Propylene resin composition, molded article, and method for producing molded article

Abstract

To provide a propylene resin composition which yields a molded article having a relatively low weld height while enabling the reuse of polypropylene; a molded article; and a method for producing the molded article.SOLUTION: A propylene resin composition includes a recycled propylene composition (A) and a virgin heterophasic propylene polymer material (B), wherein the virgin heterophasic propylene polymer material (B) has a weight-average molecular weight of 200,000 or more and less than 500,000, the ratio of [η]CXS to [η]CXIS is less than 6.0, and the virgin heterophasic propylene polymer material (B) has a melt flow rate (MFR) of 5 g / 10 min or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a propylene resin composition, a molded article, and a method for producing the molded article. [Background technology]

[0002] Conventionally, polypropylene has been widely used in automobile parts (for example, exterior parts such as bumpers, and interior parts such as door trims and instrument panels), housings for household electrical appliances, etc. Polypropylene molded articles used in the market are collected and reused as raw materials for plastic products.

[0003] As a method for obtaining a propylene resin composition, which is a reusable raw material, by using molded polypropylene bodies collected from the market, for example, Patent Document 1 discloses a resin composition obtained by heating and melting crushed car bumpers, crystalline polypropylene, an elastomer, an inorganic filler, and a light-shielding pigment. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-139421 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the resin composition described in Patent Document 1 has a problem in that, when the resin composition is melt-kneaded and then injection-molded, streaky lines with high irregularities, called welds, occur on the surface of the molded product at the points where the resin flows within the mold join.

[0006] As described above, if the weld height generated on the surface of the molded article is high, it will cause a poor appearance of the final product, and therefore molded articles with low weld height are desired.

[0007] Therefore, an object of the present invention is to provide a propylene resin composition that allows for the production of a molded article having a relatively low weld height while still allowing for the reuse of polypropylene, a molded article, and a method for producing the molded article. [Means for solving the problem]

[0008] The propylene resin composition according to the present invention comprises: A recycled propylene composition (A), and (B) a virgin heterophasic propylene polymerization material, The virgin heterophasic propylene polymerization material (B) has a weight average molecular weight of 200,000 or more and less than 500,000, and the ratio of [η]CXS to [η]CXIS is less than 6.0; The virgin heterophasic propylene polymer material (B) has a melt flow rate (MFR) of 5 g / 10 min or more.

[0009] The molded body according to the present invention is The propylene resin composition includes the propylene resin composition described above.

[0010] The method for producing a molded body according to the present invention includes the steps of: A step of mixing pellets containing a recycled propylene composition (A) with pellets containing a virgin heterophasic propylene polymerization material (B) to obtain a mixture; and molding the mixture using a molding machine to obtain a molded body, The virgin heterophasic propylene polymerization material (B) has a weight average molecular weight of 200,000 or more and less than 500,000, and the ratio of [η]CXS to [η]CXIS is less than 6.0; The virgin heterophasic propylene polymer material (B) has a melt flow rate (MFR) of 5 g / 10 min or more. [Effects of the Invention]

[0011] According to the present invention, there are provided a propylene resin composition, a molded article, and a method for producing a molded article, which are capable of producing a molded article having a relatively low weld height while recycling polypropylene. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0013] [Propylene resin composition] The propylene resin composition according to this embodiment includes a recycled propylene composition (A) and a virgin heterophasic propylene polymer material (B). In this specification, "recycled xxx" refers to a material that has been processed, such as molded, or used for some end use, and then recovered and reused. "Virgin xxx" refers to a material that has not been molded into a product such as an automobile or a part thereof, and has not been used for some end use.

[0014] <Recycled Propylene Composition (A)> The recycled propylene composition (A) may be a recycled propylene composition recovered from the market, or may be a recycled propylene composition recovered in-process.

[0015] The recycled propylene composition recovered from the market is derived from polypropylene molded articles used in the market. The recycled propylene composition recovered in a process is derived from the propylene material generated in the process of producing a polypropylene molded article, and the resulting molded article. Examples of polypropylene molded articles include automobile parts, packaging containers (e.g., food retort pouches, refill pouches, detergent bottles), housings for household electrical appliances, office supplies (e.g., trays), and household commodities (e.g., contact lens cases). Examples of automobile parts include automobile interior parts (e.g., instrument panels, door trims), automobile exterior parts (e.g., bumpers), and other automobile parts (e.g., battery cases). In one embodiment, the recycled propylene composition (A) is derived at least in part from materials recovered from automobile parts.

[0016] The content of the recycled propylene composition (A) is preferably 20% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 60% by mass or less, and even more preferably 30% by mass or more and 50% by mass or less, relative to the total mass of the propylene resin composition (100% by mass).

