example, 0.01 to 5000, preferably 0.05 to 2000. The ionic compound (Y-2) is used in an amount such that the molar ratio [(Y-2) / M] of the transition metal atom (M) in the metallocene compound to the ionic compound (Y-2) is, for example, 1 to 10, preferably 1 to 5. The organoaluminum compound (Y-3) is used in an amount such that the molar ratio [(Y-3) / M] of the transition metal atom (M) in the metallocene compound to the organoaluminum compound (Y-3) is, for example, 10 to 5000, preferably 20 to 2000.

[0067] The polymerization temperature is, for example, -50 to 200°C, preferably 0 to 100°C, and more preferably 20 to 100°C. If the polymerization temperature is too low, it tends to be industrially disadvantageous in terms of polymerization activity per unit catalyst and heat recovery efficiency. The polymerization pressure is, for example, atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by batch, semi-continuous, or continuous methods. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions.

[0068] Hydrogen can be added to control the molecular weight and polymerization activity of the 1-butene-propylene-ethylene copolymer (B) produced during polymerization, and the appropriate amount is approximately 0.001 to 100 NL per 1 kg of 1-butene-propylene-ethylene copolymer (B).

[0069] <Modified polyolefin (C) containing constituent units derived from unsaturated carboxylic acids and / or their derivatives> Modified polyolefin (C) containing constituent units derived from unsaturated carboxylic acids and / or their derivatives (hereinafter also referred to as "modified polyolefin (C)") is obtained by modifying an unmodified polyolefin with an unsaturated carboxylic acid and / or its derivative, and contains constituent units derived from the unsaturated carboxylic acid and / or its derivative. Modified polyolefin (C) is different from the ethylene-based polymer (D) described later.

[0070] Examples of the unmodified polyolefins include polypropylene (c1), ethylene-propylene-α-olefin copolymer (c2), and ethylene-α-olefin copolymer (c3).

[0071] Examples of polypropylene (c1) include propylene homopolymers and propylene-α-olefin copolymers. The α-olefin is preferably an α-olefin having 2 to 20 carbon atoms (excluding propylene). Examples of α-olefins having 2 to 20 carbon atoms (excluding propylene) include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. The α-olefin may be one type or two or more types.

[0072] The α-olefin is preferably ethylene or an α-olefin having 4 to 10 carbon atoms, and more preferably ethylene or an α-olefin having 4 to 8 carbon atoms. The content of constituent units derived from propylene in the propylene-α-olefin copolymer is 50 mol% or more and less than 100 mol%. The content of the constituent units is 13 Measurement is performed using 13C-NMR. Polypropylene (c1) does not necessarily have to contain constituent units derived from ethylene, for example.

[0073] The intrinsic viscosity [η] of polypropylene (c1) is preferably 0.1 to 10 dl / g. The intrinsic viscosity [η] of the modified polyolefin (C) obtained by modifying such polypropylene (c1) is preferably 0.1 to 6 dl / g, more preferably 0.2 to 5 dl / g, and even more preferably 0.3 to 4 dl / g. When the intrinsic viscosity [η] is within the above range, a resin composition with excellent moldability and mechanical strength can be obtained. The intrinsic viscosity [η] can be measured in accordance with ASTM D1601.

[0074] The method for producing polypropylene (c1) is not particularly limited, and well-known methods using well-known catalysts such as Ziegra-Natta catalysts and metallocene catalysts can be cited. Polypropylene (c1) is preferably a crystalline polymer. When polypropylene (c1) is a copolymer, it may be a random copolymer or a block copolymer. There are no particular restrictions on stereoregularity and molecular weight as long as it satisfies moldability and has sufficient strength to withstand use when made into a molded article such as a film. Commercial products can also be used as is. Polypropylene (c1) is, for example, homopolypropylene or propylene-α-olefin random copolymer. It may also contain several different isotactic polypropylenes. Polypropylene (c1) may be one type or two or more types.

[0075] Ethylene-propylene-α-olefin copolymer (c2) is a copolymer of ethylene, propylene, and an α-olefin having 4 to 20 carbon atoms, and satisfies, for example, the following requirements (c2-i) and (c2-ii). (c2-i) The ethylene-propylene-α-olefin copolymer (c2) contains 45 to 89 mol% of constituent units derived from propylene, 10 to 25 mol% of constituent units derived from ethylene, and 1 to 30 mol% of constituent units derived from an α-olefin having 4 to 20 carbon atoms (provided that the content of constituent units derived from propylene, constituent units derived from ethylene, and constituent units derived from an α-olefin having 4 to 20 carbon atoms is 100 mol%).

[0076] The α-olefin is preferably an α-olefin having 4 to 10 carbon atoms. Examples of the α-olefin include those similar to the α-olefins exemplified in polypropylene (c1) (excluding ethylene). The α-olefin may be one type or two or more types.

