Propylene-based resin composition and its uses

Abstract

To provide a propylene-based resin composition which has an excellent balance among flexibility, tensile strength and whitening resistance.SOLUTION: A propylene-based resin composition contains 1-99 mass% of a copolymer (A) satisfying (I) to (IV), and 1-99 mass% of a propylene-based polymer (B) that is a polymer other than the copolymer (A) and has an MFR (230°C, load of 2.16 kg and according to ASTM D 1238E) of 0.1-500 g / 10 minutes (total of (A) to (B) is 100 mass%). (I) With respect to 100 mol% of the total of a propylene-derived structural unit (i) and an α-olefin-derived structural unit (ii) having 5 to 20 carbon atoms, a content of the structural unit (i) is 75-95 mol%, and a content of the structural unit (ii) is 5-25 mol%, (II) a melting point measured by DSC is 95°C or lower or is not observed, (III) an isotactic triad fraction is 85% or more, and (IV) intrinsic viscosity (135°C, decalin) is 0.5-10 dl / g.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a propylene-based resin composition, an adhesive resin composition, pellets, a molded article, a non-oriented film, a sheet, an injection-molded article, a blow-molded article, and an automobile part. [Background technology]

[0002] BACKGROUND ART In recent years, propylene-based resin compositions containing polypropylene-based polymers as a main component have become known as polyolefin materials that are excellent in heat resistance, transparency, etc., as well as environmental friendliness and hygienic properties.

[0003] Currently, while the applications of such propylene-based resin compositions are expanding, the performance of the propylene-based resin compositions currently in use is insufficient, and there is room for improvement in terms of, for example, tensile strength and resistance to whitening during molding processing.

[0004] Patent Document 1 describes that a specific copolymer of propylene and an α-olefin having 5 or more carbon atoms has a certain degree of tensile strength and does not suffer from flex whitening. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-7731 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the propylene-based resin compositions using conventional propylene-based polymers such as those described in Patent Document 1 have room for improvement in terms of the balance between flexibility, tensile strength, and whitening resistance. The present invention has been made in view of the above, and an object of the present invention is to provide a propylene-based resin composition which is excellent in balance among flexibility, tensile strength and whitening resistance. [Means for solving the problem]

[0007] A configuration example of the present invention is as follows. In this specification, the numerical range "A to B" indicates A or more and B or less.

[0008] [1] 1 to 99% by mass of a propylene-α-olefin copolymer (A) satisfying the following requirements (I) to (IV): A propylene-based resin composition containing 1 to 99 mass% of a propylene-based polymer (B) other than the copolymer (A), which has an MFR of 0.1 to 500 g / 10 min at 230°C under a load of 2.16 kg, measured in accordance with ASTM D1238E (where the total of the copolymer (A) and the polymer (B) is 100 mass%). (I) When the total of the structural unit (i) derived from propylene and the structural unit (ii) derived from an α-olefin having 5 to 20 carbon atoms is taken as 100 mol %, the content of the structural unit (i) is 75 to 95 mol %, and the content of the structural unit (ii) is 5 to 25 mol %. (II) The melting point measured by differential scanning calorimetry (DSC) is 95°C or less or not observed. (III) 13 The isotactic triad fraction measured by C-NMR is 85% or more. (IV) The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 10 dl / g.

[0009] [2] The copolymer (A), 13 The propylene-based resin composition according to [1], wherein the isotactic triad fraction measured by C-NMR is 90% or more.

[0010] [3] The propylene-based resin composition according to [1] or [2], wherein the copolymer (A) has an MFR of 0.1 to 30 g / 10 min at 230° C. under a load of 2.16 kg, as measured in accordance with ASTM D1238E.

[0011] [4] The propylene-based resin composition according to any one of [1] to [3], wherein the α-olefin having 5 to 20 carbon atoms in the copolymer (A) is at least one selected from 1-hexene, 1-octene, 1-decene, and 1-dodecene.

[0012] [5] An adhesive resin composition comprising the propylene-based resin composition according to any one of [1] to [4]. [6] Pellets containing the propylene-based resin composition according to any one of [1] to [4] or the adhesive resin composition according to [5]. [7] A molded article comprising the propylene-based resin composition according to any one of [1] to [4] or the adhesive resin composition according to [5]. [8] An unstretched film comprising the propylene-based resin composition according to any one of [1] to [4] or the adhesive resin composition according to [5]. [9] A sheet comprising the propylene-based resin composition according to any one of [1] to [4] or the adhesive resin composition according to [5].

[10] An injection-molded article comprising the propylene-based resin composition according to any one of [1] to [4] or the adhesive resin composition according to [5].

[11] A blow-molded article comprising the propylene-based resin composition according to any one of [1] to [4] or the adhesive resin composition according to [5].

[12] An automobile part selected from an interior part and an exterior part, comprising the propylene-based resin composition according to any one of [1] to [4] or the adhesive resin composition according to [5]. [Effects of the Invention]

[0013] According to the present invention, a composition (molded article) having a good balance of flexibility, tensile strength, and whitening resistance can be easily obtained. DETAILED DESCRIPTION OF THE INVENTION

[0014] <Propylene-based resin composition> The propylene-based resin composition according to the present invention (hereinafter also referred to as "the composition") comprises 1 to 99 mass % of a propylene-α-olefin copolymer (A) satisfying the following requirements (I) to (IV): The composition contains 1 to 99% by mass of a propylene polymer (B) other than the copolymer (A), which has an MFR of 0.1 to 500 g / 10 min at 230°C under a load of 2.16 kg as measured in accordance with ASTM D1238E (where the total of the copolymer (A) and the polymer (B) is 100% by mass).

