Resin composition, and single-layer and multi-layer films

Abstract

The present invention addresses the problem of providing: a resin composition which can be used in a food packaging material, a building material, an outer packaging body for a lithium ion battery, or the like, and which has excellent whitening resistance during deformation processing; and a single-layer or multilayer film comprising a layer containing the resin composition. A resin composition according to the present invention contains: a propylene polymer (A) having a melting point of 100 DEG C or higher; a 1-butene-ethylene copolymer (B) in which the content of structural units (i) derived from 1-butene is 70-97 mol%; a polyolefin (C) containing a structural unit derived from an unsaturated carboxylic acid and / or a derivative thereof; and an ethylene polymer (D) containing 60-100 mol% of an ethylene-derived structural unit, wherein the content of the 1-butene-ethylene copolymer (B) in the composition is 7-38 mass%.

Description

Technical Field

[0001] The present invention relates to a resin composition and a single-layer and multi-layer film, and more particularly to a single-layer and multi-layer film suitable for use as a food packaging material, a building material, an outer packaging material for a lithium ion battery, etc., and a resin composition contained in these films. Background Art

[0002] Polypropylene has been widely used as a thermoplastic molding material with excellent rigidity, heat resistance, transparency, etc. Since polypropylene is a non-polar material, its adhesion to polar materials such as ethylene-vinyl alcohol copolymer is poor, and the technology of modifying polypropylene with unsaturated carboxylic acid or its derivatives for the purpose of improving adhesion is well known. In addition, since polypropylene has poor flexibility, when used as an adhesive, a soft rubber component is usually added to polypropylene.

[0003] When a soft rubber component is added to polypropylene, a polypropylene-based adhesive having improved adhesion can be obtained (e.g., Patent Documents 1 and 2). However, on the other hand, the soft rubber component causes whitening during secondary processing such as deep drawing and bending, so it is also necessary to improve whitening resistance. Specific uses that particularly require deep drawing and bending include food packaging materials, building materials, and lithium ion battery packaging materials.

[0004] Among them, the use of lithium-ion batteries in portable electronic devices and automobiles in recent years is expanding, and in lithium-ion batteries, due to the excellent lightness, heat dissipation and shapeability compared with cylindrical and square types of outer packaging materials, the use of bag-type and embossed outer packaging bodies made of multilayer films as packaging materials is expanding according to the shape freedom and miniaturization countermeasures. The packaging material formed by the multilayer film is at least composed of a base material layer, a metal foil layer, a hot-melt resin layer, and an adhesive layer for bonding two adjacent layers of these layers. Since the shape freedom of the multilayer film is large, it is easy to process when manufacturing these bag-type and embossed outer packaging bodies, but when the multilayer film is deformed, the deformed part sometimes turns white. When the outer packaging body has a whitened part, it will become the cause of short circuit, so a material with excellent whitening resistance is required.

[0005] Patent Document 3 describes a battery packaging material, wherein the battery packaging material is laminated in this order at least with a base material layer, a metal foil layer having a chemically treated layer on at least one side, an acid-modified polyolefin layer, and a heat seal layer composed of a high melting point polypropylene layer and an ethylene-propylene random copolymer layer, wherein the high melting point polypropylene layer is arranged closer to the metal foil layer than the ethylene-propylene random copolymer layer, and has a melting point of 150° C. or more. In the battery packaging material, by arranging the high melting point polypropylene layer having a melting point of 150° C. or more closer to the metal foil layer than the ethylene-propylene random copolymer layer, even if the temperature inside the outer packaging body rises due to overcharging, the high melting point polypropylene layer will not melt, and the metal terminal can be prevented from contacting the metal foil layer, thereby suppressing the occurrence of internal short circuits.

[0006] Patent document 4 describes a polypropylene resin composition for battery packaging film, which comprises a propylene-ethylene block copolymer (A) obtained by multi-stage polymerization, wherein the propylene-ethylene block copolymer (A) comprises a propylene polymer component (A1) satisfying specific conditions such as ethylene content and a propylene-ethylene random copolymer component (A2). It is also described that the film formed from the composition has excellent heat resistance, sealing properties and formability, high sealing strength and impact resistance, and the whitening resistance and crack resistance during deformation processing are well balanced and improved overall.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 9-111069

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 4-300933

[0011] Patent Document 3: Japanese Patent Application Publication No. 2007-273398

[0012] Patent Document 4: Japanese Patent Application Publication No. 2015-230777 Summary of the invention

[0013] Technical problem to be solved by the invention

[0014] However, the packaging material described in Patent Document 3 cannot be expected to have sufficient whitening resistance in battery applications. Furthermore, the composition described in Patent Document 4 cannot actually achieve the required level of whitening resistance.

[0015] In view of the above problems, the technical problem to be solved by the present invention is to provide a resin composition with excellent whitening resistance during deformation processing that can be used for food packaging materials, building materials, and outer packaging of lithium ion batteries, and a single-layer or multilayer film containing a layer containing the resin composition.

[0016] Technical solutions for solving technical problems

[0017] The present invention relates to, for example, the following [1] to

[14] . [1]

[0019] A resin composition comprising: a propylene polymer (A) satisfying the following (a); a 1-butene-ethylene copolymer (B) satisfying the following (b-1); a polyolefin (C) containing structural units derived from unsaturated carboxylic acids and / or their derivatives; and an ethylene polymer (D) containing 60 to 100 mol % of structural units derived from ethylene, wherein the content of the above-mentioned 1-butene-ethylene copolymer (B) in the composition is 7 to 38 mass %.

[0020] (a) The melting point observed in differential scanning calorimetry is 100° C. or higher.

[0021] (b-1) When the total of the structural unit (i) derived from 1-butene and the structural unit (ii) derived from ethylene is taken as 100 mol %, the content of the structural unit (i) is in the range of 70 to 97 mol %, and the content of the structural unit (ii) is in the range of 3 to 30 mol %. [2]

[0023] The resin composition as described in [1] contains: 45 to 87.9 parts by mass of the above-mentioned propylene-based polymer (A); 7 to 38 parts by mass of the above-mentioned 1-butene-ethylene copolymer (B); 0.1 to 10 parts by mass of the above-mentioned polyolefin (C); and 5 to 30 parts by mass of the above-mentioned ethylene-based polymer (D), wherein the total of (A), (B), (C) and (D) is set to 100 parts by mass. [3]

[0025] The resin composition according to [1] or [2], wherein the polyolefin (C) contains 0.01 to 5% by mass of a structural unit derived from an unsaturated carboxylic acid and / or a derivative thereof, calculated as a structural unit derived from maleic anhydride,

[0026] Furthermore, in the polyolefin (C), the content ratio of the structural unit derived from propylene in the structural units other than the structural unit derived from the unsaturated carboxylic acid and / or its derivative is 90 to 100 mol%. [4]

[0028] The resin composition according to any one of [1] to [3], wherein the 1-butene-ethylene copolymer (B) is based on 13 The isotactic pentad fraction (mmmm) calculated by C-NMR was in the range of 80 to 99.9%. [5]

[0030] The resin composition according to any one of [1] to [4], wherein the weight average molecular weight (Mw) of the 1-butene-ethylene copolymer (B) is 100,000 to 600,000. [6]

[0032] The resin composition according to any one of [1] to [5], wherein the Shore D hardness measured according to ASTM D2240 is in the range of 20 to 70. [7]

[0034] A single-layer or multi-layer film comprising at least one layer comprising the resin composition according to any one of [1] to [6]. [8]

[0036] A multilayer film comprising at least one layer comprising the resin composition according to any one of [1] to [6], wherein both surfaces of the layer comprising the resin composition are in contact with other layers. [9]

[0038] A multilayer film comprising at least one layer comprising the resin composition described in any one of [1] to [6], wherein one or both surfaces of the layer comprising the resin composition are in contact with at least one of a metal-containing layer, a polyolefin layer and a polar resin layer.

[10]

[0040] The single-layer or multi-layer film according to [7] or the multi-layer film according to [8] or [9], which is a film for food packaging.

[11]

[0042] The single-layer or multi-layer film according to [7] or the multi-layer film according to [8] or [9], which is a film for building materials.

[12]

[0044] The single-layer or multi-layer film according to [7] or the multi-layer film according to [8] or [9], which is a film for battery packaging.