[0077] The content of structural units derived from propylene in the ethylene-propylene-α-olefin copolymer (c2) is preferably 50 to 85 mol%, more preferably 55 to 80 mol%. The content of structural units derived from ethylene is preferably 10 to 22 mol%, more preferably 10 to 20 mol%. The content of structural units derived from the α-olefin is preferably 5 to 28 mol%, more preferably 10 to 28 mol%. The content of the structural units is 13 measured using 13C-NMR.

[0078] (c2-ii) The intrinsic viscosity [η] in decalin at 135°C is 0.1 to 10 dl / g. The intrinsic viscosity [η] is preferably 0.1 to 6 dl / g, more preferably 0.2 to 5 dl / g, still more preferably 0.3 to 4 dl / g. The intrinsic viscosity [η] of the modified polyolefin (C) obtained by modifying such an ethylene-propylene-α-olefin copolymer (c2) is preferably 0.1 to 6 dl / g, more preferably 0.2 to 5 dl / g, still more preferably 0.3 to 4 dl / g. When the intrinsic viscosity [η] falls within the above range, a resin composition excellent in the balance between flexibility and mechanical strength and having excellent adhesion can be obtained. The intrinsic viscosity [η] can be measured in accordance with ASTM D1601.

[0079] The method for producing the ethylene-propylene-α-olefin copolymer (c2) is not particularly limited, and known methods using known catalysts such as Ziegler-Natta catalysts and metallocene catalysts can be used.

[0080] The ethylene-propylene-α-olefin copolymer (c2) is not particularly limited in terms of stereoregularity and molecular weight as long as it satisfies the moldability of the resin composition and has strength that can withstand use when formed into a molded article such as a film. Commercial products can be used as they are. The ethylene-propylene-α-olefin copolymer (c2) may be used alone or in combination of two or more.

[0081] Ethylene-α-olefin copolymer (c3) is a copolymer of ethylene and α-olefin, and satisfies, for example, the following requirements (c3-i) and (c3-ii). (c3-i) Ethylene-α-olefin copolymer (c3) contains 50 to 99 mol% of constituent units derived from ethylene and 1 to 50 mol% of constituent units derived from α-olefins having 3 to 20 carbon atoms (provided that the content of constituent units derived from ethylene and constituent units derived from α-olefins having 3 to 20 carbon atoms is 100 mol%).

[0082] The α-olefin is preferably an α-olefin having 3 to 10 carbon atoms. Examples of the α-olefin include propylene and the same α-olefins exemplified in polypropylene (c1) (excluding ethylene). The α-olefin may be one type or two or more types. The content of constituent units derived from ethylene is preferably 55 to 98 mol%, more preferably 60 to 95 mol%. The content of constituent units derived from the α-olefin is preferably 2 to 45 mol%, more preferably 5 to 40 mol%. The content of the constituent units is 13 It is measured using C-NMR.

[0083] (c3-ii) has an intrinsic viscosity [η] of 0.1 to 10 dl / g in decalin at 135°C. The intrinsic viscosity [η] is preferably 0.1 to 6 dl / g, more preferably 0.2 to 5 dl / g, and even more preferably 0.3 to 4 dl / g. The intrinsic viscosity [η] of the modified polyolefin (C) obtained by modifying such an ethylene-α-olefin copolymer (c3) is preferably 0.1 to 6 dl / g, more preferably 0.2 to 5 dl / g, and even more preferably 0.3 to 4 dl / g. When the intrinsic viscosity [η] is within the above range, a resin composition with an excellent balance between flexibility and mechanical strength and excellent adhesion can be obtained. The intrinsic viscosity [η] can be measured in accordance with ASTM D1601.

[0084] The method for producing ethylene-α-olefin copolymer (C3) is not particularly limited, and includes well-known methods using well-known catalysts such as Ziegra-Natta catalysts and metallocene catalysts.

[0085] The ethylene-α-olefin copolymer (C3) has no particular restrictions on stereoregularity or molecular weight, as long as the resin composition exhibits excellent moldability and ensures sufficient strength for use as a molded article such as a film. Commercially available ethylene-α-olefin copolymer (C3) can also be used as is. The ethylene-α-olefin copolymer (C3) may consist of one type or two or more types.

[0086] From the viewpoint of heat resistance, the modified polyolefin (C) is preferably obtained by modifying unmodified polypropylene (c1) with an unsaturated carboxylic acid and / or its derivative, and more preferably by modifying a propylene homopolymer with an unsaturated carboxylic acid and / or its derivative.

[0087] Examples of unsaturated carboxylic acids and / or derivatives used to modify the unmodified polyolefin include unsaturated compounds containing one or more carboxyl groups per molecule, esters of compounds containing carboxyl groups with alkyl alcohols, and unsaturated compounds containing one or more carboxylic acid anhydride groups per molecule. Examples of unsaturated groups in unsaturated compounds include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups. One or more unsaturated carboxylic acids and / or derivatives may be used. Preferably, the unsaturated carboxylic acids and / or derivatives are unsaturated dicarboxylic acids or their acid anhydrides, and more preferably maleic acid, nadic acid, or their acid anhydrides.