[0017] From the viewpoint of improving the molding processability of the propylene resin composition, the melt flow rate (MFR) of the recycled propylene composition (A) is preferably 0.1 g / 10 min or more, more preferably 1 g / 10 min or more and 300 g / 10 min or less. The melt flow rate (MFR) of the recycled propylene composition (A) may be 5 g / 10 min or more and 100 g / 10 min or less, or 10 g / 10 min or more and 50 g / 10 min or less.

[0018] The melt flow rate (MFR) is measured by Method A under conditions of a temperature of 230°C and a load of 2.16 kg in accordance with the method specified in JIS K7210-1995.

[0019] The recycled propylene composition (A) according to the present embodiment may contain ash. The ash content refers to components remaining as ash after heating the recycled propylene composition (A) at 600°C for 60 minutes. The ash content can be determined by the following method.

[0020] (Method for measuring ash content) The crucible is heated at 600°C for 60 minutes using an electric furnace, removed and cooled in a desiccator for 1 hour, and then weighed on a precision balance. 10 g of recycled propylene composition (A) is weighed into the crucible and heated at 600°C for 60 minutes using an electric furnace to completely incinerate it. The crucible is then cooled in a desiccator for 1 hour, after which the weight of the ash is measured to the nearest 0.1 mg using a precision balance, and the ash content (mass%) relative to the recycled propylene composition (A) is calculated.

[0021] The ash content of the recycled propylene composition (A) is preferably 1% by mass or more, more preferably 5% by mass or more, based on 100% by mass of the total mass of the recycled propylene composition (A). The ash content is preferably 50% by mass or less, more preferably 30% by mass or less, based on 100% by mass of the total mass of the recycled propylene composition (A).

[0022] The recycled propylene composition (A) may contain a filler. When the recycled propylene composition (A) contains a filler, the content of the filler is considered to roughly correspond to the ash content of the recycled propylene composition (A).

[0023] The recycled propylene composition (A) contains a propylene polymer. The propylene polymer is a polymer containing more than 50% by mass of monomer units derived from propylene. Examples of the propylene polymer include a propylene homopolymer, a random copolymer of propylene and a monomer other than propylene, and a heterophasic propylene polymer material. The recycled propylene composition (A) may contain only one type of propylene polymer, or may contain two or more types of propylene polymers.

[0024] (propylene homopolymer) The propylene homopolymer has an intrinsic viscosity ([η]) of preferably 0.10 dL / g or more and 4.00 dL / g or less, more preferably 0.50 dL / g or more and 3.00 dL / g or less, and even more preferably 0.70 dL / g or more and 2.00 dL / g or less, from the viewpoint of improving the fluidity of the propylene resin composition when melted and the toughness of the molded product.

[0025] In this specification, the intrinsic viscosity (unit: dL / g) is a value measured at a temperature of 135°C using tetralin as a solvent by the following method.

[0026] Using an Ubbelohde viscometer, the reduced viscosity is measured at three concentrations: 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL. The reduced viscosity is plotted against the concentration, and the intrinsic viscosity is calculated by extrapolation, extrapolating the concentration to zero. The method for calculating the intrinsic viscosity using the extrapolation method is described, for example, on page 491 of "Polymer Solutions, Polymer Experiments 11" (published by Kyoritsu Shuppan Co., Ltd. in 1982).

[0027] The propylene homopolymer has a molecular weight distribution (Mw / Mn) of preferably 3.0 or more, more preferably 4.0 or more. The propylene homopolymer has a molecular weight distribution of preferably 15.0 or less, more preferably 10.0 or less. The propylene homopolymer has a molecular weight distribution of preferably 3.0 or more and 15.0 or less, more preferably 4.0 or more and 10.0 or less.

[0028] In this specification, the molecular weight distribution refers to the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), calculated using the weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) under the following conditions: Equipment: Tosoh Corporation HLC-8121 GPC / HT Separation column: Tosoh Corporation GMHHR-H(S)HT (3 columns) Measurement temperature: 140℃ Carrier: Orthodichlorobenzene Flow rate: 1.0mL / min Sample concentration: approximately 1 mg / mL Sample injection volume: 400 μL Detector: Differential refraction Calibration curve creation method: Standard polystyrene is used

[0029] The propylene homopolymer can be produced, for example, by carrying out a polymerization step in which propylene is polymerized using a polymerization catalyst.

[0030] Examples of the polymerization catalyst include Ziegler catalysts; Ziegler-Natta catalysts; catalysts containing a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; catalysts containing a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound; and modified catalysts in which a catalyst component (a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that forms an ionic complex, an organoaluminum compound, etc.) is supported on inorganic particles (silica, clay minerals, etc.).