[13]

[0046] The single-layer or multi-layer film described in [7] or the multi-layer film described in [8] or [9], which is a film for packaging pouch-type batteries.

[14]

[0048] A method for producing a single-layer or multi-layer film, comprising the step of melt-extruding the resin composition according to any one of [1] to [6].

[0049] Effects of the Invention

[0050] The single-layer or multilayer film including a layer formed from the resin composition of the present invention has excellent whitening resistance during deformation processing and can be suitably used as a food packaging material, a building material, and a packaging material forming an outer casing of a battery such as a lithium ion battery. DETAILED DESCRIPTION

[0051] The present invention is described in detail below.

[0052] In the present invention, unless otherwise specified, the description of "X to Y" indicating a numerical range means a numerical range including the lower limit and the upper limit as endpoints. Furthermore, when a numerical range is described in sections, the upper and lower limits of each numerical range may be arbitrarily combined.

[0053] <Resin composition>

[0054] The resin composition of the present invention comprises: a propylene polymer (A); a 1-butene-ethylene copolymer (B); a polyolefin (C) containing a structural unit derived from an unsaturated carboxylic acid and / or a derivative thereof; and an ethylene polymer (D).

[0055] Propylene polymer (A)

[0056] Examples of the propylene-based polymer (A) include propylene homopolymers or copolymers of propylene and at least one α-olefin having 2 to 20 carbon atoms other than propylene. Examples of the α-olefin having 2 to 20 carbon atoms other than 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, 1-eicosene, and the like, and ethylene or an α-olefin having 4 to 10 carbon atoms is preferred.

[0057] The copolymer of propylene and these α-olefins may be a random copolymer or a block copolymer. The structural unit derived from these α-olefins may be contained in the copolymer of α-olefin and propylene in a ratio of 35 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0058] The propylene polymer (A) of the present invention satisfies the following requirement (a).

[0059] (a) The melting point observed in differential scanning calorimetry is 100° C. or higher.

[0060] The melting point is preferably 100 to 170°C, more preferably 120 to 165°C.

[0061] The propylene polymer (A) preferably has a melt flow rate (MFR) of 0.01 to 1000 g / 10 min, more preferably 0.05 to 100 g / 10 min, as measured at 230°C and a load of 2.16 kg in accordance with ASTM D 1238.

[0062] The propylene polymer (A) may have an isotactic structure or a syndiotactic structure, and as described later, any structure may be selected in consideration of compatibility with the 1-butene-ethylene copolymer (B).

[0063] That is, examples of the form of the propylene-based polymer (A) include an isotactic propylene-based polymer (A1) and a syndiotactic propylene-based polymer (A2).

[0064] Examples of the isotactic propylene-based polymer (A1) include homopolypropylenes having excellent heat resistance, for example, known homopolypropylenes having a copolymer component other than propylene in an amount of 3 mol% or less, block polypropylenes having an excellent balance between heat resistance and flexibility, for example, known block polypropylenes having a n-decane-elutable rubber component in an amount of 3 to 30% by mass, and random polypropylenes having an excellent balance between flexibility and transparency, for example, known random polypropylenes having a melting peak in the range of 100°C or higher, preferably 110°C to 150°C, as measured by a differential scanning calorimeter (DSC). In order to obtain the desired physical properties, the polymer may be appropriately selected from these, or two or more of the above polypropylene components having different melting points and rigidities may be used in combination.

[0065] Such isotactic propylene polymer (A1) can be produced, for example, by polymerizing propylene using a Ziegler catalyst system or a metallocene catalyst system using a metallocene compound as one of the catalyst components, or by copolymerizing propylene with other α-olefins. The Ziegler catalyst system includes a solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, an organic aluminum compound and an electron donor.

[0066] The syndiotactic propylene polymer (A2) contains more than 90 mol% of structural units derived from propylene and less than 10 mol% of structural units derived from one or more α-olefins selected from ethylene and carbon atoms. It preferably contains more than 91 mol% of structural units derived from propylene and less than 9 mol% of structural units derived from one or more α-olefins selected from ethylene and carbon atoms. 20 (wherein the total of the structural units of the two is set to 100 mol%).

[0067] Examples of ethylene and α-olefins having 4 to 20 carbon atoms include ethylene, 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.

[0068] The syndiotactic propylene-based polymer (A2) can be produced, for example, by the method described in International Publication No. WO2011 / 078054.

[0069] The propylene polymer (A) may be used alone or in combination of two or more.

[0070] 1-Butene-ethylene copolymer (B)

[0071] The 1-butene-ethylene copolymer (B) satisfies the following requirement (b-1).

[0072] (b-1) When the total of the structural unit (i) derived from 1-butene and the structural unit (ii) derived from ethylene is taken as 100 mol %, the content of the structural unit (i) is in the range of 70 to 97 mol %, and the content of the structural unit (ii) is in the range of 3 to 30 mol %.

[0073] In addition, the 1-butene-ethylene copolymer (B) preferably satisfies at least one of the following requirements (b-2) to (b-5).

[0074] (b-2) Based on 13 The isotactic pentad fraction (mmmm) calculated by C-NMR was in the range of 80 to 99.9%.

[0075] (b-3) The intrinsic viscosity [η] in decalin solvent at 135°C is in the range of 0.7 to 2.5 dl / g.

[0076] (b-4) The melt flow rate (MFR) measured according to ASTM D1238 at 190°C and a load of 2.16 kg is in the range of 1 to 100 g / 10 minutes.

[0077] (b-5) The weight average molecular weight (Mw) is 100,000 to 600,000.

[0078] These requirements and the like concerning the 1-butene-ethylene copolymer (B) will be described in detail below.

[0079] (Requirement (b-1))

[0080] (b-1): When the total of the structural unit (i) derived from 1-butene and the structural unit (ii) derived from ethylene is taken as 100 mol%, the content of the above structural unit (i) is in the range of 70 to 97 mol%, and the content of the above structural unit (ii) is in the range of 3 to 30 mol%.

[0081] In the 1-butene-ethylene copolymer (B) of the present invention, the lower limit of the amount of the structural unit derived from 1-butene is 70 mol%. The lower limit of the structural unit is preferably 75 mol%, more preferably 80 mol%, further preferably 83 mol%, and particularly preferably 85 mol%.

[0082] On the other hand, the upper limit of the amount of the structural unit derived from 1-butene is 97 mol %, preferably 96 mol %, more preferably 95 mol %, further preferably 94 mol %, and particularly preferably 90.5 mol %.

[0083] In the 1-butene-ethylene copolymer (B) of the present invention, the upper limit of the amount of the structural unit (ii) derived from ethylene is 30 mol%. The upper limit of the structural unit is preferably 25 mol%, more preferably 20 mol%, further preferably 17 mol%, and particularly preferably 15 mol%.

[0084] On the other hand, the lower limit of the amount of structural units (ii) derived from ethylene is 3 mol %, preferably 4 mol %, more preferably 5 mol %, further preferably 6 mol %, particularly preferably 9.5 mol %.

[0085] The 1-butene-ethylene copolymer (B) of the present invention can obtain good compatibility with the propylene-based polymer (A) by making the amount of the structural unit (ii) derived from ethylene within the above range. When the amount of the structural unit derived from ethylene is below the upper limit, the mechanical strength is excellent, for example, when used as a packaging material, the adhesive strength is excellent, and the durability of the film is improved, so it is preferred. In addition, when it is above the lower limit, an appropriate crystallization rate is achieved, for example, during molding processing, the molding conditions can be expanded and the moldability can be improved, so it is preferred. When used as a packaging material, when combined with the propylene-based polymer (A), the whitening resistance during stretching and deformation processing is excellent, so it is preferred.

[0086] The content (mol %) of each structural unit constituting the 1-butene-ethylene copolymer (B) is expressed by 13 C-NMR measurement. The details of the measurement method are as described in the examples described later.

[0087] (Requirement (b-2))

[0088] (b-2): Based on 13The isotactic pentad fraction (mmmm) calculated by C-NMR was in the range of 80 to 99.9%.

[0089] The lower limit of the isotactic pentad fraction (mmmm) of the 1-butene-ethylene copolymer (B) of the present invention is preferably 85%, more preferably 90%, and further preferably 95% or more. In addition, the upper limit of the above-mentioned isotactic pentad fraction (mmmm) is preferably 99.5%, more preferably 99.0%. By making the isotactic pentad fraction (mmmm) within the above range, in the case of copolymerizing ethylene and controlling the compatibility with the propylene-based copolymer (B) described later, it is also possible to design appropriate mechanical strength and flexibility.