[0015] The breaking stress of the present composition is preferably 10 MPa or more, more preferably 20 MPa or more, even more preferably 25 MPa or more, and particularly preferably 30 MPa or more. Specifically, the breaking stress is measured by the method described in the examples below.

[0016] The Shore D hardness (instantaneous value) of the present composition is preferably 30-80, and more preferably 32-78. The Shore D hardness (instantaneous value) is specifically measured by the method described in the examples below.

[0017] <Propylene-α-olefin copolymer (A)> The propylene-α-olefin copolymer (A) satisfies the following requirements (I) to (IV). The copolymer (A) used in the present composition may be one type or two or more types. (I) When the total of the structural unit (i) derived from propylene and the structural unit (ii) derived from an α-olefin having 5 to 20 carbon atoms is taken as 100 mol %, the content of the structural unit (i) is 75 to 95 mol %, and the content of the structural unit (ii) is 5 to 25 mol %. (II) The melting point measured by differential scanning calorimetry (DSC) is 95°C or less or not observed. (III) 13 The isotactic triad fraction (mm fraction) measured by C-NMR is 85% or more. (IV) The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 10 dl / g.

[0018] The copolymer (A) is not particularly limited as long as it is a copolymer obtained using propylene and one or more α-olefins having 5 to 20 carbon atoms, but is preferably a random copolymer.

[0019] The content of the structural unit (i) is 75 to 95 mol %, preferably 80 to 95 mol %, and more preferably 85 to 95 mol %. The content of the structural unit (ii) is 5 to 25 mol %, preferably 5 to 20 mol %, and more preferably 5 to 15 mol %. The content of each of the structural units (i) and (ii) is the content when the total of the structural units (i) and (ii) is taken as 100 mol %.

[0020] When the contents of the structural units (i) and (ii) are within the above ranges, a composition (molded article) having a good balance of flexibility and mechanical strength, particularly a good balance of flexibility and tensile strength, can be easily obtained. The content of the structural units (i) and (ii) is 13 It can be measured by C-NMR, specifically by the method described in the examples below.

[0021] Examples of the α-olefins having 5 to 20 carbon atoms include 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-nonadecene, and 1-eicosene. 1-hexene, 1-octene, and 1-dodecene are preferred, with 1-octene being more preferred, because they are capable of forming a crystalline structure with many tie molecules and resulting in a copolymer with a good balance between flexibility and tensile strength. Two or more of the α-olefins having 5 to 20 carbon atoms may be used, but preferably one type.

[0022] The copolymer (A) has a melting point Tm of 95° C. or lower as measured by DSC, or no melting point is observed as measured by DSC (no melting peak is observed by DSC). When a melting point is observed, Tm is preferably 90° C. or lower, more preferably 85° C. or lower, with no particular lower limit. When the melting point is within the above range, or when no melting point is observed, a composition (molded article) with excellent flexibility can be easily obtained. The melting point is specifically measured by the method described in the Examples below. Here, the melting point refers to the temperature at the peak apex of the melting peak, and "no melting peak observed" means that no crystalline melting peak with a heat of crystalline fusion (ΔH) of 1 J / g or more is observed in the range of -100 to 200°C. When two or more melting peaks are observed, the highest temperature among the peak apex temperatures of these peaks is the melting point.

[0023] When the melting peak is observed, the heat of fusion (ΔH), which is the integrated value of the peak, is preferably 1 to 50 J / g, more preferably 5 to 45 J / g, and even more preferably 10 to 40 J / g. When ΔH is within the above range, a composition (molded article) having a good balance between flexibility and mechanical strength can be easily obtained.

[0024] The mm fraction of the copolymer (A) is 85% or more, preferably 90% or more, more preferably 92% or more, and particularly preferably 98% or more. When the mm fraction is within the above range, a composition (molded article), particularly an injection molded article, having a good balance of excellent flowability, mechanical strength, and impact resistance can be easily obtained. The mm fraction can be measured and analyzed by the method described in Japanese Patent Application Laid-Open No. 2007-186664.

[0025] The copolymer (A) has an intrinsic viscosity [η] measured in decalin at 135° C. of 0.5 to 10 dl / g, preferably 1 to 5 dl / g, and more preferably 1.5 to 2.5 dl / g. When the intrinsic viscosity [η] is within the above range, a composition (molded article) excellent in properties such as moldability and mechanical strength can be easily obtained.

[0026] The MFR of the copolymer (A), measured in accordance with ASTM D1238E at 230° C. under a load of 2.16 kg, is preferably from 0.1 to 30 g / 10 min, more preferably from 0.2 to 15 g / 10 min. When the MFR is within the above range, a composition (molded article) having a good balance of moldability and mechanical strength can be easily obtained.

[0027] The tensile modulus of the copolymer (A) is preferably 0.5 to 200 MPa, more preferably 1 to 180 MPa, and even more preferably 2 to 150 MPa. Specifically, the tensile modulus is measured by the method described in the examples below.

[0028] The breaking stress of the copolymer (A) is preferably 5 MPa or more, more preferably 10 MPa or more, and even more preferably 15 MPa or more. Specifically, the breaking stress is measured by the method described in the examples below.

