Resin compositions and single-layer and multi-layer films

Abstract

The present invention addresses the problem of providing: a resin composition that has excellent whitening resistance when being deformation processed and that can be used for food packaging materials, construction materials, exterior bodies for lithium ion batteries, and the like; and a monolayer or multilayer film that includes a layer containing the resin composition.　A resin composition according to the present invention contains a propylene-based polymer (A) having a melting point of 100°C or higher, a 1-butene / ethylene copolymer (B) in which the contained amount of a constitutional unit (i) derived from 1-butene is 70-97 mol%, a polyolefin (C) including a structural unit derived from an unsaturated carboxylic acid and / or a derivative thereof, and an ethylene-based polymer (D) in which the contained amount of a constitutional unit derived from ethylene is 60-100 mol%. In the composition, the contained amount of the 1-butene / ethylene copolymer (B) is 7-38 mass%.

Description

[Technical Field]

[0001] The present invention relates to a resin composition and a single-layer and multilayer film, and more particularly to a single-layer and multilayer film that is suitable for use as a food packaging material, a construction material, an exterior material for a lithium-ion battery, etc., and a resin composition contained in those films. [Background technology]

[0002] Polypropylene has traditionally been widely used as a thermoplastic molding material, boasting 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. To improve adhesion, a widely known technique involves modifying polypropylene with unsaturated carboxylic acids or their derivatives. Furthermore, because polypropylene lacks flexibility, soft rubber components are typically blended into polypropylene when used as an adhesive.

[0003] In this way, by blending a soft rubber component with polypropylene, a polypropylene-based adhesive with improved adhesive properties can be obtained (for example, Patent Documents 1 and 2). However, since the soft rubber component causes whitening during secondary processing such as deep drawing and bending, there has also been a demand for improved whitening resistance. Specific applications requiring deep drawing and bending in particular include food packaging materials, construction materials, and packaging materials for lithium-ion batteries.

[0004] Among these, lithium-ion batteries have seen increasing use in portable electronic devices and automobiles in recent years. Furthermore, compared to cylindrical or prismatic packaging materials, lithium-ion batteries offer superior lightness, heat dissipation, and formability. This allows for greater flexibility in design and miniaturization, leading to the widespread use of pouch-type and embossed packaging made from multilayer film. This multilayer film packaging material consists of at least a substrate layer, a metal foil layer, and a thermally adhesive resin layer, along with an adhesive layer that bonds adjacent two of these layers. Because multilayer film offers greater flexibility in design, it is easy to process these pouch-type and embossed packaging materials. However, deformation of the multilayer film can sometimes result in whitening of the deformed areas. Because whitening can cause short circuits, materials with excellent whitening resistance are needed.

[0005] Patent Document 3 describes a battery packaging material that includes at least a base layer, a metal foil layer having a chemical conversion coating layer on at least one side thereof, an acid-modified polyolefin layer, and a heat-seal layer made of a high-melting-point polypropylene layer and an ethylene-propylene random copolymer layer, laminated in this order, wherein the high-melting-point polypropylene layer is disposed closer to the metal foil layer than the ethylene-propylene random copolymer layer and has a melting point of 150°C or higher. In this battery packaging material, by disposing the high-melting-point polypropylene layer with a melting point of 150°C or higher closer to the metal foil layer than the ethylene-propylene random copolymer layer, even if a temperature rise occurs inside the exterior due to overcharging or the like, the high-melting-point polypropylene layer does not melt, preventing contact between the metal terminal 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, which is composed of a propylene-ethylene block copolymer (A) containing a propylene polymer component (A1) and a propylene-ethylene random copolymer component (A2) obtained by multistage polymerization and satisfying specific conditions such as the ethylene content. It is described that a film formed from this composition has excellent heat resistance, sealability, and formability, high seal strength, and impact resistance, and exhibits well-balanced overall improvements in properties such as whitening resistance and cracking resistance during deformation processing. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 9-111069 [Patent Document 2] Japanese Patent Application Publication No. 4-300933 [Patent Document 3] Japanese Patent Application Laid-Open No. 2007-273398 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-230777 Summary of the Invention [Problem to be solved by the invention]

[0008] However, the packaging material described in Patent Document 3 cannot be expected to have sufficient whitening resistance for battery applications, and the composition described in Patent Document 4 does not actually achieve the required level of whitening resistance.

[0009] In view of the above problems, an object of the present invention is to provide a resin composition that has excellent resistance to whitening during deformation processing and that can be used for food packaging materials, construction materials, and exterior bodies for lithium ion batteries, and a single-layer or multilayer film that includes a layer containing the resin composition. [Means for solving the problem]

[0010] The present invention relates to, for example, the following [1] to

[14] . [1] a propylene-based polymer (A) that satisfies the following (a); a 1-butene-ethylene copolymer (B) that satisfies the following (b-1); a polyolefin (C) containing structural units derived from an unsaturated carboxylic acid and / or a derivative thereof; an ethylene polymer (D) containing 60 to 100 mol % of structural units derived from ethylene; Contains A resin composition, wherein the content of the 1-butene-ethylene copolymer (B) in the composition is 7 to 38 mass %. (a) The melting point observed by differential scanning calorimetry is 100°C or higher. (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 %.

[0011] [2] 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); The resin composition according to [1], comprising 5 to 30 parts by mass of the ethylene polymer (D) (where the total of (A), (B), (C) and (D) is 100 parts by mass).

[0012] [3] the polyolefin (C) contains 0.01 to 5 mass% of structural units derived from an unsaturated carboxylic acid and / or a derivative thereof, calculated as structural units derived from maleic anhydride; The resin composition according to [1] or [2], wherein the polyolefin (C) has a content of propylene-derived structural units in structural units excluding structural units derived from the unsaturated carboxylic acid and / or a derivative thereof of 90 to 100 mol%.

[0013] [4] 1-butene-ethylene copolymer (B), 13 The resin composition according to any one of [1] to [3], wherein the isotactic pendant fraction (mmmm) calculated by C-NMR is in the range of 80 to 99.9%.

[0014] [5] The resin composition according to any one of [1] to [4], wherein the 1-butene-ethylene copolymer (B) has a weight average molecular weight (Mw) of 100,000 to 600,000.

[0015] [6] The resin composition according to any one of [1] to [5], which has a Shore D hardness in the range of 20 to 70 as measured in accordance with ASTM D2240. [7] A single-layer or multi-layer film comprising at least one layer containing the resin composition according to any one of [1] to [6]. [8] A multilayer film comprising at least one layer containing the resin composition according to any one of [1] to [6], wherein both sides of the layer containing the resin composition are in contact with other layers.

[0016] [9] A multilayer film comprising at least one layer containing the resin composition according to any one of [1] to [6], 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.

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

[0017]

[11] The monolayer or multilayer film according to [7], or the multilayer film according to [8] or [9], which is a film for construction materials.

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

[0018]

[13] The single-layer or multilayer film according to [7], or the multilayer film according to [8] or [9], which is a pouch-type battery packaging film.