[0090] In addition, the details of the method for measuring the isotactic pentad fraction (mmmm) are as described in the following Examples.

[0091] (Requirement (b-3))

[0092] (b-3): The intrinsic viscosity [η] in decalin solvent at 135°C is in the range of 0.7 to 2.5 dl / g.

[0093] The intrinsic viscosity [η] of the 1-butene-ethylene copolymer (B) of the present invention is more preferably 0.8 to 2.3 dl / g, further preferably 0.9 to 2.25 dl / g, and particularly preferably 1.0 to 2.2 dl / g. The 1-butene-ethylene copolymer (B) having an intrinsic viscosity [η] in the above range has an excellent balance between fluidity and mechanical strength.

[0094] For example, by containing a 1-butene-ethylene copolymer (B), a molded product having excellent mechanical properties can be easily obtained, and both easy moldability and durability of the packaging material can be achieved, which is preferred.

[0095] (Requirement (b-4))

[0096] (b-4): The melt flow rate (MFR) measured at 190°C and a load of 2.16 kg according to ASTM D1238 is in the range of 1 to 100 g / 10 minutes.

[0097] The MFR of the 1-butene-ethylene copolymer (B) of the present invention is preferably 1 to 50 g / 10 min, more preferably 1 to 30 g / 10 min, further preferably 1 to 10 g / 10 min, particularly preferably 2 to 8 g / 10 min.

[0098] When the MFR of the 1-butene-ethylene copolymer (B) is within the above range, the fluidity is good and the mechanical properties of the obtained molded article are good.

[0099] When the MFR is above the lower limit, the composition containing the 1-butene-ethylene copolymer (B) has fluidity and is suitable for high-speed molding. When the MFR is below the upper limit, the composition containing the 1-butene-ethylene copolymer (B) has excellent mechanical properties, excellent adhesive strength and durability, and is therefore preferred.

[0100] (Requirement (b-5))

[0101] (b-5): The weight average molecular weight (Mw) is 100,000 to 600,000.

[0102] The weight average molecular weight (Mw) of the 1-butene-ethylene copolymer (B) of the present invention is preferably 100,000 to 550,000.

[0103] When moldability is required for the 1-butene-ethylene copolymer (B) of the present invention, the weight average molecular weight (Mw) is more preferably 100,000 to 520,000, further preferably 100,000 to 500,000, and particularly preferably 100,000 to 490,000. When the weight average molecular weight is within the above range, the resin composition containing the 1-butene-ethylene copolymer (B) is suitable for high-speed moldability from the viewpoint of fluidity.

[0104] When mechanical strength is required, the weight average molecular weight (Mw) of the 1-butene-ethylene copolymer (B) of the present invention is 150,000 to 600,000, more preferably 200,000 to 600,000, and particularly preferably 202,000 to 600,000. When the weight average molecular weight is within the above range, a resin composition having excellent mechanical properties can be easily obtained.

[0105] In addition, the molecular weight distribution (Mw / Mn) of the 1-butene-ethylene copolymer (B) of the present invention is preferably 1.5 to 3.0, more preferably 1.6 to 2.8. Mw / Mn is a value measured by GPC method in terms of polystyrene. In the 1-butene-ethylene copolymer (B) having Mw / Mn in the above range, there are few low molecular weight components that reduce mechanical strength and few high molecular weight components that deteriorate fluidity, so it is preferred.

[0106] A part of the 1-butene-ethylene copolymer (B) can be graft-modified by using a polar monomer. Examples of the polar monomer include hydroxyl-containing ethylenically unsaturated compounds, amino-containing ethylenically unsaturated compounds, epoxy-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or derivatives thereof, vinyl ester compounds, vinyl chloride, and the like. The modified 1-butene-ethylene copolymer (B) can be obtained by graft-polymerizing the polar monomer with the 1-butene-ethylene copolymer (B) as described above. When the polar monomer as described above is graft-polymerized with the 1-butene-ethylene copolymer (B), the polar monomer is usually used in an amount of 1 to 100 parts by mass, preferably 5 to 80 parts by mass, relative to 100 parts by mass of the 1-butene-ethylene copolymer (B). Such graft polymerization is usually carried out in the presence of a free radical initiator. As the free radical initiator, an organic peroxide or an azo compound can be used. The free radical initiator can be directly mixed with the 1-butene-ethylene copolymer (B) and the polar monomer, or can be used after being dissolved in a small amount of an organic solvent. As the organic solvent, any organic solvent that can dissolve the free radical initiator can be used without particular limitation. Furthermore, a reducing substance can also be used when grafting the polar monomer with the 1-butene-ethylene copolymer (B). When a reducing substance is used, the grafting amount of the polar monomer can be increased.

[0107] The graft modification of the 1-butene-ethylene copolymer (B) by a polar monomer can be carried out by a conventionally known method, for example, by dissolving the 1-butene-ethylene copolymer (B) in an organic solvent, then adding a polar monomer and a free radical initiator to the solution, and reacting at a temperature of 70 to 200° C., preferably 80 to 190° C., for 0.5 to 15 hours, preferably 1 to 10 hours. Alternatively, the modified 1-butene-ethylene copolymer (B) can be produced by reacting the 1-butene-ethylene copolymer (B) with a polar monomer in the absence of a solvent using an extruder or the like. The reaction is usually preferably carried out at a temperature above the melting point of the 1-butene-ethylene copolymer (B), specifically at a temperature of 120 to 250° C., for 0.5 to 10 minutes.

[0108] The modification amount (grafting amount of polar monomer) of the modified 1-butene-ethylene copolymer thus obtained is usually 0.1 to 50% by mass, preferably 0.2 to 30% by mass, and more preferably 0.2 to 10% by mass.

[0109] When the propylene polymer composition of the present invention contains the modified 1-butene-ethylene copolymer as the 1-butene-ethylene copolymer (B), it has excellent adhesion and compatibility with other resins and may improve the wettability of the molded article surface.

[0110] The 1-butene-ethylene copolymer (B) may be used alone or in combination of two or more in the resin composition of the present invention.

[0111] <Method for producing 1-butene-ethylene copolymer (B)>

[0112] As a method for obtaining the 1-butene-ethylene copolymer (B) of the present invention, there can be cited an example of polymerizing the monomer by a known polymerization method such as a gas phase method, a bulk method, a slurry method, etc. in the presence of a catalyst such as a Ziegler-Natta catalyst, a metallocene catalyst, etc. Among them, from the viewpoint that not only the molecular weight distribution and composition distribution of the polymer are narrow, but also a molded body with excellent balance between mechanical strength and flexibility can be designed, and especially when combined with the propylene polymer (A) described later, good compatibility can be obtained and the crystallization rate can be slowed, it is preferred to use a metallocene catalyst that can uniformly control the reaction, and it is particularly preferred to use a metallocene compound (F) represented by the following general formula (1) or (2) for polymerization.

[0113]

[0114] R in the above general formula (1) or (2) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 They are selected from hydrogen, hydrocarbon groups, and silicon-containing hydrocarbon groups, and they may be the same as or different from each other.

[0115] The hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an aralkyl 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, and may include one or more ring structures. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, and the like.

[0116] The silicon-containing hydrocarbon group is preferably an alkylsilyl group or an arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include a trimethylsilyl group, a tert-butyldimethylsilyl group, and a triphenylsilyl group.

[0117] It should be noted that R 2Preferably, the hydrocarbon group or the silicon-containing hydrocarbon group is a sterically hindered hydrocarbon group, that is, a secondary or tertiary substituent is preferred, and a substituent having 4 or more carbon atoms is more preferred. Specific examples of the hydrocarbon group include isopropyl, 1,1-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, and 1,1-dimethylbutyl. Tert-butyl is particularly preferred. Examples of the silicon-containing hydrocarbon group include compounds in which a part or all of the carbon atoms of the above compounds are replaced by silicon.