[0031] Examples of the polymerization catalyst include catalysts described in JP-A-61-218606, JP-A-5-194685, JP-A-7-216017, JP-A-9-316147, JP-A-10-212319, JP-A-2004-182981, JP-A-2010-168545, and JP-A-2011-246699.

[0032] Furthermore, a polymer obtained by prepolymerizing propylene in the presence of the above polymerization catalyst can also be used as the polymerization catalyst.

[0033] Examples of polymerization methods include bulk polymerization, solution polymerization, and gas phase polymerization. Here, bulk polymerization refers to a method in which polymerization is carried out using an olefin that is liquid at the polymerization temperature as a medium. Solution polymerization refers to a method in which polymerization is carried out in an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, or octane. Gas phase polymerization refers to a method in which gaseous monomers are used as a medium and the gaseous monomers are polymerized in the medium.

[0034] The polymerization method may be, for example, a batch method, a continuous method, or a combination thereof. The polymerization method may be a multi-stage method in which a plurality of polymerization reactors are connected in series.

[0035] From the viewpoint of industrial and economical excellence, the polymerization method is preferably a continuous gas phase polymerization method or a bulk-gas phase polymerization method in which bulk polymerization and gas phase polymerization are carried out continuously.

[0036] Various conditions in the polymerization step (polymerization conditions such as polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, and polymerization time) may be appropriately determined depending on the molecular structure of the target polymer.

[0037] In the method for producing a propylene homopolymer, other steps may be carried out before or after the polymerization step. For example, after the polymerization step, the polymer may be dried at a temperature equal to or lower than the melting point of the polymer, as necessary, to remove residual solvent contained in the polymer and ultralow molecular weight oligomers produced as by-products during the production. Examples of drying methods include those described in JP-A-55-75410 and JP-A-2565753.

[0038] (Random copolymer of propylene and a monomer other than propylene) The random copolymer of propylene and a monomer other than propylene contains monomer units derived from propylene and monomer units derived from a monomer other than propylene, and preferably contains 0.01% by mass or more and 20% by mass or less of the monomer units derived from a monomer other than propylene, relative to 100% by mass of the total mass of the copolymer.

[0039] Examples of monomers other than propylene include ethylene and α-olefins having 4 to 12 carbon atoms. In this specification, α-olefins are aliphatic unsaturated hydrocarbons having a carbon-carbon unsaturated double bond at the α-position. Examples of α-olefins having 4 to 12 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 4-methyl-1-hexene.

[0040] The monomer other than propylene is preferably at least one selected from the group consisting of ethylene and α-olefins having 4 to 10 carbon atoms, more preferably at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, and 1-octene, and even more preferably at least one selected from the group consisting of ethylene and 1-butene.

[0041] Examples of random copolymers of propylene and a monomer other than propylene include propylene-ethylene random copolymers, propylene-1-butene random copolymers, propylene-1-hexene random copolymers, propylene-1-octene random copolymers, propylene-ethylene-1-butene random copolymers, propylene-ethylene-1-hexene random copolymers, and propylene-ethylene-1-octene random copolymers.

[0042] The random copolymer of propylene and a monomer other than propylene has an intrinsic viscosity ([η]) of preferably 0.10 dL / g or more and 4.00 dL / g or less, more preferably 0.50 dL / g or more and 3.00 dL / g or less, and even more preferably 0.70 dL / g or more and 2.00 dL / g or less, from the viewpoint of improving the fluidity of the propylene resin composition when melted.

[0043] The random polymer of propylene and a monomer other than propylene has a molecular weight distribution (Mw / Mn) of preferably 3.0 or more, more preferably 4.0 or more. The molecular weight distribution is preferably 10.0 or less, more preferably 7.0 or less. The molecular weight distribution of the random polymer of propylene and a monomer other than propylene is preferably 3.0 or more and 10.0 or less, more preferably 4.0 or more and 7.0 or less.

[0044] A random copolymer of propylene and a monomer other than propylene can be produced, for example, by polymerizing propylene and a monomer other than propylene in accordance with the polymerization catalyst, polymerization method, polymerization system, and polymerization conditions that can be used in the production of the above-mentioned propylene homopolymer.

[0045] (Heterophasic propylene polymerized material) The heterophasic propylene polymer material is a mixture containing a polymer I containing 80% by mass or more of monomer units derived from propylene (where the total mass of the polymer I is taken as 100% by mass), and a polymer II containing monomer units derived from at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms and monomer units derived from propylene.

[0046] The heterophasic propylene polymer material can be produced, for example, by carrying out a first polymerization step of polymerizing polymer I and a second polymerization step of polymerizing polymer II. These polymerization steps can be carried out using the same polymerization catalyst, polymerization method, polymerization system, and polymerization conditions as those usable in the production of the above-mentioned propylene homopolymer.