[14] A method for producing a monolayer or multilayer film, comprising a step of melt-extrusion molding the resin composition according to any one of [1] to [6]. [Effects of the Invention]

[0019] A single-layer or multilayer film containing a layer formed from the resin composition of the present invention has excellent resistance to whitening during deformation processing, and can be suitably used as a packaging material for forming food packaging materials, construction materials, and outer casings for batteries such as lithium-ion batteries. DETAILED DESCRIPTION OF THE INVENTION

[0020] The present invention will be specifically described below. In the present invention, unless otherwise specified, the description of "X to Y" representing a numerical range means a numerical range including the lower and upper limits, which are the endpoints. Furthermore, when a numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily.

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

[0022] Propylene polymer (A) Examples of the propylene polymer (A) include a propylene homopolymer and a copolymer of propylene and at least one α-olefin other than propylene having 2 to 20 carbon atoms. Examples of the α-olefin other than propylene having 2 to 20 carbon atoms 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, and ethylene or an α-olefin having 4 to 10 carbon atoms is preferred.

[0023] The copolymer of propylene with these α-olefins may be a random copolymer or a block copolymer. The structural units derived from these α-olefins may be contained in the copolymer of α-olefin and propylene in a proportion of 35 mol % or less, preferably 30 mol % or less, more preferably 20 mol % or less, even more preferably 10 mol % or less, and particularly preferably 5 mol % or less.

[0024] The propylene polymer (A) according to the present invention satisfies the following requirement (a). (a) The melting point 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. The propylene polymer (A) desirably has a melt flow rate (MFR) measured in accordance with ASTM D 1238 at 230°C under a load of 2.16 kg in the range of 0.01 to 1000 g / 10 min, preferably 0.05 to 100 g / 10 min.

[0025] The propylene polymer (A) may have either an isotactic structure or a syndiotactic structure, and either structure can be selected in consideration of compatibility with the 1-butene-ethylene copolymer (B), as will be described later. That is, the propylene polymer (A) may be in the form of an isotactic propylene polymer (A1) or a syndiotactic propylene polymer (A2).

[0026] Examples of the isotactic propylene polymer (A1) include homopolypropylenes having excellent heat resistance, such as known homopolypropylenes typically containing 3 mol % or less of copolymerization components other than propylene; block polypropylenes having an excellent balance between heat resistance and flexibility, such as known block polypropylenes typically containing 3 to 30 mass % of a normal decane-eluted rubber component; and random polypropylenes having an excellent balance between flexibility and transparency, such as known random polypropylenes having a melting peak typically measured by differential scanning calorimetry (DSC) of 100°C or higher, preferably in the range of 110°C to 150°C. These can be appropriately selected to obtain the desired physical properties, or two or more of the above polypropylene components having different melting points or rigidities can be used in combination.

[0027] Such an isotactic propylene polymer (A1) can be produced by polymerizing propylene or copolymerizing propylene with another α-olefin using, for example, a Ziegler catalyst system comprising a solid catalyst component containing magnesium, titanium, a halogen, and an electron donor as essential components, an organoaluminum compound, and an electron donor, or a metallocene catalyst system using a metallocene compound as one of the catalyst components.

[0028] The syndiotactic propylene polymer (A2) contains 90 mol % or more of structural units derived from propylene and 10 mol % or less of structural units derived from one or more selected from ethylene and α-olefins having 4 to 20 carbon atoms, and preferably contains 91 mol % or more of structural units derived from propylene and 9 mol % or less of structural units derived from one or more selected from ethylene and α-olefins having 4 to 20 carbon atoms (the total of both structural units is 100 mol %).

[0029] 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. The syndiotactic propylene polymer (A2) can be produced, for example, by a method such as that described in International Publication No. WO2011 / 078054. In the resin composition of the present invention, the propylene polymer (A) may be used alone or in combination of two or more.

[0030] 1-Butene-ethylene copolymer (B) The 1-butene-ethylene copolymer (B) satisfies the following requirement (b-1): (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 %.

[0031] Furthermore, the 1-butene-ethylene copolymer (B) preferably satisfies at least one of the following requirements (b-2) to (b-5): (b-2) 13 The isotactic pendant fraction (mmmm) calculated by C-NMR is in the range of 80 to 99.9%. (b-3) The intrinsic viscosity [η] in decalin solvent at 135°C is in the range of 0.7 to 2.5 dl / g. (b-4) The melt flow rate (MFR) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is in the range of 1 to 100 g / 10 min. (b-5) The weight average molecular weight (Mw) is 100,000 to 600,000.

[0032] These requirements for the 1-butene-ethylene copolymer (B) are explained in detail below. (Requirement (b-1)) (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 %. In the 1-butene-ethylene copolymer (B) according to the present invention, the lower limit of the amount of structural units derived from 1-butene is 70 mol %, preferably 75 mol %, more preferably 80 mol %, even more preferably 83 mol %, and particularly preferably 85 mol %.

[0033] On the other hand, the upper limit of the amount of structural units derived from 1-butene is 97 mol%, preferably 96 mol%, more preferably 95 mol%, even more preferably 94 mol%, and particularly preferably 90.5 mol%.

[0034] In the 1-butene-ethylene copolymer (B) according to the present invention, the upper limit of the amount of the structural unit (ii) derived from ethylene is 30 mol %, preferably 25 mol %, more preferably 20 mol %, even more preferably 17 mol %, and particularly preferably 15 mol %.

[0035] On the other hand, the lower limit of the amount of the structural unit (ii) derived from ethylene is 3 mol%, preferably 4 mol%, more preferably 5 mol%, even more preferably 6 mol%, and particularly preferably 9.5 mol%.

[0036] The 1-butene-ethylene copolymer (B) according to the present invention can achieve good compatibility with the propylene polymer (A) by adjusting the amount of the ethylene-derived structural unit (ii) within the above range. When the amount of the ethylene-derived structural unit (ii) is equal to or less than the upper limit, the copolymer exhibits excellent mechanical strength, and when used as a packaging material, for example, the copolymer exhibits excellent adhesive strength and improved film durability, which is preferable. When the amount of the ethylene-derived structural unit (ii) is equal to or greater than the lower limit, the copolymer exhibits an appropriate crystallization rate, which is preferable because it broadens the range of molding conditions during molding and improves moldability, and when used as a packaging material, when combined with the propylene polymer (A), the copolymer exhibits excellent resistance to whitening during stretching or deformation processing, which is preferable.

[0037] The content (mol %) of each structural unit constituting the 1-butene-ethylene copolymer (B) is 13 The measurement is carried out by C-NMR. Details of the measurement method are as described in the Examples below.