[0118] R on the fluorene ring 5 To R 12 Adjacent substituents may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl and dibenzofluorenyl. In addition, from the perspective of ease of synthesis, R on the fluorene ring is preferably 5 To R 12 The substituents are preferably bilaterally symmetrical, that is, R 5 =R 12 , R 6 =R 11 , R 7 =R 10 , R 8 =R 9 , more preferably unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Among them, the 3rd, 6th, 2nd and 7th positions on the fluorene ring correspond to R 7 , R 10 , R 6 , R 11 In the above general formula (1), R 3 and R 4 are selected from hydrogen and hydrocarbon groups, which may be the same or different from each other. Specific examples of preferred hydrocarbon groups include the same groups as above. Y is carbon or silicon. In the case of general formula (1), R 13 and R 14 A substituted methylene group or a substituted silylene group is bonded to Y to form a crosslinking portion. Preferred specific examples include methylene, dimethylmethylene, diisopropylmethylene, methyl-tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, dimethylsilylene, and diisopropylsilylene. More preferably, Y is carbon.

[0119] In the general formula (1) or (2), R 2 In the case of tert-butyl, R 1 It is preferably a methyl group or an ethyl group, and more preferably a methyl group. 3 , R 4 is methyl or phenyl, preferably methyl. 3 , R 4Furthermore, in the above general formula (1), R 2 is tert-butyl, R 1 When it is methyl, R 5 ~R 12 It may be hydrogen.

[0120] It is further preferred to use R in the above general formula (1) 2 is tert-butyl, R 1 When it is ethyl, R 5 , R 7 , R 8 , R 9 , R 10 , R 12 is hydrogen, R 6 , R 11 It is a tert-butyl compound.

[0121] In the case of general formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which may contain an unsaturated bond and / or an aromatic ring, to form a cycloalkylene group or a cyclomethylenesilylene group. Preferred specific examples include cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene.

[0122] M in the general formula (1) and (2) is a metal selected from Group IVB of the periodic table, and examples of M include titanium, zirconium, and hafnium. Q is selected from the same or different combinations of halogens, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands, or neutral ligands capable of coordinating with lone pairs of electrons. Specific examples of halogens include fluorine, chlorine, bromine, and iodine, and specific examples of hydrocarbon groups include the same groups as above. Specific examples of anionic ligands include hydrocarbonoxy groups such as methoxy, tert-butoxy, and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands capable of coordinating with lone pairs of electrons include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane. Among them, Q may be the same or a different combination, and preferably at least one is a halogen or an alkyl group.

[0123] The olefin polymerization catalyst used for the polymerization in producing the 1-butene-ethylene copolymer (B) of the present invention preferably contains, in addition to the metallocene compound (F) represented by the general formula (1) or (2), at least one compound (G) selected from an organic aluminum oxide compound (G-1), a compound (G-2) that reacts with the above-mentioned metallocene compound (F) to form an ion pair, and an organic aluminum compound (G-3), and may also contain a granular carrier (H) as needed.

[0124] As the organoaluminum oxy-compound (G-1) to be used, a conventionally known aluminoxane can be used as it is.

[0125] As the compound (G-2) (hereinafter sometimes referred to as "ionic compound") that reacts with the metallocene compound (F) to form an ion pair, Lewis acids, ionic compounds, borane compounds and carborane compounds described in Japanese Unexamined Patent Publication No. 1-501950 and Japanese Unexamined Patent Publication No. 2004-51676 can be mentioned. In addition, heteropoly compounds and isopoly compounds can also be mentioned.

[0126] Specific examples include triphenylboron, tri(o-tolyl)boron, tri(p-tolyl)boron, tri(3,5-dimethylphenyl)boron, trimethylboron, triisobutylboron; compounds having a fluorine-containing aromatic group such as tri(4-fluorophenyl)boron, tri(3,5-difluorophenyl)boron, tri(4-fluoromethylphenyl)boron, tri(pentafluorophenyl)boron; and compounds having a halogen-containing aromatic group; and boron trifluoride.

[0127] Examples of the organoaluminum compound (G-3) include organoaluminum compounds represented by the following general formula (3).

[0128] R am Al(OR b )H p Q q …(3) The organoaluminum compound shown.

[0129] (Where R a and R b They may be the same or different, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Q represents a halogen atom, m is 0<m≤3, n is 0≤n<3, p is 0≤p<3, q is a number of 0≤q<3, and m+n+p+q=3.)

[0130] Specific examples of such compounds include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride, and alkylaluminum alkoxides such as isobutylmethoxyaluminum and isobutylethoxyaluminum.

[0131] As the organoaluminum compound (G-3), tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum and trioctylaluminum, and tri-branched alkylaluminum such as triisobutylaluminum are preferred, and trimethylaluminum and triisobutylaluminum are particularly preferred.

[0132] In the present invention, the polymerization of 1-butene-ethylene copolymer (B) can be carried out by any method of liquid phase polymerization such as solution polymerization and suspension polymerization or gas phase polymerization. In the liquid phase polymerization method, an inert hydrocarbon solvent can be used, specifically aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, etc.; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, or mixtures thereof, etc. It is also possible to carry out bulk polymerization using olefins containing 1-butene themselves as solvents.

[0133] When the polymerization is carried out, the metallocene compound (F) can be generally 10 -8 ~10 -2 mole, preferably 10 -7 ~10 -3 The organoaluminum oxy-compound (G-1) is used in an amount in which the molar ratio [(G-1) / M] to the transition metal atom (M) in the metallocene compound (F) is usually 0.01 to 5000, preferably 0.05 to 2000. The ionic compound (G-2) is used in an amount in which the molar ratio [(G-2) / M] to the transition metal atom (M) in the metallocene compound (F) is usually 1 to 10, preferably 1 to 5. The organoaluminum compound (G-3) is used in an amount in which the molar ratio [(G-3) / M] to the transition metal atom (M) in the metallocene compound (F) is usually 10 to 5000, preferably 20 to 2000.

[0134] The polymerization temperature is usually in the range of -50 to 200° C., preferably in the range of 0 to 100° C., and more preferably in the range of 20 to 100° C. When the polymerization temperature is too low, it tends to be disadvantageous in industrial production in terms of polymerization activity per unit catalyst and heat recovery efficiency.

[0135] The polymerization pressure is usually between normal pressure and 10 MPa gauge pressure, preferably between normal pressure and 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous or continuous methods. The polymerization can also be carried out in two or more stages with different reaction conditions.

[0136] In order to control the molecular weight and polymerization activity of the 1-butene-ethylene copolymer (A) produced during polymerization, hydrogen may be added. The appropriate amount of hydrogen is about 0.001 to 100 NL per 1 kg of the 1-butene-ethylene copolymer (A).

[0137] Polyolefin (C) containing structural units derived from unsaturated carboxylic acid and / or its derivatives

[0138] The polyolefin (C) of the present invention containing structural units derived from an unsaturated carboxylic acid and / or its derivatives (hereinafter also referred to as "polyolefin (C)") is obtained by modifying a polyolefin with an unsaturated carboxylic acid and / or its derivatives, and contains structural units derived from the unsaturated carboxylic acid and / or its derivatives.

[0139] Examples of the polyolefin to be modified include polypropylene (c1), ethylene-propylene-α-olefin copolymer (c2), and ethylene-α-olefin copolymer (c3).

[0140] The polyolefin (C) may be a single species or a mixture of two or more species, for example, a modified product of polypropylene (c1), a modified product of ethylene-propylene-α-olefin copolymer (c2), and a modified product of ethylene-α-olefin copolymer (c3), or a mixture of two or more species thereof.

[0141] Polypropylene (c1) is, for example, a homopolymer of propylene and / or a propylene-α-olefin copolymer. As the α-olefin, there is no particular limitation, and preferably ethylene and α-olefins having 4 to 20 carbon atoms can be cited, and these α-olefins can be a single type or two or more. As preferred α-olefins, ethylene and α-olefins having 4 to 10 carbon atoms are used, among which ethylene and α-olefins having 4 to 8 carbon atoms are particularly suitable. Among them, the content of structural units derived from propylene in the propylene-α-olefin copolymer is at least 50 mol% or more and less than 100%.

[0142] The intrinsic viscosity [η] of the polypropylene (c1) is preferably 0.1 to 10 dl / g. The intrinsic viscosity [η] of the polyolefin (C) obtained by modifying such a polypropylene (c1) is preferably 0.1 to 6 dl / g. When the intrinsic viscosity [η] is within this range, a composition having excellent moldability and mechanical strength can be obtained.

[0143] The method for producing the polypropylene (c1) is not particularly limited, and examples thereof include known methods using known catalysts such as Ziegler-Natta catalysts and metallocene catalysts.