[0029] The copolymer (A) has a Shore A hardness (instantaneous value) of preferably 50 to 99, more preferably 60 to 98. When it is difficult to measure the Shore A hardness, a similar evaluation can be performed using the Shore D hardness instead, and the copolymer (A) has a Shore D hardness (instantaneous value) of preferably 12 to 62, more preferably 18 to 60. The Shore A hardness (instantaneous value) and the Shore D hardness (instantaneous value) are specifically measured by the method described in the examples below. When the tensile modulus (and breaking stress) is within the above range and the Shore A hardness or Shore D hardness is within the above range, a composition (molded product) having a good balance between flexibility and mechanical strength such as tensile strength can be easily obtained.

[0030] The method for producing the copolymer (A) is not particularly limited, and it can be produced by copolymerizing propylene and an α-olefin having 5 to 20 carbon atoms in the presence of a known catalyst, for example, a catalyst mainly composed of a solid titanium component and an organometallic compound, or a metallocene catalyst using a metallocene compound as one of the catalyst components. Preferably, it is obtained by copolymerizing propylene and an α-olefin having 5 to 20 carbon atoms in the presence of a metallocene catalyst, and examples of the catalyst that can be used include the catalysts described in WO 2004 / 087775, JP 2007-186664, WO 2006 / 68308, WO 2014 / 50816, and WO 2014 / 50817.

[0031] The content of copolymer (A) is 1 to 99 mass%, preferably 5 to 95 mass%, more preferably 6 to 93 mass%, even more preferably 7 to 91 mass%, and particularly preferably 8 to 90 mass%, relative to 100 mass% of the total of copolymer (A) and polymer (B). When the content of the copolymer (A) is within the above range, a composition (molded article) having a good balance of flexibility, tensile strength, and whitening resistance can be easily obtained.

[0032] <Propylene-based polymer (B)> The propylene polymer (B) is not particularly limited as long as it is a polymer other than the copolymer (A) and has an MFR of 0.1 to 500 g / 10 min at 230°C under a load of 2.16 kg, as measured in accordance with ASTM D1238E. The polymer (B) used in the present composition may be one type or two or more types.

[0033] The polymer (B) may be a homopolypropylene or a copolymer of propylene and an α-olefin other than propylene having 2 to 20 carbon atoms, etc. The copolymer may be a random copolymer (random polypropylene) or a block copolymer. The polymer (B) is preferably a homopolypropylene or a random copolymer of propylene and an α-olefin having 2 to 20 carbon atoms other than propylene. The polymer (B) may be an unmodified polymer or a modified polymer, such as the same polymers as the modified polyolefins described below.

[0034] Considering that molded articles having excellent heat resistance can be easily obtained, homopolypropylene is preferred, and considering that molded articles having excellent whitening resistance and impact properties can be easily obtained, the random copolymer is preferred. The random copolymer is preferably a copolymer of propylene and an α-olefin other than propylene having 2 to 10 carbon atoms, or a copolymer of propylene, ethylene and an α-olefin having 4 to 10 carbon atoms.

[0035] In the random copolymer, the content of structural units derived from propylene is usually 90 mol% or more, relative to the total of 100 mol% of structural units derived from propylene and structural units derived from α-olefins having 2 to 20 carbon atoms other than propylene. The content of structural units derived from α-olefins having 2 to 20 carbon atoms other than propylene is usually 10 mol% or less, preferably 8 mol% or less, more preferably 7.5 mol% or less, preferably 0.1 mol% or more, more preferably 0.2 mol% or more.

[0036] Examples of the α-olefins having 2 to 20 carbon atoms other than propylene include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-nonadecene, and 1-eicosene. Two or more of the α-olefins having 2 to 20 carbon atoms other than propylene may be used.

[0037] The MFR of the polymer (B) is 0.1 to 400 g / 10 min, preferably 0.5 g / 10 min or more, and preferably 300 g / 10 min or less, more preferably 200 g / 10 min or less, even more preferably 100 g / 10 min or less, and particularly preferably 90 g / 10 min or less. When the MFR is within the above range, a composition having excellent moldability can be easily obtained, and a composition (molded article) having excellent dispersibility with the copolymer (A) and excellent mechanical strength such as tensile strength can be easily obtained.

[0038] The melting point of the polymer (B) measured by DSC is preferably from 110 to 170°C, more preferably from 120 to 170°C, and even more preferably from 125 to 168°C. A melting point within the above range is preferable because it provides a good balance of moldability, heat resistance and transparency, and also provides good properties as a crystalline polypropylene. The melting point is the melting point (the temperature at the top of the melting peak) observed using a DSC measurement device when the sample is held at 200°C for 10 minutes, cooled to -20°C at a rate of 10°C / min, held at -20°C for 1 minute, and then heated again to 200°C at a rate of 10°C / min. The heat of fusion (ΔH), which is the integrated value of the melting peak, is preferably 50 mJ / mg or more.

[0039] The isotactic pentad fraction (mmmm fraction) of the polymer (B) is preferably 90% or more, more preferably 92% or more, and even more preferably 95% or more. When the mmmm fraction is within the above range, a composition (molded article) having a good balance between rigidity and transparency, and particularly excellent transparency, can be easily obtained. The mmmm fraction is, for example, as described in JP-A-2007-186664, 13 This is the proportion of isotactic sequences in pentad units in a molecular chain measured using C-NMR, in other words, the fraction of propylene monomer units at the center of a chain in which five consecutive propylene monomer units are meso-bonded, and can be measured by the method described in the publication.