[0038] (Requirement (b-2)) (b-2): 13 The isotactic pendant fraction (mmmm) calculated by C-NMR is in the range of 80 to 99.9%. The 1-butene-ethylene copolymer (B) according to the present invention preferably has a lower limit of the isotactic pentad fraction (mmmm) of 85%, more preferably 90%, and even more preferably 95% or more. The upper limit of the isotactic pentad fraction (mmmm) is preferably 99.5%, more preferably 99.0%. By controlling the isotactic pentad fraction (mmmm) within the above range, it becomes possible to design appropriate mechanical strength and flexibility, even when ethylene is copolymerized and the compatibility with the propylene-based copolymer (B) described below is controlled. Details of the method for measuring the isotactic pentad fraction (mmmm) are as described in the Examples below.

[0039] (Requirement (b-3)) (b-3): The intrinsic viscosity [η] in decalin solvent at 135°C is in the range of 0.7 to 2.5 dl / g. The intrinsic viscosity [η] of the 1-butene-ethylene copolymer (B) according to the present invention is more preferably 0.8 to 2.3 dL / g, even more 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] within the above range has an excellent balance between fluidity and mechanical strength. For example, by containing the 1-butene-ethylene copolymer (B), a molded article having excellent mechanical properties can be easily obtained, and it is preferable that ease of molding and durability of the packaging material can be achieved at the same time.

[0040] (Requirement (b-4)) (b-4): The melt flow rate (MFR) measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg is in the range of 1 to 100 g / 10 min. The MFR of the 1-butene-ethylene copolymer (B) according to 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, and particularly preferably 2 to 8 g / 10 min. When the MFR of the 1-butene-ethylene copolymer (B) is within the above range, the flowability is good, and the obtained molded article has good mechanical properties.

[0041] When the MFR is equal to or greater than 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 equal to or less than the upper limit, the composition containing the 1-butene-ethylene copolymer (B) is preferred because it has excellent mechanical properties, adhesive strength, and durability.

[0042] (Requirement (b-5)) (b-5): The weight average molecular weight (Mw) is 100,000 to 600,000. The 1-butene-ethylene copolymer (B) according to the present invention preferably has a weight average molecular weight (Mw) of 100,000 to 550,000. When moldability is required, the 1-butene-ethylene copolymer (B) according to the present invention preferably has a weight-average molecular weight (Mw) of 100,000 to 520,000, more preferably 100,000 to 500,000, and particularly preferably 100,000 to 490,000. When the weight-average molecular weight is within this range, the resin composition containing the 1-butene-ethylene copolymer (B) is suitable for high-speed moldability from the viewpoint of flowability. Furthermore, when mechanical strength is required, the 1-butene-ethylene copolymer (B) according to the present invention has a weight-average molecular weight (Mw) of more preferably 150,000 to 600,000, even 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.

[0043] Furthermore, the 1-butene-ethylene copolymer (B) according to the present invention preferably has a molecular weight distribution (Mw / Mn) of 1.5 to 3.0, more preferably 1.6 to 2.8. Mw / Mn is a value measured by GPC and converted into polystyrene. 1-butene-ethylene copolymer (B) having an Mw / Mn within the above range is preferred because it contains few low-molecular-weight components that reduce mechanical strength and few high-molecular-weight components that deteriorate flowability.

[0044] The 1-butene-ethylene copolymer (B) may be partially graft-modified with 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 their derivatives, vinyl ester compounds, and vinyl chloride. The modified 1-butene-ethylene copolymer (B) can be obtained by graft polymerizing a polar monomer onto the 1-butene-ethylene copolymer (B) described above. When graft polymerizing the polar monomer onto the 1-butene-ethylene copolymer (B), the polar monomer is typically used in an amount of 1 to 100 parts by mass, preferably 5 to 80 parts by mass, per 100 parts by mass of the 1-butene-ethylene copolymer (B). This graft polymerization is typically carried out in the presence of a radical initiator. Examples of the radical initiator include organic peroxides and azo compounds. The radical initiator can be used by directly mixing with the 1-butene-ethylene copolymer (B) and the polar monomer, or by dissolving it in a small amount of organic solvent. The organic solvent can be any organic solvent that can dissolve the radical initiator. A reducing substance may be used when graft-polymerizing a polar monomer onto the 1-butene-ethylene copolymer (B). The use of a reducing substance can increase the amount of polar monomer grafted.

[0045] Graft modification of the 1-butene-ethylene copolymer (B) with a polar monomer can be carried out by a conventional method. For example, the 1-butene-ethylene copolymer (B) is dissolved in an organic solvent, and then a polar monomer and a radical initiator are added to the solution. The resulting mixture is reacted 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 the polar monomer without solvent using an extruder or the like. This reaction is typically carried out at a temperature above the melting point of the 1-butene-ethylene copolymer (B), specifically at 120 to 250°C, for 0.5 to 10 minutes.

[0046] The modification amount (graft amount of polar monomer) of the modified 1-butene-ethylene copolymer obtained in this manner is generally 0.1 to 50 mass %, preferably 0.2 to 30 mass %, and more preferably 0.2 to 10 mass %. When the propylene-based polymer composition of the present invention contains the above-mentioned modified 1-butene-ethylene copolymer as the 1-butene-ethylene copolymer (B), the composition may have excellent adhesion and compatibility with other resins and may have improved wettability on the surface of a molded article. The 1-butene-ethylene copolymer (B) may be used singly or in combination of two or more in the resin composition of the present invention.

[0047] <Method for producing 1-butene-ethylene copolymer (B)> The 1-butene-ethylene copolymer (B) of the present invention can be obtained by polymerizing monomers in the presence of a catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst by known polymerization methods such as a gas-phase method, a bulk method, or a slurry method. Among these, metallocene catalysts are preferred because they can uniformly control the reaction, not only because they produce polymers with narrow molecular weight and composition distributions, enabling the design of molded articles with an excellent balance between mechanical strength and flexibility, but also because they provide good compatibility, particularly when combined with the propylene polymer (A) described below, and because they can slow the crystallization rate. Polymerization using a metallocene compound (F) represented by the following general formula (1) or (2) is particularly preferred.

[0048] [ka]

[0049] [ka] 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 are selected from hydrogen, hydrocarbon groups, and silicon-containing hydrocarbon groups, and may be the same or different.

[0050] 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, and may contain 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, and tert-butyl.

[0051] 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, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, and triphenylsilyl.

[0052] In addition, R 2 is preferably a sterically bulky hydrocarbon group or a silicon-containing hydrocarbon group, i.e., a secondary or tertiary substituent, and more preferably a substituent having 4 or more carbon atoms. Specific hydrocarbon groups 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 silicon-containing hydrocarbon groups include compounds in which some or all of the carbon atoms in the above compounds have been substituted with silicon.