[0144] As the polypropylene (c1), a crystalline polymer is preferred. In the case of a copolymer, it may be a random copolymer or a block copolymer. Furthermore, as long as the moldability is satisfied and the strength is strong enough to withstand the use of the molded body, there is no particular limitation on the stereoregularity and molecular weight. Commercially available resins may also be used directly.

[0145] The polypropylene (c1) is, for example, homopolypropylene or a propylene-α-olefin random copolymer, and may contain several different isotactic polypropylenes.

[0146] The ethylene-propylene-α-olefin copolymer (c2) is a copolymer of ethylene, propylene and an α-olefin having 4 or more carbon atoms, and satisfies the requirements specified in (i) and (ii) below, for example.

[0147] (i) It contains 45 to 90 mol% of structural units derived from propylene, 10 to 25 mol% of structural units derived from ethylene, and 1 to 30 mol% of structural units derived from an α-olefin having 4 to 20 carbon atoms.

[0148] (ii) The intrinsic viscosity [η] in decalin at 135°C is in the range of 0.1 to 10 dl / g.

[0149] As the above-mentioned α-olefin, α-olefins having 4 to 10 carbon atoms are preferably used, and may be a single type or two or more types. As for the ratio of the structural units derived from each monomer, preferably 50 to 85 mol% of propylene, 10 to 22 mol% of ethylene, and 5 to 28 mol% of α-olefin, more preferably 55 to 80 mol% of propylene, 10 to 20 mol% of ethylene, and 10 to 28 mol% of α-olefin.

[0150] Regarding (ii), the intrinsic viscosity [η] is more preferably in the range of 0.5 to 8 dl / g, and further preferably in the range of 0.8 to 6 dl / g. The intrinsic viscosity [η] of the polyolefin (C) obtained by modifying such an ethylene-propylene-α-olefin copolymer (c2) is preferably 0.5 to 8 dl / g, and more preferably 0.8 to 6 dl / g. When the intrinsic viscosity [η] is within the above range, a resin composition having an excellent balance between flexibility and mechanical strength and excellent adhesiveness can be obtained.

[0151] The method for producing the ethylene-propylene-α-olefin copolymer (c2) is not particularly limited, and the copolymer can be produced by a known method using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.

[0152] The stereoregularity and molecular weight of the ethylene-propylene-α-olefin copolymer (c2) are not particularly limited as long as the copolymer satisfies moldability and has strength sufficient to withstand use when formed into a molded article. Commercially available resins may be used as they are.

[0153] The ethylene-α-olefin copolymer (c3) is a copolymer of ethylene and an α-olefin and satisfies the requirements specified in, for example, the following (iii) and (iv).

[0154] (iii) It contains 50 to 99 mol% of structural units derived from ethylene and 1 to 50 mol% of structural units derived from an α-olefin having 3 to 20 carbon atoms.

[0155] (iv) The intrinsic viscosity [η] in decalin at 135°C is in the range of 0.1 to 10 dl / g.

[0156] As the α-olefin, α-olefins having 3 to 10 carbon atoms are more suitable, and may be one or more. The ratio of the structural units derived from each monomer is preferably 55 to 98 mol% of ethylene and 2 to 45 mol% of α-olefin, and more preferably 60 to 95 mol% of ethylene and 5 to 40 mol% of α-olefin.

[0157] Regarding (iv), the intrinsic viscosity [η] is more preferably in the range of 0.5 to 8 dl / g, and further preferably in the range of 0.8 to 6 dl / g. The intrinsic viscosity [η] of the polyolefin (C) obtained by modifying such an ethylene-α-olefin copolymer (c3) is preferably 0.5 to 8 dl / g, and more preferably 0.8 to 6 dl / g. When the intrinsic viscosity [η] is in the above range, a resin composition having an excellent balance between flexibility and mechanical strength and excellent adhesiveness can be obtained.

[0158] The method for producing the ethylene-α-olefin copolymer (c3) is not particularly limited, and examples thereof include known methods using known catalysts such as Ziegler-Natta catalysts and metallocene catalysts.

[0159] The stereoregularity and molecular weight of the ethylene-α-olefin copolymer (c3) are not particularly limited as long as the copolymer has excellent moldability and can ensure strength to withstand use when formed into a film or other shaped article. A commercially available resin may be used as is.

[0160] As unsaturated carboxylic acids and / or their derivatives modified with these polyolefins, unsaturated compounds with one or more carboxylic acid groups, esters of compounds with carboxylic acid groups and alkanols, unsaturated compounds with one or more carboxylic anhydride groups, etc. can be cited. As the unsaturated groups possessed by the unsaturated compounds, vinyl, vinylidene, unsaturated cyclic hydrocarbon groups, etc. can be cited. Unsaturated carboxylic acids and / or their derivatives can be used alone or in combination of two or more. Among them, unsaturated dicarboxylic acids or their anhydrides are suitable, and maleic acid, nadic acid or their anhydrides are particularly preferred.

[0161] The amount of the structural unit derived from the unsaturated carboxylic acid and / or its derivative contained in the polyolefin (C) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3.5% by mass, calculated as the structural unit derived from maleic anhydride. When the amount of the structural unit derived from the unsaturated carboxylic acid and / or its derivative is within the above range, a resin composition having an excellent balance of moldability and adhesiveness can be obtained.

[0162] In the polyolefin (C), the content ratio of the structural unit derived from propylene in the structural units other than the structural units derived from the unsaturated carboxylic acid and / or its derivatives is preferably 90 to 100 mol%, more preferably 95 to 100 mol%. When the content ratio of the structural unit derived from propylene is within the above range, a resin composition having excellent heat resistance can be obtained.

[0163] There are no particular restrictions on the method of grafting unsaturated carboxylic acids and / or their derivatives, and conventionally known graft polymerization methods such as solution method and melt kneading method can be used. For example, there are methods of melting polyolefin and adding unsaturated carboxylic acids and / or their derivatives thereto for grafting reaction, or methods of dissolving polyolefin in a solvent to form a solution and adding unsaturated carboxylic acids and / or their derivatives thereto for grafting reaction, etc.

[0164] In the resin composition of the present invention, the polyolefin (C) may be used alone or in combination of two or more.

[0165] Ethylene polymer (D)

[0166] The ethylene polymer (D) contains 60 to 100 mol% of structural units derived from ethylene. Specific examples of the ethylene polymer (D) of the present invention include high pressure process low density polyethylene (D1) and ethylene-α-olefin copolymer (D2).

[0167] By using the ethylene polymer (D), the obtained resin composition has excellent moldability during molding, and a molded product such as a film having well-balanced and excellent whitening resistance during deformation, impact resistance and transparency can be easily obtained.

[0168] 《High Pressure Low Density Polyethylene (D1)》

[0169] As the high pressure low density polyethylene (D1), known products can be used without limitation. High pressure low density polyethylene generally refers to polyethylene obtained by free radical polymerization of ethylene under high temperature and pressure, and its production method is not particularly limited, and examples thereof include free radical polymerization methods in which free radical polymerization is carried out under conditions of 500 to 2000 atmospheres and 150 to 300° C., and examples thereof include organic peroxides as polymerization initiators.

[0170] The density of the high pressure low density polyethylene (D1) measured according to ASTM D1505 is preferably between 900 and 925 kg / m 3 The range is more preferably 910 to 925 kg / m 3 .

[0171] The melt flow rate (MFR) of the high-pressure low-density polyethylene (D1) measured at 190°C and a load of 2.16 kg in accordance with ASTM D1238 is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, particularly preferably 1.0 g / 10 min or more, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, particularly preferably 20 g / 10 min or less.

[0172] 《Ethylene-α-olefin copolymer (D2)》

[0173] The ethylene-α-olefin copolymer (D2) contains at least a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms.

[0174] The content of the structural unit derived from ethylene in the ethylene-α-olefin copolymer (D2) is 60 to 99 mol%, preferably 65 to 99 mol%, more preferably 70 to 99 mol%, particularly preferably 80 to 99 mol%.

[0175] The ethylene-α-olefin copolymer (D2) is characterized by having fewer long chain branch structures than the high pressure process low density polyethylene (D1), and is sometimes generally referred to as linear low density polyethylene (LLDPE).

[0176] The content of the structural unit derived from the α-olefin having 3 to 20 carbon atoms in the ethylene-α-olefin copolymer (D2) is 1 to 40 mol%, preferably 1 to 35 mol%, more preferably 1 to 30 mol%, particularly preferably 1 to 20 mol%.