[0040] The polymer (B) can be produced by various known methods using a Ziegler-Natta catalyst or a metallocene catalyst.

[0041] The content of polymer (B) is 1 to 99 mass%, preferably 5 to 95 mass%, more preferably 7 to 94 mass%, even more preferably 9 to 93 mass%, and particularly preferably 10 to 92 mass%, relative to 100 mass% of the total of copolymer (A) and polymer (B). When the content of the polymer (B) is within the above range, a composition (molded article) having a good balance of flexibility, tensile strength, and whitening resistance can be easily obtained.

[0042] <Additives> The present composition may contain additives other than the copolymer (A) and polymer (B), specifically, additives such as polyolefins other than the copolymer (A) and polymer (B) or modified products thereof, weather resistance stabilizers, heat resistance stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, nucleating agents (crystal nucleating agents), lubricants, pigments, dyes, plasticizers, antioxidants, hydrochloric acid absorbers, and antioxidants, as needed, within the scope of the present invention. These additives may be used alone or in combination of two or more.

[0043] For example, a crystal nucleating agent may be used from the viewpoints of increasing the crystallization rate, shortening the molding cycle, increasing transparency, and adjusting rigidity. The crystal nucleating agent is preferably a substance that has a nucleating effect on the propylene-based resin, and specific examples include metal salts of aromatic carboxylic acids, metal salts of aromatic phosphates, alditol derivatives, and metal salts of rosin.

[0044] The aromatic carboxylic acid metal salt is preferably aluminum pt-butylbenzoate. The aromatic phosphate metal salt is preferably sodium 2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate or aluminum 2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate. The alditol derivative is preferably a hexitol derivative or a nonitol derivative, and particularly preferably p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, or 7,8,9-trideoxy-3,5:4,6-bis-O-[(4-propylphenyl)methylene]-D-glycero-L-gulo-nonitol. When a crystal nucleating agent is used, the content of the crystal nucleating agent in the present composition is usually 0.01 to 2 mass %, preferably 0.05 to 1 mass %.

[0045] <Method for preparing the present composition> The present composition can be prepared by mixing the components to be blended in the composition using various known methods, such as a Henschel mixer, V-blender, ribbon blender, tumbler blender, kneader-ruder, etc., or by melt-kneading the components using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, etc. Furthermore, granulation, pulverization, etc. may be carried out as necessary. When mixing or kneading these components, the components to be blended may be added all at once or in stages.

[0046] ≪Adhesive resin composition≫ The adhesive resin composition according to the present invention contains the present composition. The adhesive resin composition may consist of the present composition alone, or may contain the present composition together with other components. The content of the present composition in the adhesive resin composition is preferably 1 to 50% by mass, more preferably 1 to 40% by mass.

[0047] It is preferable that the adhesive resin composition contains a modified polyolefin, as this has better adhesion and compatibility with the substrate (other resin) and may further improve the wettability of the surface of the resulting molded article. Specific examples of the modified polyolefin include those obtained by graft-modifying the copolymer (A) or polymer (B) with one or more polar monomers.

[0048] Suitable examples of the polar monomer include unsaturated carboxylic acids and / or derivatives thereof, such as unsaturated compounds having one or more carboxylic acid groups, esters of unsaturated carboxylic acid compounds having a carboxylic acid group with alkyl alcohols, and unsaturated compounds having one or more carboxylic acid anhydride groups (e.g., acid anhydrides of unsaturated dicarboxylic acids). Examples of the unsaturated moiety in these compounds include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. The polar monomer is preferably an unsaturated dicarboxylic acid or an acid anhydride thereof, more preferably maleic acid, nadic acid or an acid anhydride thereof.

[0049] The modification amount (graft amount of polar monomer) in the modified polyolefin is usually 0.1% by mass or more, preferably 0.2% by mass or more, relative to 100% by mass of the modified polyolefin, in order to obtain better adhesion and compatibility with the substrate (other resin), and is usually 50% by mass or less, preferably 30% by mass or less, and more preferably 10% by mass or less. The degree of modification can be controlled, for example, by appropriately selecting the grafting conditions.

[0050] The method for grafting the polar monomer is not particularly limited, and any conventionally known graft polymerization method can be used, such as a solution method, a melt-kneading method, etc. Specific examples include a method in which the copolymer (A) or the polymer (B) is melted or dissolved in a solvent to form a solution, and the graft monomer is added thereto to cause a graft reaction.

[0051] When the modified polyolefin is blended into the adhesive resin composition, the content of the modified polyolefin is preferably 40 to 90% by mass, more preferably 40 to 80% by mass, relative to 100% by mass of the adhesive resin composition. When the content of the modified polyolefin is within the above range, a composition exhibiting high adhesive strength can be easily obtained.

[0052] The adhesive resin composition is usually laminated on one or both sides of a single-layer or multi-layer substrate to form a multilayer film. Specifically, the adhesive resin composition is used as a multilayer film by co-extruding the adhesive resin composition and a substrate layer using a known multilayer film molding method such as a T-die film molding method or an inflation film molding method, or by providing the adhesive resin composition on a pre-formed substrate.