[0053] R on the fluorene ring 5 From R 12 Adjacent substituents up to may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl and dibenzofluorenyl. In addition, when R on the fluorene ring 5 From R 12 The substituents are symmetrical for ease of synthesis, i.e., R 5 =R 12 , R 6 =R 11, R 7 =R 10 , R 8 =R 9 Preferably, the fluorene is unsubstituted, 3,6-disubstituted, 2,7-disubstituted, or 2,3,6,7-tetrasubstituted fluorene, and more preferably, the fluorene is unsubstituted, 3,6-disubstituted, 2,7-disubstituted, or 2,3,6,7-tetrasubstituted fluorene. Here, the 3-, 6-, 2-, and 7-positions on the fluorene ring are each represented by R 7 , R 10 , R 6 , R 11 R of the above general formula (1) 3 and R 4 are selected from hydrogen and hydrocarbon groups, and may be the same or different. Specific examples of preferred hydrocarbon groups include those mentioned above. Y is carbon or silicon. In the case of general formula (1), R 13 and R 14 is bonded to Y to form a substituted methylene group or a substituted silylene group as a bridging moiety. Preferred examples include methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, dimethylsilylene, diisopropylsilylene, etc. More preferred is carbon.

[0054] R in general formula (1) or (2) 2 When is a tert-butyl group, R 1 is preferably a methyl or ethyl group, and more preferably a methyl group. 3 , R 4 is a methyl or phenyl group, preferably a methyl group. 3 , R 4 It is preferable that R in the general formula (1) are the same as each other. 2 is a tert-butyl group, R 1 When is a methyl group, R 5 ~R 12 may be hydrogen.

[0055] Furthermore, R 2is a tert-butyl group, R 1 When is an ethyl group, R 5 , R 7 , R 8 , R 9 , R 10 , R 12 is hydrogen and R 6 , R 11 is preferably a tert-butyl group.

[0056] 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 a partially unsaturated bond and / or an aromatic ring, to form a cycloalkylidene group, a cyclomethylenesilylene group, etc. Preferred specific examples include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, etc.

[0057] In general formulas (1) and (2), M represents a metal selected from Group 4 of the periodic table, including titanium, zirconium, and hafnium. Q represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and may be selected from these groups, either identically or in different combinations. Specific examples of halogen atoms include fluorine, chlorine, bromine, and iodine, and specific examples of hydrocarbon groups include those described above. Specific examples of anionic ligands include alkoxy 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 a lone electron pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane. Among these, Q may be the same or different in combination, but at least one is preferably a halogen or an alkyl group.

[0058] The olefin polymerization catalyst used in the polymerization for producing the 1-butene-ethylene copolymer (B) according to the present invention preferably contains, in addition to the metallocene compound (F) represented by the above-mentioned general formula (1) or (2), at least one compound (G) selected from an organoaluminum oxy-compound (G-1), a compound (G-2) that reacts with the metallocene compound (F) to form an ion pair, and an organoaluminum compound (G-3), and may further contain a particulate support (H) as necessary.

[0059] As the organoaluminum oxy compound (G-1) used, a conventionally known aluminoxane can be used as it is. Examples of the compound (G-2) (hereinafter sometimes referred to as "ionic compound") that reacts with the metallocene compound (F) to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-1-501950 and JP-A-2004-51676, etc. Furthermore, heteropoly compounds and isopoly compounds can also be used.

[0060] Specific examples 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, such as tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, and tris(pentafluorophenyl)boron; and trifluoroboron.

[0061] Examples of the organoaluminum compound (G-3) include organoaluminum compounds represented by the following general formula (3). R am Al(OR b )H p Q q ···(3) (In the formula, R a and R bmay be the same as or different from each other, and represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Q represents a halogen atom, m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3. An organoaluminum compound represented by (). Specific examples of such compounds include dialkylaluminum hydrides such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, diisopropylaluminum hydride, and diisobutylaluminum hydride, and alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide.

[0062] As the organoaluminum compound (G-3), tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, and trioctylaluminum, and tri-branched-chain alkylaluminums such as triisobutylaluminum are preferred, and particularly trimethylaluminum and triisobutylaluminum are preferably used.

[0063] In the present invention, the polymerization of the 1-butene / ethylene copolymer (B) can be carried out by any of liquid-phase polymerization methods such as solution polymerization and suspension polymerization or gas-phase polymerization methods. In the liquid-phase polymerization method, an inert hydrocarbon solvent may be used. Specifically, 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 can be mentioned. Also, bulk polymerization using olefins containing 1-butene themselves as a solvent can be carried out.

[0064] When carrying out the polymerization, the metallocene compound (F) is usually 10 in terms of the Group 4 metal atom of the periodic table per liter of the reaction volume. -8 ~ 10 -2 mol, preferably 10 -7 ~ 10 -3The organoaluminum oxy compound (G-1) is used in an amount such that the molar ratio [(G-1) / M] to the transition metal atom (M) in the metallocene compound (F) is usually 0.01 to 5,000, preferably 0.05 to 2,000. The ionic compound (G-2) is used in an amount such that 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 such that the molar ratio [(G-3) / M] to the transition metal atom (M) in the metallocene compound (F) is usually 10 to 5,000, preferably 20 to 2,000.

[0065] The polymerization temperature is usually in the range of −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, heat recovery efficiency, etc.

[0066] The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous, and continuous systems. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0067] Hydrogen can be added to control the molecular weight and polymerization activity of the 1-butene-ethylene copolymer (A) produced during polymerization. The appropriate amount of hydrogen is approximately 0.001 to 100 nL per kg of 1-butene-ethylene copolymer (A).

[0068] Polyolefin (C) containing structural units derived from unsaturated carboxylic acid and / or its derivative The polyolefin (C) containing structural units derived from an unsaturated carboxylic acid and / or a derivative thereof according to the present invention (hereinafter also referred to as "polyolefin (C)") is obtained by modifying a polyolefin with an unsaturated carboxylic acid and / or a derivative thereof, and contains structural units derived from the unsaturated carboxylic acid and / or a derivative thereof.

[0069] Examples of polyolefins to be modified include polypropylene (c1), ethylene-propylene-α-olefin copolymer (c2) and ethylene-α-olefin copolymer (c3). The polyolefin (C) may be a single type or a mixture of two or more types, such as a modified polypropylene (c1), a modified ethylene-propylene-α-olefin copolymer (c2), or a modified ethylene-α-olefin copolymer (c3), or a mixture of two or more types thereof.

[0070] The polypropylene (c1) is, for example, a propylene homopolymer and / or a propylene-α-olefin copolymer. The α-olefin is not limited, but preferably includes ethylene and α-olefins having 4 to 20 carbon atoms, and these α-olefins may be used alone or in combination of two or more. Preferred α-olefins are ethylene and α-olefins having 4 to 10 carbon atoms, and among these, ethylene and α-olefins having 4 to 8 carbon atoms are particularly preferred. The content of structural units derived from propylene in the propylene-α-olefin copolymer is at least 50 mol % and less than 100%.

[0071] The polypropylene (c1) preferably has an intrinsic viscosity [η] of 0.1 to 10 dL / g. The polyolefin (C) obtained by modifying such polypropylene (c1) preferably has an intrinsic viscosity [η] of 0.1 to 6 dL / g. When the intrinsic viscosity [η] is within this range, a composition excellent in moldability and mechanical strength can be obtained. The method for producing polypropylene (c1) is not particularly limited, and examples thereof include well-known methods using well-known catalysts such as Ziegler-Natta catalysts and metallocene catalysts.