[0047] The heterophasic propylene polymer material may be such that the sum of polymer I and polymer II contained in the heterophasic propylene polymer material is 100% by mass relative to the total mass of the heterophasic propylene polymer material (100% by mass).

[0048] As described above, polymer I contains 80% by mass or more of monomer units derived from propylene (where the total mass of polymer I is 100% by mass). Polymer I may be, for example, a propylene homopolymer, or may contain monomer units derived from a monomer other than propylene. When polymer I contains monomer units derived from a monomer other than propylene, the content of such units may be, for example, 0.01% by mass or more and less than 20% by mass, relative to the total mass of polymer I (100% by mass).

[0049] Examples of the monomer other than propylene include ethylene and α-olefins having 4 or more carbon atoms. Examples of the α-olefins having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 4-methyl-1-hexene.

[0050] The monomer other than propylene is preferably at least one selected from the group consisting of ethylene and α-olefins having 4 to 10 carbon atoms, more preferably at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, and 1-octene, and even more preferably at least one selected from the group consisting of ethylene and 1-butene.

[0051] Examples of polymer I containing monomer units derived from a monomer other than propylene include propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene copolymer.

[0052] From the viewpoint of improving the dimensional stability of the molded article, polymer I is preferably a propylene homopolymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-ethylene-1-butene copolymer, and more preferably a propylene homopolymer.

[0053] The isotactic pentad fraction of Polymer I is preferably 1.000 or less, and may be, for example, 0.998 or less, 0.995 or less, 0.990 or less, or 0.985 or less. The lower limit of the isotactic pentad fraction is not particularly limited, and may be, for example, 0.900 or more, 0.925 or more, 0.930 or more, 0.961 or more, 0.965 or more, or 0.968 or more.

[0054] The content of polymer I is preferably 50% by mass or more and 99% by mass or less, and more preferably 60% by mass or more and 95% by mass or less, relative to the total mass (100% by mass) of the heterophasic propylene polymer material.

[0055] As described above, polymer II contains monomer units derived from at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms, and monomer units derived from propylene. Examples of α-olefins having 4 to 12 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 4-methyl-1-hexene.

[0056] Polymer II preferably contains 30% by mass or more of monomer units derived from at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms, and also contains monomer units derived from propylene (where the total mass of Polymer II is taken as 100% by mass).

[0057] In Polymer II, the content of monomer units derived from at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms may be 30% by mass or more and 70% by mass or less, or 35% by mass or more and 60% by mass or less (where the total mass of Polymer II is taken as 100% by mass).

[0058] In Polymer II, the at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms is preferably at least one selected from the group consisting of ethylene and α-olefins having 4 to 10 carbon atoms, more preferably at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, 1-octene, and 1-decene, and even more preferably at least one selected from the group consisting of ethylene and 1-butene.

[0059] Examples of polymer II include propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, propylene-ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-1-decene copolymer, etc. Among these, polymer II is preferably a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-ethylene-1-butene copolymer, and more preferably a propylene-ethylene copolymer.

[0060] The content of polymer II is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, relative to the total mass (100% by mass) of the heterophasic propylene polymer material.

[0061] In the heterophasic propylene polymerization material, the content of monomer units derived from at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms may be 0.3% by mass or more and 35% by mass or less, or 0.7% by mass or more and 24% by mass or less (where the total mass of the heterophasic propylene polymerization material is 100% by mass).

[0062] The content of xylene-insoluble components (CXIS components) in the heterophasic propylene polymerization material (hereinafter also referred to as "CXIS amount") is preferably 50% by mass or more and 99% by mass or less, and more preferably 60% by mass or more and 95% by mass or less, relative to 100% by mass of the total mass of the heterophasic propylene polymerization material.

[0063] The content of xylene soluble components (CXS components) in the heterophasic propylene polymerization material (hereinafter also referred to as "CXS amount") is preferably 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 40% by mass or less, relative to the total mass of the heterophasic propylene polymerization material (100% by mass).

[0064] In this specification, the xylene-insoluble component (CXIS component) refers to a component contained in a polymer that is insoluble in p-xylene and is a solid obtained by the following method: A method in which about 2 g of the polymer is dissolved in boiling p-xylene for 2 hours to obtain a solution, and then the solution is cooled to 20°C to precipitate a solid.

[0065] In this specification, the xylene soluble component (CXS component) means a component other than the "CXIS component" in the polymer.

[0066] In this specification, the amounts of CXIS and CXS can be determined by the following method.