[0088] The modified polyolefin (C) contains, preferably, 0.01 to 5% by mass, more preferably 0.1 to 4.7% by mass, even more preferably 0.3 to 4.5% by mass, even more preferably 0.5 to 4.3% by mass, and particularly preferably 0.7 to 4.0% by mass, of constituent units derived from unsaturated carboxylic acids and / or their derivatives, converted to constituent units derived from maleic anhydride. The resin composition containing such a modified polyolefin (C) tends to have an excellent balance of moldability and adhesion. The content of constituent units derived from unsaturated carboxylic acids and / or their derivatives, converted to constituent units derived from maleic anhydride, refers to the content of constituent units derived from maleic anhydride relative to 100% by mass of maleic anhydride-modified polyolefin, when the constituent units derived from unsaturated carboxylic acids and / or their derivatives are considered as constituent units derived from maleic anhydride. When the amount of constituent units derived from unsaturated carboxylic acids and / or their derivatives is within the above range, a resin composition with an excellent balance of moldability and adhesion can be obtained.

[0089] The content of constituent units derived from unsaturated carboxylic acids and / or their derivatives, converted to constituent units derived from maleic anhydride, can be measured by the following method. First, a modified polyolefin (C) sample is treated at 250°C, preheated for 5 minutes, and pressed for 3 minutes to create a pressed film. An IR measurement is then performed on the pressed film using a Fourier transform infrared spectrophotometer (e.g., FT-IR410, manufactured by JASCO Corporation) by transmission. The amount of graft modification based on unsaturated carboxylic acids and / or their derivatives can be calculated from the peak intensity in the obtained IR spectrum. By using the molecular weight of the unsaturated carboxylic acid and / or its derivative and the molecular weight of maleic anhydride, the content converted to constituent units derived from maleic anhydride can be calculated from the amount of graft modification. When maleic anhydride is used for graft modification, for example, 1860 cm⁻¹ -1 and 4321cm -1The amount of graft modification can be calculated from the peak intensity. Specifically, the content of constituent units derived from unsaturated carboxylic acids and / or their derivatives, converted to constituent units derived from maleic anhydride, is calculated as [amount of graft modification based on unsaturated carboxylic acids and / or their derivatives] × [molecular weight of maleic anhydride] / [molecular weight of unsaturated carboxylic acids and / or their derivatives].

[0090] In the modified polyolefin (C), the content of propylene-derived structural units in the structural units excluding those derived from the unsaturated carboxylic acid and / or its derivatives is preferably 90 to 100 mol%, more preferably 95 to 100 mol%. The content of propylene-derived structural units in the modified polyolefin (C), excluding those derived from the unsaturated carboxylic acid and / or its derivatives, refers to the content of propylene-derived structural units relative to 100 mol% of the total content of structural units excluding those derived from the unsaturated carboxylic acid and / or its derivatives from all polymerizable monomers in the modified polyolefin (C). When the content of propylene-derived structural units is within the above range, a resin composition with excellent heat resistance can be obtained. The content of the structural units is, 13 It is measured using C-NMR.

[0091] The method for modifying polypropylene (c1) and the like using an unsaturated carboxylic acid and / or its derivative, particularly the graft modification method, is not particularly limited, and conventionally known graft polymerization methods such as the solution method and the melt kneading method can be employed. Examples of such methods include a method in which polypropylene (c1) and the like are melted and an unsaturated carboxylic acid and / or its derivative is added to carry out a graft reaction, and a method in which polypropylene (c1) and the like are dissolved in a solvent to form a solution and an unsaturated carboxylic acid and / or its derivative is added to carry out a graft reaction. One type of modified polyolefin (C) may be used, or two or more types may be used.

[0092] <Ethylene-based polymer (D)> The ethylene-based polymer (D) contains 60 to 100 mol% of ethylene-derived structural units out of 100 mol% of the total structural units derived from polymerizable monomers. Examples of ethylene-based polymer (D) include high-pressure low-density polyethylene (D1) and ethylene-α-olefin copolymer (D2). The ethylene-based polymer (D) preferably contains high-pressure low-density polyethylene (D1) and ethylene-α-olefin copolymer (D2).

[0093] By using an ethylene-based polymer (D), the resulting resin composition allows for easy production of molded articles such as films that exhibit excellent moldability during molding processes and a good balance of whitening resistance, impact resistance, and transparency during deformation processes.

[0094] <High-Pressure Method Low-Density Polyethylene (D1)> Known polymers can be used as high-pressure method low-density polyethylene (D1). High-pressure method low-density polyethylene is generally polyethylene obtained by radical polymerization of ethylene under high temperature and high pressure. A method for producing high-pressure method low-density polyethylene is, for example, a radical polymerization method in which radical polymerization is carried out under conditions of 500 to 2000 atmospheres and 150 to 300°C. An example of a polymerization initiator is an organic peroxide.