[0072] The polypropylene (c1) is preferably a crystalline polymer, and in the case of a copolymer, it may be a random copolymer or a block copolymer. Furthermore, there are no particular restrictions on the stereoregularity or molecular weight as long as it satisfies the moldability and has strength sufficient for use when molded into a molded product. Commercially available resins can also be used as they are. The polypropylene (c1) may be, for example, a homopolypropylene or a propylene-α-olefin random copolymer, or may contain several different isotactic polypropylenes.

[0073] 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, for example, the requirements specified in (i) and (ii) below. (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. (ii) The intrinsic viscosity [η] in decalin at 135°C is in the range of 0.1 to 10 dl / g.

[0074] The α-olefin is preferably an α-olefin having 4 to 10 carbon atoms, and may be used alone or in combination of two or more. The proportions of structural units derived from each monomer are preferably 50 to 85 mol % of propylene, 10 to 22 mol % of ethylene, and 5 to 28 mol % of the α-olefin, and more preferably 55 to 80 mol % of propylene, 10 to 20 mol % of ethylene, and 10 to 28 mol % of the α-olefin.

[0075] With regard to (ii), the intrinsic viscosity [η] is more preferably in the range of 0.5 to 8 dL / g, and even more 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, 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.

[0076] The method for producing the ethylene-propylene-α-olefin copolymer (c2) is not particularly limited, and it can be produced by a known method using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.

[0077] The ethylene-propylene-α-olefin copolymer (c2) is not particularly limited in terms of its stereoregularity or molecular weight, as long as it satisfies the moldability requirements and has sufficient strength to withstand use when molded. Commercially available resins can also be used as they are.

[0078] The ethylene-α-olefin copolymer (c3) is a copolymer of ethylene and an α-olefin, and satisfies, for example, the requirements specified in (iii) and (iv) below. (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. (iv) The intrinsic viscosity [η] in decalin at 135°C is in the range of 0.1 to 10 dl / g.

[0079] The α-olefin is more preferably an α-olefin having 3 to 10 carbon atoms, and may be a single type or a combination of two or more types. The proportions of structural units derived from the respective monomers are 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.

[0080] With regard to (iv), the intrinsic viscosity [η] is more preferably in the range of 0.5 to 8 dL / g, and even more 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, 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.

[0081] The method for producing the ethylene-α-olefin copolymer (c3) is not particularly limited, and examples thereof include well-known methods using well-known catalysts such as Ziegler-Natta catalysts and metallocene catalysts.

[0082] Ethylene-α-olefin copolymer (c3) has excellent moldability, and as long as it has sufficient strength to withstand use when molded into films and other forms, there are no particular restrictions on its stereoregularity or molecular weight. Commercially available resins can be used as ethylene-α-olefin copolymer (c3) as is.

[0083] Examples of unsaturated carboxylic acids and / or derivatives thereof used to modify these polyolefins include unsaturated compounds having one or more carboxylic acid groups, esters of compounds having a carboxylic acid group with alkyl alcohols, and unsaturated compounds having one or more carboxylic acid anhydride groups. Examples of unsaturated groups in unsaturated compounds include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups. The unsaturated carboxylic acids and / or derivatives thereof can be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, with maleic acid, nadic acid, and their acid anhydrides being particularly preferred.

[0084] The amount of structural units derived from unsaturated carboxylic acid and / or its derivatives contained in polyolefin (C) is preferably 0.01 to 5 mass %, more preferably 0.05 to 3.5 mass %, calculated as structural units derived from maleic anhydride. When the amount of structural units derived from unsaturated carboxylic acid and / or its derivatives is within the above range, a resin composition having an excellent balance between moldability and adhesiveness can be obtained.

[0085] In the polyolefin (C), the content of propylene-derived structural units in the structural units excluding the structural units derived from the unsaturated carboxylic acid and / or its derivative is preferably 90 to 100 mol %, more preferably 95 to 100 mol %. When the content of propylene-derived structural units is within the above range, a resin composition having excellent heat resistance can be obtained.

[0086] The method for grafting the unsaturated carboxylic acid and / or its derivative is not particularly limited, and any conventionally known graft polymerization method can be used, such as a solution method, a melt-kneading method, etc. For example, there is a method in which a polyolefin is melted and an unsaturated carboxylic acid and / or its derivative is added thereto for graft reaction, or a method in which a polyolefin is dissolved in a solvent to form a solution and an unsaturated carboxylic acid and / or its derivative is added thereto for graft reaction. The polyolefin (C) may be used singly or in combination of two or more kinds in the resin composition of the present invention.

[0087] Ethylene polymer (D) The ethylene polymer (D) contains 60 to 100 mol % of structural units derived from ethylene. Specific examples of the ethylene polymer (D) according to the present invention include high-pressure low-density polyethylene (D1) and ethylene-α-olefin copolymer (D2).

[0088] By using the ethylene polymer (D), the resin composition obtained has excellent moldability, particularly during molding, and a molded article such as a film can be easily obtained that has a well-balanced excellent resistance to whitening during deformation processing, impact resistance, and transparency.

[0089] <High-pressure low-density polyethylene (D1)> As the high-pressure low-density polyethylene (D1), known polyethylenes can be used without restriction. High-pressure low-density polyethylene is generally polyethylene obtained by radical polymerization of ethylene under high temperature and high pressure, and its production method is not particularly limited, but examples thereof include a radical polymerization method in which radical polymerization is carried out under conditions of 500 to 2000 atmospheres and 150 to 300°C, and examples of the polymerization initiator used here include organic peroxides.

[0090] High-pressure low-density polyethylene (D1) has a density of 900 to 925 kg / m as measured in accordance with ASTM D1505. 3 It is preferable that the range is 910 to 925 kg / m 3 is.

[0091] The high-pressure low-density polyethylene (D1) has a melt flow rate (MFR), measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg, of 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, and preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, particularly preferably 20 g / 10 min or less.

[0092] Ethylene-α-olefin copolymer (D2) The ethylene-α-olefin copolymer (D2) contains at least structural units derived from ethylene and structural units derived from an α-olefin having 3 to 20 carbon atoms.

[0093] The content of structural units 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 %, and particularly preferably 80 to 99 mol %.

[0094] Ethylene-α-olefin copolymer (D2) is characterized by having fewer long-chain branched structures than high-pressure low-density polyethylene (D1), and is sometimes generally referred to as linear low-density polyethylene (LLDPE).

[0095] The content of structural units derived from an 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 %, and particularly preferably 1 to 20 mol %.

[0096] These contents are amounts relative to 100 mol % in total of structural units derived from ethylene and α-olefins having 3 to 20 carbon atoms. When the content of the structural unit is within the above range, a molded article such as a film having a good balance of excellent whitening resistance during deformation processing, impact resistance, and flexibility can be easily obtained from the resulting resin composition.