[0053] The substrate is not particularly limited, but is preferably a substrate made of a thermoplastic resin. Examples of the thermoplastic resin include polypropylene-based resins (e.g., homopolypropylene, copolymers of propylene and a small amount of α-olefin), polyethylene-based resins (e.g., low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene), known ethylene-based polymers (e.g., ethylene-α-olefin copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-vinyl alcohol copolymer), poly-4-methyl-pentene-1, and mixtures thereof. The substrate may be surface-treated by a conventionally known method, or may be colored or printed.

[0054] The multilayer film can be suitably used as a surface protection film for protecting metal plates such as aluminum plates, steel plates, and stainless steel plates, and their coated plates, glass plates, synthetic resin plates, and other processing members, as well as home appliances, automobile parts, and electronic parts that use these members.Specifically, the multilayer film can be suitably used as, for example, an optical plate protective film, a lens protective film, a film used in the electronics field such as a backgrinding tape for semiconductor wafers, a dicing tape, and a protective tape for printed circuit boards, a window glass protective film, and a film for baking coating.

[0055] The adhesive resin composition can be prepared by mixing the components to be blended in the composition by various known methods, such as a method using a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, a kneader-ruder, etc., or by melt-kneading the components by a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, etc. Furthermore, granulation, pulverization, etc. may be carried out as necessary. When mixing or kneading these components, the components to be blended may be added all at once or in stages.

[0056] <Pellets> The pellet according to the present invention contains the present composition or the adhesive resin composition. The shape, size, etc. of the pellets are not particularly limited and may be appropriately selected depending on the desired application. The pellets can be produced by melting the present composition or the adhesive resin composition in a kneader such as a Banbury mixer, a roll or an extruder, and granulating the melted composition.

[0057] <Molded body> The molded article according to the present invention comprises the present composition or the adhesive resin composition. The molded article can be produced by molding the present composition or the adhesive resin composition by a conventionally known molding method, such as sheet (film) molding, blow molding, injection molding, press molding, extrusion molding, inflation molding, extrusion blow molding, injection blow molding, vacuum molding, calendar molding, or melt T-die casting.

[0058] The molded article is not particularly limited, but since the present composition and the adhesive resin composition exhibit the above-mentioned effects, it is preferable that the molded article is one in which the effects are more effectively exhibited. Specific examples of the molded article include (unstretched) films, sheets, injection-molded articles, blow-molded articles, and automobile parts (e.g., automobile interior parts, automobile exterior parts). More specific examples include civil engineering and building materials such as multilayer hoses, pipes, tubes, decorative sheets, and flooring mats, covering materials for electric wires and cables (e.g., insulating layers, sheath layers), nonwoven fabrics, stretch films, food packaging films, packaging sheets, food packaging trays and beverage cups (thermoformed from the sheet), and plastic containers (folded from the sheet).

[0059] <Non-stretched film> The non-stretched film is not particularly limited as long as it is a non-stretched film, and the shape, size (thickness), etc. may be appropriately selected depending on the desired application. The non-stretched film may be a single layer or a multilayer. If it is a multilayer film, at least one layer of the film may contain the present composition or the adhesive resin composition. When the non-stretched film is a multilayer film, all of the layers are not stretched.

[0060] The thickness of the unstretched film (total thickness if multi-layered) is preferably 5 to 150 μm, more preferably 10 to 100 μm. In this specification, no particular distinction is made between film and sheet, but a film usually refers to a membranous body with a thickness of less than 250 μm, and a sheet usually refers to a thin plate-like body with a thickness of 250 μm or more.

[0061] Specific applications of the non-stretched film include, for example, packaging films for packaging foods, liquids, medicines, and the like.

[0062] <Sheet> The sheet is not particularly limited, and its shape, size (thickness), etc. may be appropriately selected depending on the desired application. The sheet may be single-layered or multi-layered. If it is multi-layered, at least one layer of the sheet may contain the present composition or the adhesive resin composition.

[0063] The thickness of the sheet (total thickness if multi-layered) is preferably 250 to 2000 μm, more preferably 250 to 1500 μm.

[0064] Specific uses of the sheet include, for example, packaging sheets for packaging food, liquids, medicines, etc., and containers formed from the sheet (e.g., trays and cups thermoformed from the sheet, and containers formed by folding the sheet).

[0065] <Injection molded products and blow molded products> The injection molded article is not particularly limited, but examples thereof include molded articles produced by injection molding into a desired shape using a conventionally known injection molding apparatus under known conditions. The injection molded articles can be used in a wide range of applications, such as trim materials for automobile interiors, exterior parts for automobiles, housings for home appliances, containers, tubes, and pipes.

[0066] The blow molded article is not particularly limited, but examples thereof include molded articles produced by blow molding into a desired shape using a conventionally known blow molding apparatus under known conditions. The blow molded article may be a multi-layered article, in which case at least one layer contains the present composition or the adhesive resin composition.

[0067] Specific applications of the injection molded articles and blow molded articles include, for example, food containers, beverage containers, caps, pharmaceutical containers, various other containers, daily necessities (e.g., clothing cases, buckets, washbasins, stationery such as writing implements, containers, toys, cooking utensils, and various other cases), housings for home appliances, automobile parts, tubes, and pipes.