[0095] The density of high-pressure low-density polyethylene (D1), measured in accordance with ASTM D1505, is preferably 900 to 925 kg / m³. 3 More preferably 910 to 925 kg / m 3 When the density is within the aforementioned range, molded articles such as films with a good balance of impact resistance, rigidity, and transparency can be easily obtained. The density can be measured by the method described in the examples.

[0096] According to ASTM D1238, the melt flow rate (MFR) of high-pressure low-density polyethylene (D1), measured at 190°C and a 2.16 kg load, is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, even more preferably 1.0 g / 10 min or more, particularly preferably 5.0 g / 10 min or more, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, even more preferably 20 g / 10 min or less, particularly preferably 15 g / 10 min or less, for example, between 0.1 and 50 g / 10 min. When the MFR of high-pressure low-density polyethylene (D1) is within the above range, the resin composition exhibits excellent fluidity during melt extrusion molding.

[0097] <Ethylene-α-olefin copolymer (D2)> Ethylene-α-olefin copolymer (D2) contains constituent units derived from ethylene and constituent units derived from α-olefins having 3 to 20 carbon atoms.

[0098] Examples of the α-olefin 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. The α-olefin is preferably an α-olefin having 3 to 10 carbon atoms, more preferably an α-olefin having 3 to 8 carbon atoms, even more preferably propylene, 1-butene, or 1-octene, and particularly preferably propylene. The α-olefin may be used individually or in combination of two or more types.

[0099] The content of ethylene-derived structural units in the ethylene-α-olefin copolymer (D2) is, for example, 60 to 99 mol%, preferably 65 to 99 mol%, more preferably 70 to 99 mol%, and even more preferably 80 to 99 mol%, based on 100 mol% of the total content of ethylene-derived structural units and α-olefin-derived structural units. The content of α-olefin-derived structural units is, for example, 1 to 40 mol%, preferably 1 to 35 mol%, more preferably 1 to 30 mol%, and even more preferably 1 to 20 mol%. When the content of each structural unit is within the above range, a molded article such as a film with a good balance of whitening resistance, impact resistance, and flexibility during deformation processing can be easily obtained from the resulting resin composition. The content of the structural units is, by the method described in the examples, 13 It is measured using C-NMR.

[0100] In ethylene-α-olefin copolymers (D2), there are fewer long-chain branched structures compared to high-pressure low-density polyethylene (D1), and ethylene-α-olefin copolymers (D2) are generally sometimes referred to as linear low-density polyethylene (LLDPE).

[0101] Examples of ethylene-α-olefin copolymers (D2) include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-1-butene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, and ethylene-1-octene copolymer. The ethylene-α-olefin copolymer (D2) is preferably ethylene-propylene copolymer or ethylene-1-butene copolymer.

[0102] The density of the ethylene-α-olefin copolymer (D2) is preferably 840 kg / m³. 3 More preferably, 850 kg / m 3 More preferably, 55 kg / m 3 The above is preferable, preferably 940 kg / m 3 More preferably, 899 kg / m 3 More preferably, 890 kg / m3 The following is particularly preferred: 885 kg / m 3 The following are examples, for instance, 840-940 kg / m 3 When the density is within the aforementioned range, molded articles such as films with a good balance of impact resistance, rigidity, and transparency can be easily obtained. The density can be measured by the method described in the examples.

[0103] According to ASTM D1238, the melt flow rate (MFR) of the ethylene-α-olefin copolymer (D2), measured at 190°C under a 2.16 kg load, is preferably 0.01 g / 10 min or more, more preferably 0.1 g / 10 min or more, even more preferably 0.3 g / 10 min or more, preferably 40 g / 10 min or less, more preferably 20 g / 10 min or less, and even more preferably 10 g / 10 min or less, for example, between 0.01 and 40 g / 10 min. When the MFR is within the above range, molded articles such as films with a good balance of impact resistance, rigidity, and transparency can be easily obtained.

[0104] MFR of ethylene-α-olefin copolymer (D2) measured under conditions of 190°C and 10 kg load in accordance with ASTM D1238. 10 The MFR measured under the conditions of 190°C and a load of 2.16 kg. 2.16 Ratio to (MFR) 10 / MFR 2.16 ) is preferably 4.0 or higher, more preferably 5.0 or higher, preferably 8.0 or lower, more preferably 7.0 or lower, for example, 4.0 to 8.0. MFR 10 / MFR 2.16 When the range is within the aforementioned range, it is easy to obtain molded articles such as films that have a good balance of transparency and impact resistance.