[0097] 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 these, α-olefins having 3 to 10 carbon atoms are preferred, α-olefins having 3 to 8 carbon atoms are more preferred, propylene, 1-butene, and 1-octene are even more preferred, and propylene is particularly preferred.

[0098] The α-olefins having 3 to 20 carbon atoms may be used alone or in combination of two or more. In addition to the above-mentioned structural units, the ethylene-α-olefin copolymer (D2) may contain one or more structural units derived from other polymerizable monomers, provided that the object of the present invention is not impaired.

[0099] Examples of such other polymerizable monomers include vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids or derivatives thereof such as maleic anhydride; and non-conjugated polyenes such as dicyclopentadiene, cyclohexadiene, and 5-ethylidene-2-norbornene.

[0100] Specific examples of the ethylene-α-olefin copolymer (D2) include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-ethylidenenorbornene copolymer, ethylene-1-butene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, and ethylene-1-octene copolymer. Among these, for example, ethylene-propylene copolymer and ethylene-1-butene copolymer are preferred.

[0101] The density of the ethylene-α-olefin copolymer (D2) is preferably 840 kg / m 3 More preferably, 850 kg / m 3 More preferably, 855 kg / m 3 or more, preferably 940 kg / m 3 Less than or equal to 899 kg / m 3 or less, more preferably 890 kg / m 3 Particularly preferably 885 kg / m or less 3 The following is the result.

[0102] When the density is within the above range, a molded article having a good balance of excellent impact resistance, rigidity, and transparency can be easily obtained. The density can be measured by a density gradient tube method.

[0103] The MFR of the ethylene-α-olefin copolymer (D2) (measured in accordance with ASTM D1238 at 190°C under a load of 2.16 kg) is preferably 0.01 g / 10 min or more, more preferably 0.1 g / 10 min or more, and is preferably 40 g / 10 min or less, more preferably 20 g / 10 min or less, particularly preferably 10 g / 10 min or less. When the MFR is within the above range, a molded article having a good balance of excellent impact resistance, rigidity, and transparency can be easily obtained.

[0104] The MFR of ethylene-α-olefin copolymer (D2) was measured at 190°C under a load of 10 kg in accordance with ASTM D1238. 10 and 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 more, more preferably 5.0 or more, and is preferably 8.0 or less, more preferably 7.0 or less. MFR 10 / MFR 2.16 When the viscosity is within the above range, a molded article having a good balance of transparency and impact resistance can be easily obtained.

[0105] The ethylene-α-olefin copolymer (D2) can be produced by a conventional method using a vanadium catalyst, a titanium catalyst, a metallocene catalyst, etc. Preferably, a metallocene catalyst is used for production, which allows the production of a copolymer having a narrow molecular weight distribution and composition distribution, and is more preferable in terms of mechanical properties, transparency, and impact resistance. The ethylene polymer (D) may be used singly or in combination of two or more in the resin composition of the present invention.

[0106] In the present invention, the monomers used in producing the propylene polymer (A), the 1-butene-ethylene copolymer (B), the polyolefin (C), and the ethylene polymer (D) may be any of fossil fuel-derived monomers, biomass-derived monomers, and chemically recycled monomers, or a combination of one or more of these monomers.

[0107] Other ingredients The resin composition of the present invention may 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, each of which has a different composition from that of the present invention, within a range that does not impair the effects of the present invention. Furthermore, the resin composition of the present invention may contain known additives, such as antioxidants, ultraviolet absorbers, neutralizing agents, nucleating agents, light stabilizers, antistatic agents, antiblocking agents, lubricants, odor absorbents, antibacterial agents, pigments, inorganic and organic fillers, and various synthetic resins, as needed.

[0108] resin composition 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 a derivative thereof, and ethylene polymer (D). The resin composition of the present invention can be produced by a conventionally known method, for example, by melt-kneading the above-mentioned components.

[0109] The content of the 1-butene-ethylene copolymer (B) in the composition of the present invention is 7 to 38% by mass. If the content is less than 7% by mass, the effect of improving whitening resistance cannot be obtained. If the content exceeds 38% by mass, the mechanical properties of an article molded from the composition are reduced. Furthermore, the resin composition of the present invention preferably contains the polyolefin (C) in a content of 0.1 to 10% by mass. When the content of the polyolefin (C) in the composition satisfies this range, the composition can exhibit adhesive strength without impairing its mechanical properties, resulting in a composition with excellent mechanical properties and adhesive strength.

[0110] The contents of the propylene polymer (A), 1-butene-ethylene copolymer (B), polyolefin (C), and ethylene polymer (D) in the resin composition of the present invention are preferably 45 to 87.9 parts by mass of propylene polymer (A), 7 to 38 parts by mass of 1-butene-ethylene copolymer (B), 0.1 to 10 parts by mass of polyolefin (C), and 5 to 30 parts by mass of ethylene polymer (D), based on 100 parts by mass of the total contents of the propylene polymer (A), 1-butene-ethylene copolymer (B), polyolefin (C), and ethylene polymer (D). More preferably, the contents are 55 to 78 parts by mass of propylene polymer (A), 10 to 30 parts by mass of 1-butene-ethylene copolymer (B), 2 to 5 parts by mass of polyolefin (C), and 10 to 20 parts by mass of ethylene polymer (D). When the contents of these components in the resin composition of the present invention are within the above ranges, films containing layers obtained from this composition are less likely to whiten during deformation processing.

[0111] The resin composition of the present invention may contain, in addition to the above-mentioned propylene polymer (A), 1-butene-ethylene copolymer (B), polyolefin (C), and ethylene polymer (D), other components within the scope of the present invention. Examples of other components include resin components other than the above components (A) to (D), and additives such as antioxidants, heat stabilizers, weather stabilizers, slip agents, antiblocking agents, crystal nucleating agents, pigments, etc. The content of these other components is not particularly limited, but is usually 10 parts by mass or less, preferably in the range of 0.01 to 5 parts by mass, per 100 parts by mass of the total of components (A) to (D). Furthermore, the resin composition of the present invention may contain a biomass-derived raw material.

[0112] The resin composition of the present invention preferably has a Shore D hardness in the range of 20 to 70 as measured in accordance with ASTM D2240. The Shore D hardness (according to ASTM D2244) of the resin composition of the present invention is more preferably 25 to 65, and even more preferably 31 to 60. The Shore D hardness is an index of crystallinity, and when the Shore D hardness is equal to or less than the upper limit, a composition having low crystallinity, excellent flexibility, and excellent resistance to whitening during stretching can be obtained. When the Shore D hardness is equal to or greater than the lower limit, a composition having excellent mechanical properties can be obtained.

[0113] <Single-layer film and multi-layer film> The monolayer and multilayer films of the present invention are monolayer or multilayer films containing at least one layer containing the polypropylene-based resin composition. That is, the monolayer film of the present invention is a film consisting of a layer containing the polypropylene-based resin composition, and the multilayer film is a multilayer film containing at least one layer containing the polypropylene-based resin composition.