[0067] Weigh out 4 g of the sample and reflux it in boiling xylene for 5 hours using a cylindrical filter paper and a Soxhlet extraction tube. The extract is then concentrated under reduced pressure using a rotary evaporator to obtain a polymer component. Weigh the resulting polymer component (hereafter, "weight of polymer component" will be referred to as "a"). Weigh out 2 g of polymer component a and heat-dissolve it in boiling xylene for 2 hours. After cooling to 20°C, filter it using filter paper. The filtrate is concentrated under reduced pressure using a rotary evaporator to obtain a CXS component. Weigh the resulting CXS component (hereafter, "weight of CXS component" will be referred to as "b"). The amounts of CXIS and CXS in the sample are calculated using the values ​​a and b according to the following formula. The solid remaining on the filter paper is then vacuum-dried to obtain the CXIS component. The resulting CXIS component is used to evaluate the molecular weight distribution. CXS amount (mass%)=(b / a)×100 CXIS amount (mass%) = 100-CXS amount (mass%)

[0068] In this embodiment, it is considered that the CXIS component in the heterophasic propylene polymer material is mainly composed of polymer I, and the CXS component in the heterophasic propylene polymer material is mainly composed of polymer II.

[0069] Examples of heterophasic propylene polymer materials include (propylene)-(propylene-ethylene) polymer materials, (propylene)-(propylene-ethylene-1-butene) polymer materials, (propylene)-(propylene-ethylene-1-hexene) polymer materials, (propylene)-(propylene-ethylene-1-octene) polymer materials, (propylene)-(propylene-1-butene) polymer materials, (propylene)-(propylene-1-hexene) polymer materials, (propylene)-(propylene-1-octene) polymer materials, and (propylene)-(propylene-1-decene) polymer materials. materials, (propylene-ethylene)-(propylene-ethylene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-hexene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-octene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-decene) polymerization materials, (propylene-ethylene)-(propylene-1-butene) polymerization materials, (propylene-ethylene)-(propylene-1-hexene) polymerization materials, (propylene-ethylene) (propylene)-(propylene-1-octene) polymerization materials, (propylene-ethylene)-(propylene-1-decene) polymerization materials, (propylene-1-butene)-(propylene-ethylene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-butene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-hexene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-octene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-decene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-decene) polymerization materials, (propylene-1-butene)-( (propylene-1-butene) polymerization materials, (propylene-1-butene)-(propylene-1-hexene) polymerization materials, (propylene-1-butene)-(propylene-1-octene) polymerization materials, (propylene-1-butene)-(propylene-1-decene) polymerization materials, (propylene-1-hexene)-(propylene-1-hexene) polymerization materials, (propylene-1-hexene)-(propylene-1-octene) polymerization materials, (propylene-1-hexene)-(propylene-1-decene) polymerization materials, (propylene-1-octene)-(propylene-1-octene) polymerization materials,(propylene-1-octene)-(propylene-1-decene) polymer materials, etc.

[0070] Here, the expression "(propylene)-(propylene-ethylene) polymer material" means "a heterophasic propylene polymer material in which polymer I is a propylene homopolymer and polymer II is a propylene-ethylene copolymer." The same applies to other similar expressions.

[0071] The heterophasic propylene polymeric material is preferably a (propylene)-(propylene-ethylene) polymeric material, a (propylene)-(propylene-ethylene-1-butene) polymeric material, a (propylene-ethylene)-(propylene-ethylene) polymeric material, a (propylene-ethylene)-(propylene-ethylene-1-butene) polymeric material, or a (propylene-1-butene)-(propylene-1-butene) polymeric material, and more preferably a (propylene)-(propylene-ethylene) polymeric material.

[0072] The molecular weight distribution (Mw(I) / Mn(I)) of Polymer I is preferably 3.0 or more, and more preferably 4.0 or more.

[0073] The molecular weight distribution of the CXIS component (Mw(CXIS) / Mn(CXIS)) is preferably 3.0 or more, and more preferably 4.0 or more.

[0074] The amount of CXIS in the recycled propylene composition (A) is preferably 50% by mass or more and 99% by mass or less, more preferably 60% by mass or more and 95% by mass or less, relative to 100% by mass of the total mass of the recycled propylene composition (A).

[0075] The amount of CXS in the recycled propylene composition (A) is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, relative to 100% by mass of the total mass of the recycled propylene composition (A).

[0076] <Virgin heterophasic propylene polymer material (B)> In the virgin heterophasic propylene polymer material (B), the heterophasic propylene polymer material is the same as the heterophasic propylene polymer material in the recycled propylene composition (A). The virgin heterophasic propylene polymer material (B) has a weight average molecular weight of 200,000 or more and less than 500,000, preferably 220,000 or more and 450,000 or less, and more preferably 250,000 or more and 410,000 or less.