[0105] Ethylene-α-olefin copolymer (D2) can be produced by conventionally known methods using vanadium-based catalysts, titanium-based catalysts, or metallocene-based catalysts. Ethylene-α-olefin copolymer (D2) produced using metallocene-based catalysts has a relatively narrow molecular weight distribution and composition distribution, making it more preferable in terms of mechanical properties, transparency, and impact resistance.

[0106] The ethylene polymer (D) is an unmodified polymer. The copolymer (D) does not contain any constituent units derived from, for example, unsaturated carboxylic acids and / or their derivatives. One type of ethylene polymer (D) may be used, or two or more types may be used.

[0107] <Other Components> The resin composition may contain components other than the propylene polymer (A), 1-butene-propylene-ethylene copolymer (B), modified polyolefin (C), and ethylene polymer (D) (hereinafter also referred to as "other components"), to the extent that they do not impair the effects of the present invention. Examples of other components include polymers with different compositions from the propylene polymer (A), 1-butene-propylene-ethylene copolymer (B), modified polyolefin (C), and ethylene polymer (D) (hereinafter also referred to as "other polymers"), antioxidants, ultraviolet absorbers, neutralizing agents, nucleating agents, light stabilizers, antistatic agents, antiblocking agents, lubricants, odor adsorbents, antibacterial agents, pigments, inorganic and organic fillers, and synthetic resins. Examples of other polymers include styrene elastomers.

[0108] <Resin Composition> The resin composition contains a propylene polymer (A), a 1-butene-propylene-ethylene copolymer (B), a modified polyolefin (C), and an ethylene polymer (D). The resin composition can be produced by conventionally known methods, for example, by melt-kneading each of the above components.

[0109] The content of 1-butene-propylene-ethylene copolymer (B) per 100% by mass of the resin composition is 10.1 to 49.9% by mass. When the content is 10.1% by mass or more, the resin composition exhibits excellent whitening resistance. When the content is 49.9% by mass or less, the resin composition exhibits excellent mechanical properties, particularly at high temperatures (e.g., about 80°C).

[0110] The content of the propylene polymer (A) is preferably 45.0 to 84.8 parts by mass, more preferably 45.0 to 70.0 parts by mass, and even more preferably 45.0 to 60.0 parts by mass. The content of the 1-butene-propylene-ethylene copolymer (B) is preferably 10.1 to 49.9 parts by mass, more preferably 15.0 to 40.0 parts by mass, and even more preferably 15.0 to 35.0 parts by mass. The content of the modified polyolefin (C) is preferably 0.1 to 10.0 parts by mass, more preferably 2.0 to 8.0 parts by mass, and even more preferably 3.0 to 7.0 parts by mass. The content of the ethylene polymer (D) is preferably 5.0 to 30.0 parts by mass, more preferably 10.0 to 20.0 parts by mass, and even more preferably 15.0 to 20.0 parts by mass. The aforementioned content is the amount relative to 100 parts by mass of the total content of the propylene polymer (A), 1-butene-propylene-ethylene copolymer (B), modified polyolefin (C), and ethylene polymer (D). When the content of each component is within the aforementioned range, a film comprising a layer containing the resin composition exhibits an excellent balance between whitening resistance and mechanical properties, particularly between whitening resistance and mechanical properties at high temperatures (e.g., about 80°C).

[0111] The content of the other components is not particularly limited, but is preferably 10.0 parts by mass or less, and more preferably 0.01 to 5.0 parts by mass, based on 100 parts by mass of the total content of the propylene polymer (A), 1-butene-propylene-ethylene copolymer (B), modified polyolefin (C), and ethylene polymer (D).

[0112] [Single-layer or multi-layer film] The single-layer or multi-layer film of the present invention comprises at least one layer containing the resin composition. The single-layer film consists of layers containing the resin composition, and the multi-layer film comprises at least one layer containing the resin composition.

[0113] The single-layer or multi-layer film exhibits an excellent balance between resistance to whitening during deformation and mechanical properties. When the single-layer or multi-layer film is used in food packaging, building materials, and lithium-ion battery casings, whitening is less likely to occur during secondary processing such as drawing and folding. Furthermore, the single-layer or multi-layer film has a particularly high tensile fracture energy at high temperatures (e.g., about 80°C), so when used in pouch form, the energy required to break the seal is high, resulting in particularly excellent durability at high temperatures. For these reasons, the single-layer or multi-layer film can be suitably used as a film for food packaging, building materials, and battery packaging.

[0114] Examples of battery packaging materials include pouch-type and embossed-type packaging. Examples of pouch-type battery packaging materials include bag shapes such as three-sided seal, four-sided seal, and pillow-type packaging. Examples of embossed-type battery packaging materials include those in which a recess is formed in one or both outer materials, the battery body is housed in this recess, and the surrounding flange is heat-sealed to create a sealed structure. The single-layer or multi-layer film is suitably used as a pouch-type battery packaging material (film for pouch-type battery packaging).