[0114] 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, construction materials, exterior materials for lithium-ion batteries, etc., whitening is unlikely to occur during secondary processing of the film, such as drawing or folding. Therefore, the monolayer and multilayer films of the present invention can be suitably used as food packaging films, construction material films, and battery packaging films such as pouch-type battery packaging films.

[0115] In particular, polypropylene-based resins have been used as packaging materials for forming the exterior bodies of lithium-ion batteries. However, the present invention uses the specific combination of the above-mentioned propylene-based polymer (A), 1-butene-ethylene copolymer (B), polyolefin (C), and ethylene-based polymer (D) to prevent whitening, which could not be prevented with conventional polypropylene-based resins.

[0116] The multilayer film of the present invention includes, for example, at least one layer containing the polypropylene resin composition, and one or both sides of the layer containing the composition are in contact with other layers. Examples of other layers in contact with the layer containing the composition 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(4-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.

[0117] The monolayer and multilayer films of the present invention can be suitably obtained by melt extrusion molding or the like, and can be produced by a casting method, inflation method, extrusion lamination method or the like which are generally used industrially. [Example]

[0118] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples in any way as long as it does not depart from the gist of the invention.

[0119] (Various measurement methods) In the present examples, measurements were carried out according to the following method. Melt Flow Rate (MFR) Melt flow rate measurements were carried out at 230°C under a load of 2.16 kg in accordance with ASTM D1238. [Intrinsic viscosity [η]] The intrinsic viscosity [η] was measured in accordance with ASTM D1601.

[0120] [Evaluation of whitening resistance] A 0.5 mm thick pressed sheet (single-layer film) was prepared using a press molding machine under the following conditions: preheating and pressing temperature 200°C, preheating time 6 min, pressure 10 MPa, pressing time 4 min, cooling temperature 20°C, cooling time 4 min, and pressure 10 MPa. JIS K6301 No. 2 dumbbells were punched out of the pressed sheet to prepare test specimens. The test specimens were then stretched at room temperature at a rate of 200 mm / min to 0 mm and 20 mm. The hue change of the test specimens was measured using a Shimadzu ATX tensile tester (Konica Minolta CM-3700A) using the reflection method. ΔL was the hue change from the initial value (0 mm) to the 20 mm stretch.

[0121] [Elastic modulus measurement] A 2.0 mm thick pressed sheet (single layer film) was prepared using a press molding machine under the following conditions: preheating and pressing temperature 220°C, preheating time 8 min, pressure 5 MPa, pressing time 5 min, cooling temperature 20°C, cooling time 12 min, and pressure 5 MPa. JIS K7161-2 5A dumbbells were punched out of the pressed sheet to prepare test specimens. A tensile test was performed on the test specimens at room temperature at a tensile speed of 500 mm / min using an Insteco 2005X-5 tensile testing machine, and the elastic modulus was measured.

[0122] [Adhesive strength] A 40 μm thick film was molded from the resin composition described in the Examples or Comparative Examples using an extruder equipped with a T-die. The resulting film was sandwiched between 300 μm thick aluminum foil and heat-sealed for 10 seconds using a heat sealer at 180°C and 0.1 MPa to obtain a multilayer film. The resulting multilayer film was cut into 15 mm widths, and the adhesive strength (unit: N / 15 mm) between the aluminum foil and the resin composition layer was measured using a tensile tester at room temperature of 23°C using the 180° peel method.

[0123] [Polymer composition] The content of structural units derived from propylene, structural units derived from α-olefins, and structural units of 1-butene-ethylene copolymer (B) in a propylene copolymer is measured by 13 C-NMR was performed using the following equipment and conditions. The propylene and α-olefin contents were quantified using a JECX400P nuclear magnetic resonance spectrometer manufactured by JEOL Ltd., using a mixed solvent of deuterated orthodichlorobenzene / deuterated benzene (80 / 20% by volume) as the solvent, a sample concentration of 60 mg / 0.6 mL, a measurement temperature of 120°C, an observation nucleus of 13C (100 MHz), a sequence of single pulse proton decoupling, a pulse width of 4.62 μsec (45° pulse), a repetition time of 5.5 sec, an accumulation count of 8,000, and a chemical shift reference value of 29.73 ppm. The 1-butene and ethylene contents were quantified using a Bruker Biospin AVANCE cryo-500 nuclear magnetic resonance spectrometer as follows: the solvent was a mixed solvent of o-dichlorobenzene and deuterated benzene (volume ratio: 80 / 20), the sample concentration was 20 mg / 0.6 mL, the measurement temperature was 120 °C, and the observation angle was 100°C. 13 C (125 MHz), sequence was single pulse proton broadband decoupling, pulse width was 4.7 μs (45° pulse), repetition time was 5.5 s, number of accumulations was 128, and chemical shift reference value was set to 27.50 ppm for the carbon signal of the butene side chain methylene group. 13 The compositions of 1-butene (C4 content; mol%) and ethylene (C2 content; mol%) were quantified by C-NMR spectroscopy.

[0124] [Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)] As a GPC device, a Waters gel permeation chromatograph Alliance GPC-2000 was used, and polystyrene-equivalent Mw and Mn were measured under the following conditions, and Mw / Mn was calculated. Separation columns: two TSKgel GNH6-HT columns manufactured by Tosoh Corporation, and two TSKgel GNH6-HTL columns manufactured by Tosoh Corporation (column size: diameter 7.5 mm, length 300 mm) Column temperature: 140℃ Mobile phase: o-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) containing 0.025 wt% BHT (manufactured by Takeda Pharmaceutical Co., Ltd.) as an antioxidant Travel speed: 1.0mL / min Sample concentration: 15 mg / 10 mL Sample injection volume: 400 μL Detector: differential refractometer Standard polystyrene: When the molecular weight was Mw<1000 and Mw>4×10^6, a product manufactured by Tosoh Corporation was used; when the molecular weight was 1000≦Mw≦4×10^6, a product manufactured by Pressure Chemical Co. was used.

[0125] [Shore D hardness] Using a D-type measuring instrument, the indenter was brought into contact with the test piece, and the maximum value on the scale was read off to determine the Shore D hardness (in accordance with ASTM D2240).

[0126] Melting point (Tm) The melting point (Tm) was measured using a PerkinElmer DSC8500 differential scanning calorimeter (DSC). 5 to 10 mg of sample was sealed in an aluminum pan. The temperature profile was as follows: the temperature was increased from room temperature to 230°C at 10°C / min, then held at 230°C for 5 minutes, then decreased to -80°C at 10°C / min, held at -80°C for 5 minutes, and then increased to 230°C at 10°C / min. The melting point (Tm) was obtained from the chart obtained during this second temperature increase. The propylene-ethylene-α-olefin copolymer (E) alone was heated from -70°C to 200°C at a heating rate of 20°C / min (first heating), held at 200°C for 10 minutes, then cooled to -70°C at a cooling rate of 20°C / min (first heating), held at -70°C for 1 minute, and then heated again from -70°C to 200°C at a heating rate of 20°C / min (second heating). The peak observed in the first heating was taken as the melting point (Tm).