[0068] <Automotive interior and exterior parts> The automobile interior and exterior parts are not particularly limited, and examples thereof include automobile parts molded by injection molding or the like. Specific examples of the automobile interior parts include trim, instrument panels, and column covers, while specific examples of the automobile exterior parts include fenders, bumpers, side moldings, mudguards, and mirror covers. [Example]

[0069] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0070] [Production Example 1] Production of propylene-α-olefin copolymer (A-1) Dry hexane was fed at a rate of 1,807 mL / hr through one feed port into a 950 mL continuous polymerization reactor that had been thoroughly purged with nitrogen, and 1-octene was fed at a rate of 355 mL / hr and a hexane solution of triisobutylaluminum (4.5 mmol / L) was fed at a rate of 57 mL / hr through another feed port. Simultaneously, propylene was supplied at a rate of 1,080 mL / hr, hydrogen at a rate of 0.19 mL / hr, and a hexane solution (0.03 mmol / L, zirconium / methylaluminoxane molar ratio of 1 / 300) of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride (hereinafter also referred to as "Catalyst a") synthesized according to Synthesis Example 4 of Japanese Patent No. 5,980,339 in contact with methylaluminoxane (manufactured by Tosoh Finechem Corporation) was supplied into the polymerization reactor at a rate of 60 mL / hr through another supply port of the continuous polymerization reactor. Continuous solution polymerization was carried out under the conditions of a polymerization temperature of 65°C, a total pressure of 3.6 MPaG, a residence time of 17 min, and an agitation speed of 700 rpm. The polymerization was then terminated by adding a methanol / hexane solution (methanol / hexane = 2 / 98 volume ratio) at a rate of 100 mL / hr. The mixture was then dried at 180 °C under a nitrogen atmosphere for 30 minutes and then under vacuum for 30 minutes, producing propylene-α-olefin copolymer (A-1) at a production rate of 163 g / hr.

[0071] [Production Example 2] Production of propylene-α-olefin copolymer (A-2) Propylene-α-olefin copolymer (A-2) was produced in the same manner as in Production Example 1, except that the feed rate of dry hexane was changed to 1718 mL / hr, the feed rate of 1-octene to 440 mL / hr, the concentration and feed rate of the hexane solution of triisobutylaluminum to 4 mmol / L and 61 mL / hr, respectively, the feed rate of hydrogen to 0.15 mL / hr, and the feed rate of the hexane solution in contact with catalyst a and methylaluminoxane to 52 mL / hr.

[0072] [Production Example 3] Production of propylene-α-olefin copolymer (A-3) Propylene-α-olefin copolymer (A-3) was produced in the same manner as in Production Example 1, except that the feed rate of dry hexane was changed to 1891 mL / hr, the feed rate of 1-octene to 265 mL / hr, the concentration and feed rate of the hexane solution of triisobutylaluminum to 4 mmol / L and 80 mL / hr, respectively, the feed rate of hydrogen to 0.1 Nl / hr, and the feed rate of the hexane solution in contact with catalyst a and methylaluminoxane to 69 mL / hr.

[0073] [Production Example 4] Production of propylene-α-olefin copolymer (A-4) Dry hexane was supplied to a 950 mL continuous polymerization reactor that had been thoroughly purged with nitrogen through one supply port at a rate of 1,852 mL / hr, and 1-octene was supplied to another supply port at a rate of 585 mL / hr. A hexane solution (0.05 mmol / L, zirconium / methylaluminoxane / triisobutylaluminum molar ratio of 1 / 250 / 200) of diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride (hereinafter also referred to as "catalyst b") synthesized according to Synthesis Example 4 of WO 2006 / 025540 in contact with methylaluminoxane and triisobutylaluminum was supplied to the polymerization reactor at a rate of 82 mL / hr. Simultaneously, propylene was fed at a rate of 1340 mL / hr and hydrogen at a rate of 0.03 NL / hr through a separate feed port of the continuous polymerization reactor. Continuous solution polymerization was carried out under the following conditions: polymerization temperature 65 °C, total pressure 3.6 MPaG, residence time 15 min, and agitation speed 700 rpm. Subsequently, a methanol / hexane solution (methanol / hexane = 2 / 98 volume ratio) was added at a rate of 100 mL / hr to terminate the polymerization. The mixture was then dried under a nitrogen atmosphere at 180 °C for 30 minutes and then under vacuum for 30 minutes, producing propylene-α-olefin copolymer (A-4) at a production rate of 146 g / hr.

[0074] [Production Example 5] Production of propylene-α-olefin copolymer (A-5) Propylene-α-olefin copolymer (A-5) was produced in the same manner as in Production Example 4, except that the feed rates of dry hexane, 1-octene, and hexane solution in which catalyst b, methylaluminoxane, and triisobutylaluminum had been contacted were changed to 1737 mL / hr, 695 mL / hr, and 101 mL / hr, respectively.

[0075] [Production Example 6] Production of propylene-α-olefin copolymer (A-6) Propylene-α-olefin copolymer (A-6) was produced in the same manner as in Production Example 4, except that the feed rates of dry hexane were changed to 1552 mL / hr, 1-octene to 395 mL / hr, the feed rate of a hexane solution in which catalyst b, methylaluminoxane, and triisobutylaluminum had been in contact with each other was changed to 72 mL / hr, propylene to 1300 mL / hr, hydrogen to 0.01 Nl / hr, polymerization temperature to 74°C, and residence time to 17 min.