[0115] The multilayer film comprises, for example, at least one layer containing the resin composition. One or both sides of the layer containing the resin composition are in contact with other layers. Examples of other layers include a metal-containing layer, a polyolefin layer, and a polar resin layer. Examples of metal-containing layers include an aluminum layer, a copper layer, and a stainless steel layer. Examples of polyolefin layers include a polypropylene layer, a poly-methylpentene layer, and a polyethylene layer. Examples of polar resin layers include a polyamide layer, an EVOH (ethylene-vinyl alcohol copolymer resin) layer, a PET (polyethylene terephthalate) layer, and a PBT (polybutylene terephthalate) layer. In the multilayer film, one or both sides of the layer containing the resin composition may be in contact with at least one layer selected from the group consisting of a metal-containing layer, a polyolefin layer, and a polar resin layer, or may be in contact with at least one layer selected from the group consisting of a metal-containing layer and a polyolefin layer, or may be in contact with at least one layer selected from the group consisting of a metal-containing layer and a polar resin layer, or may be in contact with a metal-containing layer, or may be in contact with a polyolefin layer, or may be in contact with a polar resin layer.

[0116] A portion of the surface of the layer containing the resin composition that faces the other layer may be in contact with the other layer, or all of the surface that faces the other layer may be in contact with the other layer.

[0117] The thickness of the single-layer or multilayer film can be appropriately selected depending on the application, but is, for example, 5 to 1000 μm, preferably 10 to 800 μm, more preferably 20 to 800 μm, and particularly preferably 30 to 500 μm. The film thickness is measured, for example, by observing the cross-section of the film in a direction perpendicular to the surface of the film using a scanning electron microscope (SEM). The single-layer or multilayer film may or may not be stretched. Preferably, the single-layer or multilayer film is not stretched.

[0118] The single-layer or multi-layer film can be obtained by melt extrusion molding and can be manufactured by commonly used industrial methods such as casting, inflation, and extrusion lamination.

[0119] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples as long as it does not exceed the gist of the invention.

[0120] (Various Measurement Methods) In this example, measurements were performed according to the following methods. [Melt Flow Rate (MFR)] The MFRs of propylene polymer (A), 1-butene-propylene-ethylene copolymer (B), propylene-ethylene copolymer, and propylene-ethylene-α-olefin copolymer were measured in accordance with ASTM D1238 under conditions of 230°C and a 2.16 kg load. The MFR of ethylene polymer (D) was measured in accordance with ASTM D1238 under conditions of 190°C and a 2.16 kg load.

[0121] [Density] Density was measured at 25°C in accordance with ASTM D1505. [Intrinsic viscosity [η]] Intrinsic viscosity [η] was measured in accordance with ASTM D1601.

[0122] [1-Butene Content, Propylene Content, and Ethylene Content] The content of constituent units derived from 1-butene (1-butene content), the content of constituent units derived from propylene (propylene content), and the content of constituent units derived from ethylene (ethylene content) in propylene polymers (A), 1-butene-propylene-ethylene copolymers (B), ethylene polymers (D), propylene-ethylene copolymers, and propylene-ethylene-α-olefin copolymers is determined under the following conditions: 13 C-NMR measurements were performed, and the results were obtained 13 The results were calculated by analyzing the C-NMR spectrum. Instrument: Bruker BioSpin AVANCE cryo-500 Nuclear Magnetic Resonance Spectrometer Observed nuclei: 13C (125 MHz) Solvent: o-dichlorobenzene / deuterated benzene mixed solvent (volume ratio: 80 / 20) Sample concentration: 20 mg / 0.6 mL Measurement temperature: 120 °C Sequence: Single pulse proton broadband decoupling Pulse width: 4.7 μs (45° pulse) Repetition time: 5.5 sec Number of integrations: 128 Chemical shift reference value: Carbon signal of butene side chain methylene group: 27.50 ppm

[0123] [Weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn)] A Waters Alliance GPC-2000 gel permeation chromatograph was used as the GPC instrument, and Mw and Mn in polystyrene equivalent were measured under the following conditions, and Mw / Mn was calculated. Separation columns: Two TSKgel GNH6-HT columns and two TSKgel GNH6-HTL columns manufactured by Tosoh Corporation (both columns are 7.5 mm in diameter and 300 mm in length) 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 Company Limited) as an antioxidant Transfer rate: 1.0 mL / min Sample concentration: 15 mg / 10 mL Sample injection volume: 400 μL Detector: Differential refractometer Standard polystyrene: Molecular weight Mw < 1000 and Mw > 4 × 10 ６ In this case, use a product manufactured by Tosoh Corporation, with a molecular weight of 1000 ≤ Mw ≤ 4 × 10 ６ In this case, a product from Pressure Chemical Co., Ltd. was used.