[0127] (Polyolefin used) The polyolefins used in the examples and comparative examples are shown below. Unless otherwise specified, all polyolefins were prepared by polymerization according to conventional methods.

[0128] Propylene polymer (A) Hereinafter, both PP-1 and PP-2 are considered to be isotactic propylene polymers (A1). PP-1: Random polypropylene (Propylene 96 mol%, ethylene 4 mol%, MFR = 3.0 g / 10 min, Tm 140°C) PP-2: Random polypropylene (Propylene content 96 mol%, ethylene content 4 mol%, MFR = 7.0 g / 10 min, Tm = 138 ° C)

[0129] 1-Butene-ethylene copolymer (B) BER-1: 1-butene-ethylene copolymer (15 mol% ethylene-derived structural units, 85 mol% butene-derived structural units, MFR = 6 g / 10 min, isotactic pendant fraction (mmmm) 98.0%, intrinsic viscosity [η] 1.71 dl / g, Mw = 366,000) synthesized by the following method.

[0130] [BER-1 manufacturing example] n-Hexane was supplied at a rate of 14.2 L / h to one supply inlet of a 300-liter continuous polymerization reactor, and a mixed hexane solution of isopropyldene(3-tert-butyl-5-methylcyclopentadienyl-fluorenyl)zirconium dichloride (main catalyst 1), modified methylaluminoxane, and triisobutylaluminum (main catalyst 1) with a zirconium-equivalent concentration of 0.5 mmol / L, modified methylaluminoxane with an aluminum-equivalent concentration of 4 mmol / L, and triisobutylaluminum with an aluminum-equivalent concentration of 100 mmol / L) was continuously supplied at a rate of 0.22 L / h from the other supply inlet (total hexane: 10 L / h). Simultaneously, 1-butene was continuously fed at a rate of 27.0 kg / h, ethylene at 1.0 kg / h, and hydrogen at 0.6 NL / h through another feed port of the polymerization reactor. Continuous solution polymerization was 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 1-butene-ethylene copolymer (BER-1).

[0131] BER-2: 1-Butene-ethylene copolymer (15 mol% ethylene-derived structural units, 85 mol% butene-derived structural units, MFR = 3 g / 10 min, isotactic pendant fraction (mmmm) 98.0%, intrinsic viscosity [η] 2.14 dL / g, Mw = 490,000) was produced in the same manner as in Production Example BER-1, except that ethylene and hydrogen were fed at 0.9 kg / h and 0.1 NL / h, respectively, through separate feed ports into the polymerization reactor.

[0132] BER-3: 1-Butene-ethylene copolymer (ethylene-derived structural units 6 mol%, butene-derived structural units 94 mol%, MFR = 6 g / 10 min, isotactic pendant fraction (mmmm) 93.0%, intrinsic viscosity [η] 1.71 dl / g, Mw = 360,000) was produced in the same manner as in Production Example BER-1, except that ethylene was supplied at 0.4 kg / h through a separate supply port in the polymerization reactor and the polymerization pressure was 0.6 MPaG.

[0133] BER-4: Mitsui Chemicals BL3540M (2 mol% ethylene-derived structural units, 98 mol% butene-derived structural units, MFR = 9 g / 10 min, isotactic pendant fraction (mmmm) 93.0%, intrinsic viscosity [η] 1.50 dl / g, Mw = 337,000)

[0134] Polyolefin (C) Modified PP-1: Modified homopolypropylene (Maleic anhydride graft amount 3.0 mass%, intrinsic viscosity [η] 0.4 dl / g)

[0135] Ethylene polymer (D) D-1: Low-density polyethylene (MFR=18g / 10min, density 0.92g / cm 3 ) D-2: EPR-1: (80 mol% structural units derived from ethylene, 20 mol% structural units derived from propylene, MFR = 0.8 g / 10 min)

[0136] Propylene-ethylene-α-olefin copolymer(E) Structural units derived from ethylene 16 mol%, structural units derived from propylene 78 mol%, structural units derived from butene 6 mol%, MFR = 6 g / 10 min, Tm = 48 ° C

[0137] [Example 1] 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.

[0138] [Examples 2 to 9, Comparative Examples 1 to 4] In Examples 2 to 9 and Comparative Examples 1 to 4, resin compositions were produced in the same manner as in Example 1 according to the formulations shown in Table 1.

[0139] Table 1 shows the MFR of the resin compositions obtained in the examples and comparative examples, as well as the whitening resistance, elastic modulus, hardness and adhesive strength of the press sheets made from these resin compositions with respect to the multilayer films. As shown in Examples 1 to 9, the use of the composition of the present invention makes it possible to provide a multilayer film excellent in whitening resistance, elastic modulus, and adhesiveness. Furthermore, the use of this multilayer film makes it possible to provide a battery exterior material excellent in whitening resistance, heat resistance, mechanical properties, durability, and adhesiveness.

[0140] [Table 1]

Claims

1. a propylene-based polymer (A) that satisfies the following (a); a 1-butene / ethylene copolymer (B) that satisfies the following (b-1); a polyolefin (C) containing structural units derived from an unsaturated carboxylic acid and / or a derivative thereof; an ethylene polymer (D) containing 60 to 100 mol % of structural units derived from ethylene; Contains A resin composition, wherein the content of the 1-butene-ethylene copolymer (B) in the composition is 7 to 38 mass %. (a) The melting point observed by differential scanning calorimetry is 100°C or higher. (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. 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); The resin composition according to claim 1, comprising 5 to 30 parts by mass of the ethylene polymer (D) (wherein the total of (A), (B), (C), and (D) is 100 parts by mass).

3. the polyolefin (C) contains 0.01 to 5 mass% of structural units derived from an unsaturated carboxylic acid and / or a derivative thereof, calculated as structural units derived from maleic anhydride; The resin composition according to claim 1, wherein the polyolefin (C) has a content of propylene-derived structural units in structural units excluding structural units derived from the unsaturated carboxylic acid and / or a derivative thereof of 90 to 100 mol%.

4. 1-butene / ethylene copolymer (B), 13 The resin composition according to claim 1, wherein the isotactic pendant fraction (mmmm) calculated by C-NMR is in the range of 80 to 99.9%.

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

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

7. A single-layer or multi-layer film comprising at least one layer comprising the resin composition according to any one of claims 1 to 6.

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

9. A multilayer film comprising at least one layer containing the resin composition according to any one of claims 1 to 6, 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.

10. The monolayer or multilayer film according to claim 7, which is a food packaging film.

11. The monolayer or multilayer film according to claim 7, which is a film for construction materials.

12. The monolayer or multilayer film according to claim 7, which is a film for packaging batteries.

13. The monolayer or multilayer film according to claim 7, which is a pouch-type film for packaging batteries.

14. A method for producing a monolayer or multilayer film, comprising a step of melt-extrusion molding the resin composition according to any one of claims 1 to 6.

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