[0077] In the present specification, the weight average molecular weight (Mw) of the virgin heterophasic propylene polymer material can be measured by gel permeation chromatography (GPC) under the following conditions. Equipment: Tosoh Corporation HLC-8121 GPC / HT Separation column: Tosoh Corporation GMHHR-H(S)HT (3 columns) Measurement temperature: 140℃ Carrier: Orthodichlorobenzene Flow rate: 1.0mL / min Sample concentration: approximately 1 mg / mL Sample injection volume: 400 μL Detector: Differential refraction Calibration curve creation method: Standard polystyrene is used

[0078] The virgin heterophasic propylene polymer material (B) has a melt flow rate (MFR) of 5 g / 10 min or more, preferably 10 g / 10 min or more, and more preferably 12 g / 10 min or more, from the viewpoint of improving the molding processability of the propylene resin composition. The virgin heterophasic propylene polymer material (B) has a melt flow rate (MFR) of 100 g / 10 min or less, more preferably 80 g / 10 min or less, and even more preferably 50 g / 10 min or less, from the viewpoint of the impact resistance of the molded product.

[0079] The melt flow rate (MFR) is measured by Method A under conditions of a temperature of 230°C and a load of 2.16 kg in accordance with the method specified in JIS K7210-1995.

[0080] In the virgin heterophasic propylene polymer material, the intrinsic viscosity ([η]I) of polymer I is preferably 0.10 dL / g or more and 4.00 dL / g or less, more preferably 0.50 dL / g or more and 3.00 dL / g or less, and even more preferably 0.70 dL / g or more and 2.00 dL / g or less.

[0081] In the virgin heterophasic propylene polymer material, the intrinsic viscosity ([η]II) of polymer II is preferably 1.00 dL / g or more and 10.00 dL / g or less, more preferably 2.00 dL / g or more and 10.00 dL / g or less, and even more preferably 2.00 dL / g or more and 9.00 dL / g or less.

[0082] The ratio ([η]II / [η]I) of the intrinsic viscosity ([η]II) of polymer II to the intrinsic viscosity ([η]I) of polymer I is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less.

[0083] The intrinsic viscosity ([η]I) of polymer I can be measured, for example, by extracting polymer I from a reactor in which polymer I is polymerized and measuring the intrinsic viscosity of the polymer.

[0084] The intrinsic viscosity ([η]II) of polymer II can be calculated, for example, by the following formula (i) using the intrinsic viscosity ([η]Total) of the virgin heterophasic propylene polymerization material, the intrinsic viscosity ([η]I) of polymer I, and the contents of polymer II and polymer I.

[0085] [η]II=([η]Total-[η]I×XI) / XII ···(i) [η]Total: Intrinsic viscosity (dL / g) of virgin heterophasic propylene polymer material (B) [η]I: Intrinsic viscosity of polymer I (dL / g) XI: Ratio of the mass of polymer I to the total mass of virgin heterophasic propylene polymer material (mass of polymer I / mass of virgin heterophasic propylene polymer material) XII: Ratio of the mass of polymer II to the total mass of virgin heterophasic propylene polymer material (mass of polymer II / mass of virgin heterophasic propylene polymer material)

[0086] Here, XI and XII can be determined from the material balance during polymerization.

[0087] XII may be calculated using the following formula by measuring the heat of fusion of polymer I and the heat of fusion of the virgin heterophasic propylene polymer material. XII=1-(ΔHf)T / (ΔHf)P (ΔHf)T: Heat of fusion of virgin heterophasic propylene polymer material (J / g) (ΔHf)P: Heat of fusion of polymer I (J / g)

[0088] The intrinsic viscosity ([η]CXS) of the xylene soluble component (CXS component) of the virgin heterophasic propylene polymerization material (B) is preferably 5.00 dL / g or more and 9.00 dL / g or less, more preferably 5.50 dL / g or more and 8.00 dL / g or less, and even more preferably 6.00 dL / g or more and 7.00 dL / g or less.

[0089] The intrinsic viscosity ([η]CXIS) of the xylene-insoluble component (CXIS component) of the virgin heterophasic propylene polymerization material (B) is preferably 0.50 dL / g or more and 2.00 dL / g or less, more preferably 0.70 dL / g or more and 1.80 dL / g or less, and even more preferably 0.90 dL / g or more and 1.60 dL / g or less.

[0090] The ratio of [η]CXS to [η]CXIS ([η]CXS / [η]CXIS) of the virgin heterophasic propylene polymerization material (B) is less than 6.0, preferably 3.0 or more and less than 6.0, more preferably 3.5 or more and 5.8 or less, and even more preferably 4.0 or more and 5.6 or less.

[0091] The intrinsic viscosity (unit: dL / g) can be measured by the method described above.