[0124] [Melting Point (Tm)] The melting point (Tm) of the propylene polymer (A) was measured using a PerkinElmer DSC8500 differential scanning calorimeter (DSC). 5-10 mg of the propylene polymer (A) was sealed in an aluminum pan to prepare the sample. The temperature profile was obtained by raising the temperature from room temperature to 230°C at a rate of 10°C / min, holding at 230°C for 5 minutes, then lowering the temperature to -80°C at a rate of 10°C / min, holding at -80°C for 5 minutes, and then raising the temperature again to 230°C at a rate of 10°C / min. The melting point (Tm) was calculated from the chart obtained during this second heating cycle.

[0125] [Whitening Resistance Evaluation] A 0.5 mm thick press sheet (single-layer film) was prepared using a press molding machine under the following conditions: preheating and pressurizing temperature: 200°C, preheating time: 6 minutes, pressure: 10 MPa, pressurizing time: 4 minutes, cooling temperature: 20°C, cooling time: 4 minutes. A JIS K6301 No. 2 dumbbell was punched out from the press sheet to prepare a test specimen for measurement. Using a Shimadzu ATX tensile testing machine, the hue change of the test specimen when it was pulled 20 mm at a tensile speed of 200 mm / min at room temperature was measured by the reflection method using a Konica Minolta CM-3700A. The hue change when pulled 20 mm from the initial value (0 mm) is defined as ΔL.

[0126] [Breaking Strength and Tensile Breaking Energy] Using a hydraulic hot press molding machine set to 210°C, the resin composition obtained in the example or comparative example was heated for 8 minutes, molded under a pressure of 10 MPa for 4 minutes, and then cooled for 4 minutes at 20°C under a pressure of 10 MPa to produce a 2 mm thick sheet (test specimen). After 7 days or more had elapsed at room temperature since molding, a No. 5A dumbbell was made from the sheet in accordance with JIS K7161-2, and the breaking strength and tensile breaking energy of the dumbbell were measured under the conditions of temperature: 23°C (room temperature) or 80°C (high temperature) and tensile speed: 500 mm / min.

[0127] [AL Adhesion Strength] A 100 μm thick film was formed from the resin composition using an extrusion molding machine with a T-die. The obtained film was sandwiched between two 200 μm thick aluminum foils and heat-sealed in a heat sealer at 180°C and 0.1 MPa for 10 seconds to obtain a multilayer film for adhesion strength measurement, having an aluminum layer, a resin composition layer, and an aluminum layer in this order in the lamination direction. The multilayer film for adhesion strength measurement was cut to a width of 20 mm, and the adhesion strength (unit: N / 20 mm) between the aluminum layer and the resin composition layer was measured using a tensile testing machine by the 180° peel method at room temperature of 23°C. The crosshead speed was set to 200 mm / min.

[0128] (Polymers Used) The polymers used in the examples and comparative examples are listed below. Unless otherwise specified, all polymers were prepared according to conventional methods.

[0129] <Propylene Polymer (A)> Both PP-1 and PP-2 below fall under the category of isotactic propylene polymer (A1). • PP-1: Homopolypropylene (MFR: 3.0 g / 10 min, melting point: 163°C, density: 910 kg / m³) 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 / m³) 3 )

[0130] <1-Butene-Propylene-Ethylene Copolymer (B)> • BPER-1: A 1-butene-propylene-ethylene copolymer synthesized by the method shown below. The physical properties of BPER-1 are shown in Table 1.

[0131]

[0132] <Production of BPER-1> N-hexane was supplied at a rate of 14.2 L / h to one feed port of a 300-liter continuous polymerizer, and a mixed hexane solution of isopropylidene (3-tert-butyl-5-methylcyclopentadienyl-fluorenyl) zirconium dichloride (main catalyst), modified methylaluminoxane, and triisobutylaluminum was continuously supplied at a rate of 0.22 L / h from the other feed port (total hexane 10 L / h). In the mixed solution, the concentration of the main catalyst in terms of zirconium atoms was 0.5 mmol / L, the concentration of the modified methylaluminoxane in terms of aluminum atoms was 4 mmol / L, and the concentration of the triisobutylaluminum in terms of aluminum atoms was 100 mmol / L. Simultaneously, 1-butene was continuously supplied from another supply port of the polymerizer at a rate of 23.5 kg / h, propylene at 1.3 kg / h, ethylene at 0.4 kg / h, and hydrogen at 4.4 NL / h. Continuous solution polymerization was carried out under conditions of polymerization temperature: 60°C, polymerization pressure: 0.79 MPaG, and residence time: 1.5 hours to obtain BPER-1.