[0076] [Production Example 7] Production of propylene-α-olefin copolymer (A-7) Dry hexane was fed at a rate of 1,506 mL / hr through one feed port into a 950 mL continuous polymerization reactor that had been thoroughly purged with nitrogen, and 1-octene was fed at a rate of 560 mL / hr and a hexane solution of triisobutylaluminum (7.5 mmol / L) was fed at a rate of 60 mL / hr through another feed port. Simultaneously, propylene was supplied at a rate of 1180 mL / hr, hydrogen at a rate of 0.04 mL / hr, and a hexane solution (0.05 mmol / L, zirconium / methylaluminoxane = 1 / 300 molar ratio) of a metallocene catalyst (synthesized according to Synthesis Example 2 of Japanese Patent No. 6568082, hereinafter also referred to as "Catalyst c") represented by the following formula was contacted with methylaluminoxane. The hexane solution was supplied at a rate of 55 mL / hr from another supply port of the continuous polymerization reactor. Continuous solution polymerization was carried out under the conditions of a polymerization temperature of 65 °C, a total pressure of 3.6 MPaG, a residence time of 17 min, and an agitator rotation speed of 700 rpm. Subsequently, a methanol / hexane solution (methanol / hexane = 2 / 98 volume ratio) was added at a rate of 100 mL / hr to terminate the polymerization. The mixture was then dried at 180°C under a nitrogen atmosphere for 30 minutes and then under vacuum for 30 minutes to produce propylene-α-olefin copolymer (A-7) at a production rate of 219 g / hr.

[0077] [ka]

[0078] [Propylene-α-olefin copolymer for comparison] For comparison, the following propylene-α-olefin copolymers (cA-1) and (cA-2) were used. Propylene-α-olefin copolymer (cA-1): Propylene-ethylene copolymer manufactured by ExxonMobil Chemical Corporation (trade name: Vistamaxx 3980, MFR (230°C, 2.16 kg load) = 8 g / 10 min) Propylene-α-olefin copolymer (cA-2): A propylene-ethylene copolymer manufactured by ExxonMobil Chemical Corporation (trade name: Vistamaxx3000, MFR (230°C, 2.16 kg load) = 7 g / 10 min) was used.

[0079] <Physical Properties of Copolymers (A-1) to (A-7) and (cA-1) to (cA-2)> The physical properties of the copolymers (A-1) to (A-7) and (cA-1) to (cA-2) obtained in the above Production Examples were measured by the following methods. The results are shown in Table 1.

[0080] a) Propylene and α-olefin content The propylene and α-olefin contents in the copolymer were determined under the following conditions: 13 C-NMR measurement was performed and the obtained 13 It was calculated by analyzing the C-NMR spectrum. In this specification, the content of structural units derived from α-olefins is also referred to as the “α-olefin content.” Equipment: Bruker BioSpin AVANCE III cryo-500 nuclear magnetic resonance spectrometer Measurement nuclei: 13 C(125MHz) Measurement mode: Single pulse proton broadband decoupling Pulse width: 45° (5.00 μsec) Number of points: 64k Measurement range: 250 ppm (-55 to 195 ppm) Repeat time: 5.5 seconds Accumulation count: 64 times Measurement solvent: orthodichlorobenzene / benzene-d6 (4 / 1 [v / v]) Sample concentration: ca. 60 mg / 0.6 mL Measurement temperature: 120℃ Window function: exponential (BF: 1.0 Hz) Chemical shift reference: CH3(P)mmmm signal (21.59 ppm)

[0081] b) Isotactic triad fraction (mm fraction) In an orthodichlorobenzene / benzene-d6 (4 / 1 [v / v]) solution (CH3(P)mmmm signal: 21.59 ppm as reference) 13 C-NMR measurement was performed and the obtained 13The ratio (%) of the area of ​​the peak appearing between 21.0 and 22.2 ppm to the total area (100%) of the peaks appearing between 19.2 and 22.2 ppm in the C-NMR spectrum was calculated, and the ratio (%) of the area of ​​the peak was defined as the mm fraction.

[0082] c) MFR The MFR of the copolymer was measured at 230°C under a load of 2.16 kg in accordance with ASTM D1238E.

[0083] d) Intrinsic viscosity [η] The intrinsic viscosity [η] of the copolymer was measured at 135°C using decalin as a solvent.

[0084] e) Melting point Tm, heat of fusion ΔH Using a hydraulic heat press molding machine set at 200°C, the copolymer was heated for 6 minutes, molded under a pressure of 10 MPa for 2 minutes, and then cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a 500 μm thick sheet (test piece). After 72 hours at room temperature from molding, a test piece weighing approximately 10 mg was cooled in a nitrogen atmosphere from 20°C to -20°C at a rate of 10°C / min and held at that temperature for 5 minutes. The test piece was then heated to 200°C at a rate of 10°C / min and held at that temperature for 10 minutes. The test piece was then cooled to -100°C at a rate of 10°C / min and held at that temperature for 5 minutes. The test piece was then heated to 200°C at a rate of 10°C / min. The heat of fusion ΔH was calculated from the integrated value of the crystalline melting peak when the temperature was raised for the first time. The melting point Tm was taken as the temperature at the peak apex of the crystalline melting peak when the temperature was raised for the second time. When two or more melting peaks were observed, the highest temperature among the peak apex temperatures of these peaks was taken as the melting point.

[0085] f) Tensile modulus, breaking stress Using a hydraulic hot press molding machine set at 200°C, the copolymer was heated for 6 minutes, molded under a pressure of 10 MPa for 2 minutes, and then cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a 2 mm thick sheet. After 72 hours at room temperature from molding, 5A-type dumbbells as specified in JIS K 7161-2:2014 were made from the obtained sheet in accordance with ASTM D638, and the tensile modulus and breaking stress of the dumbbells were measured under conditions of 23°C and a pulling rate of 50 mm / min.