[0177] These contents are amounts relative to 100 mol% of the total of structural units derived from ethylene and α-olefins having 3 to 20 carbon atoms.

[0178] When the content of the structural unit is within the above range, a molded product such as a film having excellent and well-balanced whitening resistance during deformation processing, impact resistance, and flexibility can be easily obtained from the obtained resin composition.

[0179] Examples of the 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 them, 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 further preferred, and propylene is particularly preferred.

[0180] The above-mentioned α-olefins having 3 to 20 carbon atoms may be used alone or in combination of two or more.

[0181] The ethylene-α-olefin copolymer (D2) may contain one or two or more structural units derived from other polymerizable monomers in addition to the above-mentioned structural units within a range not impairing the object of the present invention.

[0182] Examples of such other polymerizable monomers include vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane, and vinyl norbornene; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or their derivatives; and non-conjugated polyenes such as dicyclopentadiene, cyclohexadiene, and 5-ethylidene-2-norbornene.

[0183] Specific examples of the ethylene-α-olefin copolymer (D2) include ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-propylene-1-butene copolymers, ethylene-propylene-ethylidene norbornene copolymers, ethylene-1-butene-1-octene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-1-hexene copolymers, and ethylene-1-octene copolymers. Among them, ethylene-propylene copolymers and ethylene-1-butene copolymers are preferred.

[0184] The density of the ethylene-α-olefin copolymer (D2) is preferably 840 kg / m 3 More preferably 850kg / m 3 Above, particularly preferably 855 kg / m 3 Above, preferably 940kg / m 3 Below, more preferably 899kg / m 3 Below, more preferably 890kg / m 3 Below, especially preferably 885kg / m 3 the following.

[0185] When the density is within the above range, a molded product having well-balanced and excellent impact resistance, rigidity, and transparency can be easily obtained.

[0186] The density can be measured by the density gradient tube method.

[0187] The MFR (measured in accordance with ASTM D1238 at 190°C and a load of 2.16 kg) of the ethylene-α-olefin copolymer (D2) is preferably 0.01 g / 10 min or more, more preferably 0.1 g / 10 min or more, preferably 40 g / 10 min or less, more preferably 20 g / 10 min or less, particularly preferably 10 g / 10 min or less.

[0188] When the MFR is within the above range, a molded product having well-balanced and excellent impact resistance, rigidity, and transparency can be easily obtained.

[0189] MFR of ethylene-α-olefin copolymer (D2) measured at 190°C and load 10 kg in accordance with ASTM D1238 10 Compared with the MFR measured at 190°C and a load of 2.16 kg 2.16 MFR 10 / MFR 2.16 ) 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.

[0190] When MFR 10 / MFR 2.16 When the amount is within the above range, a molded product having well-balanced and excellent transparency and impact resistance can be easily obtained.

[0191] The ethylene-α-olefin copolymer (D2) can be produced by a conventionally known method using a vanadium-based catalyst, a titanium-based catalyst or a metallocene-based catalyst, etc. Preferably, the copolymer is produced using a metallocene-based catalyst, which can obtain a copolymer having a narrow molecular weight distribution and a narrow composition distribution, and is more suitable in terms of mechanical properties, transparency and impact resistance.

[0192] In the resin composition of the present invention, the vinyl polymer (D) may be used alone or in combination of two or more.

[0193] In the present invention, the monomers used in the production of the above-mentioned propylene polymer (A), 1-butene-ethylene copolymer (B), polyolefin (C) and ethylene polymer (D) may be any one of monomers derived from fossil fuels, monomers derived from biomass, and monomers derived from chemical recycling, or more than one of them may be used in combination.

[0194] Other Ingredients

[0195] The resin composition of the present invention may also appropriately contain a propylene-ethylene block copolymer, a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-ethylene-butene random copolymer, or a styrene-based elastomer having a composition different from that of the present invention within a range that does not impair the effects of the present invention.

[0196] In addition, the resin composition of the present invention may also contain known additives such as antioxidants, ultraviolet absorbers, neutralizers, nucleating agents, light stabilizers, antistatic agents, antiblocking agents, lubricants, odor adsorbents, antibacterial agents, pigments, inorganic and organic fillers, and various synthetic resins as needed.

[0197] Resin composition

[0198] The resin composition of the present invention contains the above-mentioned propylene polymer (A), 1-butene-ethylene copolymer (B), polyolefin (C) containing structural units derived from an unsaturated carboxylic acid and / or its derivatives, and ethylene polymer (D).

[0199] The resin composition of the present invention can be produced by a conventionally known method, for example, by melt-kneading the above-mentioned components.

[0200] The content of the above-mentioned 1-butene-ethylene copolymer (B) in the composition of the present invention is 7 to 38% by mass. When the content is less than 7% by mass, the effect of improving the whitening resistance cannot be obtained. In addition, when the content exceeds 38% by mass, the mechanical properties of the molded body of the composition are reduced. In addition, regarding the resin composition of the present invention, the content of the above-mentioned polyolefin (C) in the composition is preferably 0.1 to 10% by mass. When the content of the above-mentioned polyolefin (C) in the composition satisfies this range, it is possible to exhibit adhesion without damaging the mechanical properties of the composition, and a composition having excellent mechanical properties and adhesion can be obtained.

[0201] The content of the propylene polymer (A), 1-butene-ethylene copolymer (B), polyolefin (C) and ethylene polymer (D) in the resin composition of the present invention is preferably 45 to 87.9 parts by mass of the propylene polymer (A), 7 to 38 parts by mass of the 1-butene-ethylene copolymer (B), 0.1 to 10 parts by mass of the polyolefin (C) and 5 to 30 parts by mass of the ethylene polymer (D), and more preferably 55 to 78 parts by mass of the propylene polymer (A), 10 to 30 parts by mass of the 1-butene-ethylene copolymer (B), 2 to 5 parts by mass of the polyolefin (C) and 10 to 20 parts by mass of the ethylene polymer (D), when the total content of the propylene polymer (A), 1-butene-ethylene copolymer (B), polyolefin (C) and ethylene polymer (D) is 100 parts by mass. When the content of the above components in the resin composition of the present invention is within the above range, a film including a layer obtained from the composition is less likely to whiten during deformation processing.

[0202] The resin composition of the present invention may contain other components in addition to the propylene polymer (A), 1-butene-ethylene copolymer (B), polyolefin (C) and ethylene polymer (D) as long as the object of the present invention is not impaired.

[0203] As other components, for example, additives such as resin components other than the above components (A) to (D), antioxidants, heat stabilizers, weather stabilizers, lubricants, anti-blocking agents, crystal nucleating agents, pigments, etc. can be cited. The content of these other components is not particularly limited, but is usually in the range of 10 parts by mass or less, preferably in the range of 0.01 to 5 parts by mass, relative to 100 parts by mass of the total of components (A) to (D).

[0204] Furthermore, the resin composition of the present invention may also contain a biomass-derived raw material.

[0205] The resin composition of the present invention preferably has a Shore D hardness measured in accordance with ASTM D2240 in the range of 20 to 70.

[0206] The Shore D hardness (according to ASTM D2244) of the resin composition of the present invention is more preferably 25 to 65, and further preferably 31 to 60. The Shore D hardness is an index of crystallinity. When the Shore D hardness is below the upper limit, a composition having low crystallinity, excellent flexibility, and excellent whitening resistance during stretching can be obtained. When the Shore D hardness is above the lower limit, a composition having excellent mechanical properties can be obtained.

[0207] <Single-layer film and multi-layer film>

[0208] The monolayer and multilayer films of the present invention are monolayer or multilayer films comprising at least one layer containing the above-mentioned polypropylene resin composition. That is, the monolayer film of the present invention is a film composed of a layer containing the above-mentioned polypropylene resin composition, and the multilayer film is a multilayer film comprising at least one layer containing the above-mentioned polypropylene resin composition.

[0209] The monolayer and multilayer films of the present invention have excellent resistance to whitening during deformation processing. Therefore, when the monolayer and multilayer films of the present invention are used as food packaging materials, building materials, outer packaging materials for lithium ion batteries, etc., whitening is not easy to occur during secondary processing of the film such as drawing and bending. Therefore, the monolayer and multilayer films of the present invention can be appropriately used as food packaging films, building material films, pouch-type battery packaging films and other battery packaging films.