[0133] <Modified Polyolefin (C)> ・MAH-PP-1: Maleic anhydride-modified homopolypropylene (Maleic anhydride graft amount: 3.0% by mass, intrinsic viscosity [η]: 0.4 dl / g)

[0134] <Ethylene-based polymer (D)> ・EPR-1: Ethylene-propylene copolymer (Ethylene content: 81.4 mol%, Propylene content: 18.6 mol%, MFR: 0.6 g / 10 min, Density: 870 kg / m³) 3 ) ・PE-1: Low-density polyethylene (MFR: 7.0 g / 10 min, density: 917 kg / m³) 3 )

[0135] <Propylene-ethylene copolymer> ・PER-1: Propylene-ethylene copolymer (commercial product, ethylene content: 12.5 mol%, propylene content: 87.5 mol%, MFR (230°C, 2.16 kg load): 8 g / 10 min) <Propylene-ethylene-α-olefin copolymer> ・PBER-1: Propylene-ethylene-1-butene copolymer (ethylene content: 16 mol%, propylene content: 78 mol%, 1-butene content: 6 mol%, MFR (230°C, 2.16 kg load): 6 g / 10 min)

[0136] [Example 1] A resin composition was produced by melt-kneading 21.0 parts by mass of PP-1, 36.5 parts by mass of PP-2, 20.0 parts by mass of BPER-1, 5.0 parts by mass of MAH-PP-1, 10.5 parts by mass of EPR-1, and 7.0 parts by mass of PE-1 at 230°C using a single-screw extruder.

[0137] [Example 2, Comparative Examples 1-6] In Example 2 and Comparative Examples 1-6, resin compositions were prepared in the same manner as in Example 1, according to the formulations shown in Table 2.

[0138] Table 2 shows the whitening resistance and adhesive strength to multilayer films of press sheets made from the resin compositions obtained in the examples and comparative examples.

[0139]

Claims

1. A resin composition comprising: an unmodified propylene polymer (A) containing 60 to 100 mol% of constituent units derived from propylene and satisfying the following requirement (a); an unmodified 1-butene-propylene-ethylene copolymer (B) satisfying the following requirements (b-1) and (b-2); a modified polyolefin (C) containing constituent units derived from an unsaturated carboxylic acid and / or its derivative; and an unmodified ethylene polymer (D) containing 60 to 100 mol% of constituent units derived from ethylene, wherein the content of the 1-butene-propylene-ethylene copolymer (B) is 10.1 to 49.9% by mass (provided the resin composition is 100% by mass). (a) The melting point observed in differential scanning calorimetry is 100°C or higher. (b-1) The content of constituent unit (i) derived from 1-butene is 50 to 96 mol%, the content of constituent unit (ii) derived from propylene is 1 to 40 mol%, and the content of constituent unit (iii) derived from ethylene is 3 to 20 mol% (provided that the sum of constituent units (i), (ii), and (iii) is 100 mol%). (b-2) The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent (Mw / Mn) is 3.0 or less.

2. The resin composition according to claim 1, comprising: 45.0 to 84.8 parts by mass of the propylene polymer (A); 10.1 to 49.9 parts by mass of the 1-butene-propylene-ethylene copolymer (B); 0.1 to 10.0 parts by mass of the modified polyolefin (C); and 5.0 to 30.0 parts by mass of the ethylene polymer (D) (provided that the total of the propylene polymer (A), the 1-butene-propylene-ethylene copolymer (B), the modified polyolefin (C), and the ethylene polymer (D) is 100 parts by mass).

3. The resin composition according to claim 1, wherein the modified polyolefin (C) contains 0.01 to 5% by mass of constituent units derived from an unsaturated carboxylic acid and / or its derivatives, converted to constituent units derived from maleic anhydride, and the content of constituent units derived from propylene in the constituent units of the modified polyolefin (C), excluding the constituent units derived from the unsaturated carboxylic acid and / or its derivatives, is 90 to 100 mol%.

4. The resin composition according to claim 1, wherein the 1-butene-propylene-ethylene copolymer (B) satisfies at least one selected from the group consisting of the following requirements (b-3) and (b-4): (b-3) The melt flow rate (MFR), measured in accordance with ASTM D1238 at 230°C and a 2.16 kg load, is 1 to 100 g / 10 min. (b-4) The molar ratio (content of component unit (i) / content of component unit (iii)) of the content of component unit (i) derived from 1-butene to the content of component unit (iii) derived from ethylene is 6 or more.

5. A single-layer or multilayer film comprising at least one layer containing the resin composition according to any one of claims 1 to 4.

6. A multilayer film comprising at least one layer containing the resin composition described in any one of claims 1 to 4, wherein both sides of the layer containing the resin composition are in contact with other layers.

7. A multilayer film comprising at least one layer containing the resin composition described in any one of claims 1 to 4, wherein one or both sides of the layer containing the resin composition are in contact with at least one layer selected from the group consisting of a metal-containing layer, a polyolefin layer, and a polar resin layer.

8. A single-layer or multi-layer film according to claim 5, which is a film for food packaging.

9. A single-layer or multi-layer film according to claim 5, which is a film for building materials.

10. A single-layer or multi-layer film according to claim 5, which is a film for packaging pouch-type batteries.

11. A method for producing a single-layer or multilayer film, comprising the step of melt-extruding a resin composition according to any one of claims 1 to 4.

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