[0086] g) Shore A hardness (instantaneous value) Using a hydraulic hot press molding machine set at 200°C, the copolymer was heated for 6 minutes, molded under a pressure of 10 MPa for 2 minutes, and then cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a 2 mm thick sheet. After 72 hours had passed at room temperature from molding, a durometer hardness tester (Type A) was used, and the indenter was brought into contact with a test piece consisting of three stacked sheets, and the scale was immediately read (in accordance with ASTM D2240).

[0087] h) Shore D hardness (instantaneous value) Using a hydraulic hot press molding machine set at 200°C, the copolymer was heated for 6 minutes, molded under a pressure of 10 MPa for 2 minutes, and then cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a 2 mm thick sheet. After 72 hours had passed at room temperature from molding, a durometer hardness tester (D type) was used, and the indenter was brought into contact with a test piece consisting of three stacked sheets, and the scale was immediately read (in accordance with ASTM D2240).

[0088] [Table 1]

[0089] [Examples 1 to 7 and Comparative Examples 1 to 2] The raw materials shown in the composition in Table 2 were placed in a Laboplastomill (manufactured by Toyo Seiki Seisakusho, Ltd.) in the amounts (mass%) shown in Table 2, and kneaded for 5 minutes at 200°C and 60 rpm to prepare a propylene-based resin composition. The propylene polymers (B-1) used in the examples and comparative examples are as follows: Propylene polymer (B-1): Random polypropylene (Prime Polymer Co., Ltd., Prime Polypro F227, MFR (230°C, 2.16 kg load) = 7 g / 10 min, melting point = 150°C, mmmm fraction = 96%)

[0090] The tensile modulus, breaking stress, and Shore D hardness (instantaneous value) were measured in the same manner as above, except that the obtained propylene-based resin composition was used. The results are shown in Table 2.

[0091] <Whitening resistance> The obtained propylene-based resin composition was heated for 6 minutes using a hydraulic hot press molding machine set at 200°C, then molded under a pressure of 10 MPa for 2 minutes, and then cooled at 20°C under a pressure of 10 MPa for 2 minutes to produce a sheet with a thickness of 500 μm. After 72 hours at room temperature from molding, a No. 2 dumbbell shape as specified in JIS K 6251 was made from the obtained sheet and stretched 15 mm at a tensile speed of 50 mm / min. The hue (L value) before and after stretching was measured using a spectrophotometer (CM-3700d, manufactured by Konica Minolta, Inc.), and the hue change (ΔL) was calculated based on the following formula. A smaller ΔL value indicates better whitening resistance. ΔL = L value (after stretching) - L value (before stretching)

[0092] [Table 2]

Claims

1. 1 to 99% by mass of a propylene / α-olefin copolymer (A) satisfying the following requirements (I) to (V): A propylene-based resin composition comprising 1 to 99% by mass of a propylene-based polymer (B) other than the copolymer (A), the propylene-based polymer (B) having an MFR of 0.1 to 500 g / 10 min at 230°C under a load of 2.16 kg, as measured in accordance with ASTM D1238E (where the total of the copolymer (A) and the polymer (B) is taken as 100% by mass). (I) When the total of the structural unit (i) derived from propylene and the structural unit (ii) derived from an α-olefin having 5 to 20 carbon atoms is taken as 100 mol %, the content of the structural unit (i) is more than 85 mol % and not more than 95 mol %, and the content of the structural unit (ii) is 5 mol % or more and less than 15 mol %. (II) The melting point measured by differential scanning calorimetry (DSC) is 95°C or less or not observed. (III) １３ The isotactic triad fraction measured by C-NMR is 85% or more. (IV) The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 10 dl / g. (V) The α-olefin having 5 to 20 carbon atoms is at least one selected from 1-hexene, 1-octene, 1-decene, and 1-dodecene.

2. The copolymer (A), １３ 2. The propylene-based resin composition according to claim 1, wherein the isotactic triad fraction measured by C-NMR is 90% or more.

3. 3. The propylene-based resin composition according to claim 1, wherein the copolymer (A) has an MFR of 0.1 to 30 g / 10 min at 230°C under a load of 2.16 kg, as measured in accordance with ASTM D1238E.

4. An adhesive resin composition comprising the propylene-based resin composition according to any one of claims 1 to 3.

5. A pellet comprising the propylene-based resin composition according to any one of claims 1 to 3 or the adhesive resin composition according to claim 4.

6. A molded article comprising the propylene-based resin composition according to any one of claims 1 to 3 or the adhesive resin composition according to claim 4.

7. An unstretched film comprising the propylene-based resin composition according to any one of claims 1 to 3 or the adhesive resin composition according to claim 4.

8. A sheet comprising the propylene-based resin composition according to any one of claims 1 to 3 or the adhesive resin composition according to claim 4.

9. An injection-molded article comprising the propylene-based resin composition according to any one of claims 1 to 3 or the adhesive resin composition according to claim 4.

10. A blow-molded article comprising the propylene-based resin composition according to any one of claims 1 to 3 or the adhesive resin composition according to claim 4.

11. An automobile part selected from interior and exterior parts, comprising the propylene-based resin composition according to any one of claims 1 to 3 or the adhesive resin composition according to claim 4.

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