[0210] In particular, polypropylene resins are currently used as packaging materials for the outer packaging of lithium-ion batteries, but the present invention achieves prevention of the whitening that is inevitable with existing polypropylene resins by adopting a specific combination of the above-mentioned propylene polymer (A), 1-butene-ethylene copolymer (B), polyolefin (C) and ethylene polymer (D).

[0211] The multilayer film of the present invention, for example, comprises at least one layer containing the above-mentioned polypropylene resin composition, and one or both sides of the layer containing the above-mentioned composition are in contact with other layers. As other layers in contact with the layer containing the above-mentioned composition, for example, metal-containing layers, polyolefin layers and polar resin layers can be cited. As metal-containing layers, aluminum layers, copper layers, stainless steel layers, etc. can be cited, and as polyolefin layers, polypropylene layers, poly-4-methylpentene layers, polyethylene layers, etc. can be cited. As polar resin layers, polyamide layers, EVOH (ethylene-vinyl alcohol copolymer resin) layers, PET (polyethylene terephthalate) layers, PBT (polybutylene terephthalate) layers, etc. can be cited.

[0212] The single-layer and multilayer films of the present invention can be appropriately obtained by melt extrusion molding or the like, and can be produced by a casting method, an inflation method, an extrusion lamination method or the like which are generally performed industrially.

[0213] Example

[0214] 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 unless the scope of the present invention exceeds the scope of the present invention.

[0215] (Various measurement methods)

[0216] In the present examples and the like, the measurements were performed according to the following method.

[0217] [Melt flow rate (MFR)]

[0218] The melt flow rate was measured in accordance with ASTM D1238 at 230° C. and a load of 2.16 kg.

[0219] [Intrinsic viscosity [η]]

[0220] The intrinsic viscosity [η] was measured in accordance with ASTM D1601.

[0221] [Whitening resistance evaluation]

[0222] A pressure molding machine was used to mold the preheating and pressurizing temperature at 200°C, preheating time for 6 minutes, pressure of 10 MPa, pressurizing time for 4 minutes, cooling temperature of 20°C, cooling time of 4 minutes, and pressure of 10 MPa to produce a 0.5 mm thick pressed sheet (single-layer film). A JIS K6301 No. 2 dumbbell sheet was punched out from the pressed sheet to make a test piece for measurement. The test piece for measurement was stretched 0 mm and 20 mm at a tensile speed of 200 mm / min at room temperature using a tensile testing machine ATX manufactured by Shimadzu Corporation. The color change of the test piece for measurement at this time was measured by the reflection method using a CM-3700A manufactured by Konica Minolta. The color change when stretched 20 mm from the initial value (0 mm) is set as ΔL.

[0223] [Elastic modulus measurement]

[0224] The pressure molding machine was used to mold the preheating and pressurizing temperature at 220°C, preheating time at 8 minutes, pressure at 5 MPa, pressurizing time at 5 minutes, cooling temperature at 20°C, cooling time at 12 minutes, and pressure at 5 MPa to produce a 2.0 mm thick pressed sheet (single-layer film). A JIS K7161-2 5A dumbbell sheet was punched out from the pressed sheet to make a test piece for measurement. A tensile tester 2005X-5 manufactured by INTESCO was used to perform a tensile test on the test piece for measurement at a tensile speed of 500 mm / min at room temperature to measure the elastic modulus.

[0225] [Adhesion]

[0226] A film with a thickness of 40 μm was formed from the resin composition described in the examples or comparative examples using an extruder with a T die. The obtained film was sandwiched between aluminum foils with a thickness of 300 μm, and heat-sealed for 10 seconds at 180°C and 0.1 MPa using a heat sealer to obtain a multilayer film. The obtained multilayer film was cut into 15 mm wide pieces, and the adhesion between the aluminum foil and the resin composition layer (unit: N / 15 mm) was measured at room temperature of 23°C using a tensile tester using a 180° peeling method.

[0227] [Polymer composition]

[0228] use 13 C-NMR was performed using the following apparatus and conditions to measure the contents of the structural unit derived from propylene, the structural unit derived from α-olefin, and the structural unit of the 1-butene-ethylene copolymer (B) in the propylene-based copolymer.

[0229] The quantification of propylene and α-olefin contents was carried out using a JECX400P nuclear magnetic resonance apparatus manufactured by JEOL Ltd., using a mixed solvent of deuterated o-dichlorobenzene / deuterated benzene (80 / 20 volume %) as the solvent, at a sample concentration of 60 mg / 0.6 mL, a measurement temperature of 120 °C, and an observation nucleus. 13 The measurement was carried out under the conditions of C (100 MHz), single pulse proton decoupling sequence, pulse width 4.62 μs (45° pulse), cycle time 5.5 s, cumulative number 8000 times, and chemical shift reference value 29.73 ppm.

[0230] The quantification of 1-butene and ethylene contents was carried out using a Bruker Biospin AVANCE cryo-500 nuclear magnetic resonance apparatus as follows. A mixed solvent of o-dichlorobenzene / deuterated benzene (volume ratio: 80 / 20) was used as the solvent. The sample concentration was 20 mg / 0.6 mL, the measurement temperature was 120°C, and the observation nucleus was 1.3 Å.13 C (125MHz), sequence is single pulse proton broadband decoupling, pulse width 4.7μs (45° pulse), cycle time 5.5s, cumulative number 128 times, chemical shift reference value of the carbon signal of the methylene side chain of butene is 27.50ppm. 13 The compositions of 1-butene (C4 content; mol %) and ethylene (C2 content; mol %) were quantified by C-NMR spectroscopy.

[0231] [Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]

[0232] As a GPC apparatus, a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters Corporation was used, and Mw and Mn in terms of polystyrene were measured under the following conditions, and Mw / Mn was calculated.

[0233] Separation columns: 2 TSKgel GNH6-HT manufactured by Tosoh Corporation and 2 TSKgel GNH6-HTL manufactured by Tosoh Corporation (column dimensions: 7.5 mm in diameter, 300 mm in length)

[0234] Column temperature: 140°C

[0235] Mobile phase: o-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) containing 0.025 wt% of BHT (manufactured by Takeda Pharmaceutical Co., Ltd.) as an antioxidant

[0236] Moving speed: 1.0mL / min

[0237] Sample concentration: 15mg / 10mL

[0238] Sample injection volume: 400μL

[0239] Detector: Differential Refractometer

[0240] Standard polystyrene: in the molecular weight range of Mw < 1000 and Mw > 4×10 6 When the molecular weight is 1000≤Mw≤4×10 6 When using, use products from Pressure Chemical.

[0241] [Shore D hardness]

[0242] Use a D-type tester to make the indenter contact the test piece and read the maximum value on the scale as the Shore D hardness. (According to ASTM D2240)

[0243] [Melting point (Tm)]

[0244] The melting point (Tm) was measured using a DSC8500 manufactured by PerkinElmer as a differential scanning calorimeter (DSC). 5 to 10 mg of the sample was sealed in an aluminum pan as a sample. Regarding the temperature distribution, the temperature was raised from room temperature to 230°C at 10°C / min, then maintained at 230°C for 5 minutes, then cooled to -80°C at 10°C / min, maintained at -80°C for 5 minutes, and then raised to 230°C at 10°C / min. The melting point (Tm) was obtained from the curve during the second heating.

[0245] Only the propylene-ethylene-α-olefin copolymer (E) was heated from -70°C to 200°C at a heating rate of 20°C / min (first heating), maintained at 200°C for 10 minutes, then cooled to -70°C at a cooling rate of 20°C / min (first cooling), maintained at -70°C for 1 minute, and then heated from -70°C to 200°C at a heating rate of 20°C / min (second heating), and the peak observed in the first heating at this time was taken as the melting point (Tm).

[0246] (Polyolefin used)

[0247] The polyolefins used in the examples and comparative examples are shown below. Unless otherwise specified, any polyolefin was prepared by polymerization according to a conventional method.

[0248] Propylene polymer (A)

[0249] Both PP-1 and PP-2 below correspond to the isotactic propylene-based polymer (A1).