[0092] The amount of CXS in the virgin heterophasic propylene polymerization material (B) is preferably 15% by mass or more and 30% by mass or less, more preferably 16% by mass or more and 28% by mass or less, and even more preferably 17% by mass or more and 26% by mass or less, based on 100% by total mass of the virgin heterophasic propylene polymerization material (B).

[0093] The amount of CXS can be determined by the method described above.

[0094] The content of the virgin heterophasic propylene polymer material (B) is preferably 1% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 12% by mass or less, and even more preferably 5% by mass or more and 10% by mass or less, relative to the total mass of the propylene resin composition (100% by mass).

[0095] In one aspect of the propylene resin composition according to this embodiment, the virgin heterophasic propylene polymerization material (B) has an [η]CXS of 5.00 dL / g or more and 9.00 dL / g or less, an [η]CXIS of 0.50 dL / g or more and 2.00 dL / g or less, a ratio of [η]CXS to [η]CXIS of the virgin heterophasic propylene polymerization material (B) of 3.0 or more and less than 6.0, and the amount of CXS in the virgin heterophasic propylene polymerization material (B) is 15 mass% or more and 30 mass% or less, relative to the total mass of the virgin heterophasic propylene polymerization material (B) (100%).

[0096] <Virgin heterophasic propylene polymer material (C)> In one embodiment, the propylene resin composition according to the present embodiment further contains a virgin heterophasic propylene polymer material (C). In the virgin heterophasic propylene polymer material (C), the heterophasic propylene polymer material is the same as the heterophasic propylene polymer material in the recycled propylene composition (A) described above.

[0097] The virgin heterophasic propylene polymerization material (C) is preferably at least one selected from the group consisting of virgin heterophasic propylene polymerization material (C1) having a weight-average molecular weight of less than 200,000, virgin heterophasic propylene polymerization material (C2) having a weight-average molecular weight of 500,000 or more, and virgin heterophasic propylene polymerization material (C3) having a weight-average molecular weight of 200,000 or more but less than 500,000 and a ratio of [η]CXS to [η]CXIS of 6.0 or more, and more preferably virgin heterophasic propylene polymerization material (C1) having a weight-average molecular weight of less than 200,000 or virgin heterophasic propylene polymerization material (C2) having a weight-average molecular weight of 500,000 or more.

[0098] The virgin heterophasic propylene polymer material (C1) may have a weight average molecular weight of 100,000 or more and less than 200,000. The virgin heterophasic propylene polymer material (C2) may have a weight average molecular weight of 500,000 or more and 1,000,000 or less. The weight average molecular weight of the virgin heterophasic propylene polymer material (C) can be calculated by the above-mentioned measurement method.

[0099] The content of the virgin heterophasic propylene polymer material (C) is preferably 15% by mass or more and 79% by mass or less, more preferably 20% by mass or more and 60% by mass or less, and even more preferably 25% by mass or more and 55% by mass or less, based on 100% by mass of the total mass of the propylene resin composition.

[0100] From the viewpoint of improving the molding processability of the propylene resin composition, the virgin heterophasic propylene polymer material (C) preferably has a melt flow rate (MFR) of 0.1 g / 10 min or more, more preferably 1 g / 10 min or more and 300 g / 10 min or less. The virgin heterophasic propylene polymer material (C) may have a melt flow rate (MFR) of 5 g / 10 min or more and 100 g / 10 min or less, or 10 g / 10 min or more and 50 g / 10 min or less.

[0101] The melt flow rate (MFR) is measured by Method A under conditions of a temperature of 230°C and a load of 2.16 kg in accordance with the method specified in JIS K7210-1995.

[0102] In one aspect of the propylene resin composition of this embodiment, the content of the recycled propylene composition (A) is 20% by mass or more and 80% by mass or less, the content of the virgin heterophasic propylene polymerization material (B) is 1% by mass or more and 20% by mass or less, and the content of the virgin heterophasic propylene polymerization material (C) is 5% by mass or more and 79% by mass or less, relative to 100% by mass of the total mass of the recycled propylene composition (A), the virgin heterophasic propylene polymerization material (B), and the virgin heterophasic propylene polymerization material (C).

[0103] <Ethylene-α-olefin copolymer (D)> In one embodiment, the propylene resin composition according to the present embodiment further contains an ethylene-α-olefin copolymer (D). The ethylene-α-olefin copolymer (D) may be contained in the recycled propylene composition (A). Specifically, the recycled propylene composition (A) may contain the ethylene-α-olefin copolymer (D). Furthermore, the ethylene-α-olefin copolymer (D) may be a virgin ethylene-α-olefin copolymer or a recycled ethylene-α-olefin copolymer.

[0104] The ethylene-α-olefin copolymer (D) may be an ethylene-α-olefin random copolymer. The ethylene-α-olefin copolymer (D) refers to a copolymer containing monomer units derived from ethylene and monomer units derived from an α-olefin having 4 or more carbon atoms, and substantially free of monomer units derived from propylene.