[0250] PP-1: Random Polypropylene

[0251] (propylene 96 mol%, ethylene 4 mol%, MFR = 3.0 g / 10 min, Tm 140°C)

[0252] PP-2: Random Polypropylene

[0253] (Propylene content 96 mol%, ethylene content 4 mol%, MFR = 7.0 g / 10 min, Tm = 138°C)

[0254] 1-Butene-ethylene copolymer (B)

[0255] BER-1:

[0256] 1-Butene-ethylene copolymer synthesized according to the method shown below (15 mol% of structural units derived from ethylene, 85 mol% of structural units derived from butene, MFR = 6 g / 10 min, isotactic pentad fraction (mmmm) 98.0%, intrinsic viscosity [η] 1.71 dl / g, Mw = 366,000)

[0257] [BER-1 Production Example]

[0258] To one supply port of a continuous polymerization vessel having a volume of 300 liters, n-hexane was supplied at a ratio of 14.2 L / h, and a mixed hexane solution of isopropylidene(3-tert-butyl-5-methylcyclopentadienyl-fluorenyl)zirconium dichloride (main catalyst 1), modified methylaluminoxane, and triisobutylaluminum was continuously supplied at 0.22 L / h from another supply port (total hexane 10 L / h), wherein the zirconium conversion concentration of the main catalyst 1 was 0.5 mmol / L, the aluminum conversion concentration of the modified methylaluminoxane was 4 mmol / L, and the aluminum conversion concentration of the triisobutylaluminum was 100 mmol / L. At the same time, 1-butene was continuously supplied at a rate of 27.0 kg / h, ethylene was continuously supplied at a rate of 1.0 kg / h, and hydrogen was continuously supplied at a rate of 0.6 NL / h from another supply port of the polymerizer, and solution polymerization was continuously carried out under the conditions of a polymerization temperature of 60°C, a polymerization pressure of 0.8 MPaG, and a residence time of 1.5 hours to obtain a 1-butene-ethylene copolymer (BER-1).

[0259] BER-2:

[0260] The same procedure as in BER-1 production example was followed except that the ethylene supplied from another supply port of the polymerizer was set to 0.9 kg / h and the hydrogen was set to 0.1 NL / h, to obtain a 1-butene-ethylene copolymer (structural units derived from ethylene: 15 mol%, structural units derived from butene: 85 mol%, MFR = 3 g / 10 min, isotactic pentad fraction (mmmm) 98.0%, intrinsic viscosity [η] 2.14 dl / g, Mw = 490,000).

[0261] BER-3:

[0262] The same procedure as in BER-1 production example was followed except that the ethylene supplied from another supply port of the polymerizer was set to 0.4 kg / h and the polymerization pressure was set to 0.6 MPaG, thereby obtaining a 1-butene-ethylene copolymer (structural units derived from ethylene 6 mol%, structural units derived from butene 94 mol%, MFR = 6 g / 10 min, isotactic pentad fraction (mmmm) 93.0%, intrinsic viscosity [η] 1.71 dl / g, Mw = 360,000).

[0263] BER-4:

[0264] BL3540M manufactured by Mitsui Chemicals, Inc. (2 mol% of structural units derived from ethylene, 98 mol% of structural units derived from butene, MFR = 9 g / 10 min, isotactic pentad fraction (mmmm) 93.0%, intrinsic viscosity [η] 1.50 dl / g, Mw = 337,000).

[0265] Polyolefin (C)

[0266] Modified PP-1: Modified homopolypropylene

[0267] (Maleic anhydride grafting amount 3.0% by mass, intrinsic viscosity [η] 0.4 dl / g)

[0268] Ethylene polymer (D)

[0269] D-1: Low density polyethylene

[0270] (MFR = 18 g / 10 min, density 0.92 g / cm 3 )

[0271] D-2: EPR-1: (80 mol% of structural units derived from ethylene, 20 mol% of structural units derived from propylene, MFR = 0.8 g / 10 min)

[0272] Propylene-ethylene-α-olefin copolymer (E)

[0273] The structural unit derived from ethylene is 16 mol%, the structural unit derived from propylene is 78 mol%, and the structural unit derived from butene is 6 mol%. MFR=6 g / 10 min, Tm=48°C.

[0274] [Example 1]

[0275] A resin composition was produced by melt-kneading 25.0 parts by mass of PP-1, 42.5 parts by mass of PP-2, 10 parts by mass of BER-1, 5 parts by mass of modified PP-1, 7 parts by mass of D-1 and 10.5 parts by mass of D-2 at 230°C using a single-screw extruder.

[0276] [Examples 2 to 9, Comparative Examples 1 to 4]

[0277] In Examples 2 to 9 and Comparative Examples 1 to 4, resin compositions were prepared according to the formulations shown in Table 1 in the same manner as in Example 1.

[0278] Table 1 shows the MFR of the resin compositions obtained in Examples and Comparative Examples, and the whitening resistance, elastic modulus, hardness of the pressed sheets made from the resin compositions, and the adhesive strength of the multilayer films.

[0279] As shown in Examples 1 to 9, by using the composition of the present invention, a multilayer film having excellent whitening resistance, elastic modulus and adhesiveness can be provided. Also, by using the multilayer film, a battery outer packaging material having excellent whitening resistance, heat resistance, mechanical properties, durability and adhesiveness can be provided.

[0280] [Table 1]

[0281]

Claims

1. A resin composition, characterized in that contain: A propylene polymer (A) satisfying the following (a); A 1-butene-ethylene copolymer (B) satisfying the following (b-1); A polyolefin (C) containing structural units derived from an unsaturated carboxylic acid and / or a derivative thereof; and An ethylene polymer (D) containing 60 to 100 mol% of structural units derived from ethylene, The content of the 1-butene-ethylene copolymer (B) in the composition is 7 to 38% by mass. (a) a melting point of 100° C. or higher as observed in differential scanning calorimetry, (b-1) When the total of the structural unit (i) derived from 1-butene and the structural unit (ii) derived from ethylene is taken as 100 mol %, the content of the structural unit (i) is in the range of 70 to 97 mol %, and the content of the structural unit (ii) is in the range of 3 to 30 mol %.

2. The resin composition according to claim 1, characterized in that contain: 45 to 87.9 parts by weight of the propylene polymer (A); 7 to 38 parts by weight of the 1-butene-ethylene copolymer (B); 0.1 to 10 parts by mass of the polyolefin (C); and 5 to 30 parts by weight of the ethylene polymer (D), However, the total of (A), (B), (C), and (D) is 100 parts by mass.

3. The resin composition according to claim 1, wherein: The polyolefin (C) contains 0.01 to 5% by mass of a structural unit derived from an unsaturated carboxylic acid and / or a derivative thereof, calculated as a structural unit derived from maleic anhydride. Furthermore, in the polyolefin (C), the content ratio of the structural unit derived from propylene in the structural units other than the structural unit derived from the unsaturated carboxylic acid and / or its derivative is 90 to 100 mol%.

4. The resin composition according to claim 1, wherein: 1-Butene-ethylene copolymer (B) based on 13 The isotactic pentad fraction (mmmm) calculated by C-NMR was in the range of 80 to 99.9%.

5. The resin composition according to claim 1, wherein: The weight average molecular weight (Mw) of the 1-butene-ethylene copolymer (B) is 100,000 to 600,000.

6. The resin composition according to claim 1, wherein: The Shore D hardness measured according to ASTM D2240 is in the range of 20 to 70.

7. A single-layer or multi-layer film, characterized in that: The present invention comprises at least one layer comprising the resin composition according to any one of claims 1 to 6.

8. A multilayer film, characterized in that: The invention comprises at least one layer comprising the resin composition according to any one of claims 1 to 6, and both surfaces of the layer comprising the resin composition are in contact with other layers.

9. A multilayer film, characterized in that: The invention comprises at least one layer comprising the resin composition according to any one of claims 1 to 6, wherein one or both surfaces of the layer comprising the resin composition are in contact with at least one of the metal-containing layer, the polyolefin layer and the polar resin layer.

10. The monolayer or multilayer film according to claim 7, characterized in that: It is a film for food packaging.

11. The monolayer or multilayer film according to claim 7, characterized in that: It is a membrane for building materials.

12. The monolayer or multilayer film according to claim 7, characterized in that: It is a film for battery packaging.

13. The monolayer or multilayer film according to claim 7, characterized in that: It is a film for packaging pouch-type batteries.

14. A method for manufacturing a single-layer or multi-layer film, characterized in that: The method comprises the step of melt-extruding the resin composition according to any one of claims 1 to 6.

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