[0105] The ethylene-α-olefin copolymer (D) may have a total content of monomer units derived from ethylene and monomer units derived from α-olefins having 4 or more carbon atoms of 100% by mass, where 100% by mass is the total mass of the copolymer.

[0106] Examples of α-olefins having 4 or more carbon atoms include α-olefins having 4 to 12 carbon atoms. Examples of α-olefins having 4 to 12 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene. The α-olefins having 4 to 12 carbon atoms are preferably 1-butene, 1-hexene, or 1-octene. The α-olefins having 4 to 12 carbon atoms may be α-olefins having a cyclic structure, such as vinylcyclopropane and vinylcyclobutane.

[0107] Examples of the ethylene-α-olefin copolymer (D) include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, ethylene-(3-methyl-1-butene) copolymer, and copolymers of ethylene and an α-olefin having a cyclic structure.

[0108] In the ethylene-α-olefin copolymer (D), the content of monomer units derived from α-olefins having 4 or more carbon atoms is preferably 1% by mass or more and 49% by mass or less, more preferably 5% by mass or more and 49% by mass or less, and even more preferably 24% by mass or more and 49% by mass or less, relative to 100% by mass of the total mass of the ethylene-α-olefin copolymer.

[0109] The density of the ethylene-α-olefin copolymer (D) is preferably 0.85 g / cm from the viewpoint of the impact resistance of the molded product. 3 More than 0.89g / cm 3 or less, more preferably 0.85 g / cm 3 More than 0.88g / cm 3 More preferably, it is 0.85 g / cm or less. 3 More than 0.87g / cm 3 The following is the result.

[0110] The ethylene-α-olefin copolymer (D) preferably has a melt flow rate (MFR) of 0.1 g / 10 min or more and 80 g / 10 min or less at a temperature of 190° C. and a load of 2.16 kg. The melt flow rate (MFR) can be measured by Method A under conditions of a temperature of 190° C. and a load of 2.16 kg in accordance with the method specified in JIS K7210-1995.

[0111] The content of the ethylene-α-olefin copolymer (D) is preferably 1% by mass or more, more preferably 5% by mass or more, based on 100% by mass of the total mass of the propylene resin composition, and is preferably 50% by mass or less, more preferably 30% by mass or less, based on 100% by mass of the total mass of the propylene resin composition.

[0112] The ethylene-α-olefin copolymer (D) can be produced by polymerizing ethylene and an α-olefin having 4 or more carbon atoms using a polymerization catalyst.

[0113] Examples of the polymerization catalyst include homogeneous catalysts such as metallocene catalysts, and Ziegler-Natta catalysts.

[0114] Examples of homogeneous catalysts include catalysts containing a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; catalysts containing a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound; and modified catalysts in which a catalyst component (a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that forms an ionic complex, an organoaluminum compound, etc.) is supported on inorganic particles (silica, clay minerals, etc.).

[0115] Examples of Ziegler-Natta catalysts include catalysts that combine a titanium-containing solid transition metal component with an organometallic component.

[0116] The ethylene-α-olefin copolymer (D) may be a commercially available product. Examples of commercially available ethylene-α-olefin copolymers include Engage (registered trademark) manufactured by Dow Chemical Japan, Tafmer (registered trademark) manufactured by Mitsui Chemicals, Inc., Neozex (registered trademark) and Ultozex (registered trademark) manufactured by Prime Polymer Co., Ltd., and Excellen FX (registered trademark), Sumikathene (registered trademark), and Esprene SPO (registered trademark) manufactured by Sumitomo Chemical Co., Ltd.

[0117] <Filling material> In one aspect, the propylene resin composition according to the present embodiment further includes a filler. The filler may be a virgin filler or a recycled filler.

[0118] Examples of the filler include inorganic fillers and organic fillers. The propylene resin composition according to this embodiment may contain only one type of filler, or may contain two or more types of fillers. In one aspect, the propylene resin composition according to this embodiment further contains an inorganic filler (E).

[0119] Examples of the inorganic filler (E) include glass, silicate minerals, alumina, silica, silicon dioxide, titanium oxide, iron oxide, aluminum oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, carbonate minerals, calcium sulfate, magnesium sulfate, basic magnesium sulfate, calcium sulfite, carbon black, and cadmium sulfide.

[0120] Examples of organic fillers include polyester, aromatic polyamide, cellulose, vinylon, and the like.

[0121] The shape of the filler may be plate-like, needle-like, or fibrous.

[0122] From the viewpoint of improving the rigidity, impact resistance and dimensional stability of the molded body, the filler is preferably an inorganic filler (E), more preferably talc, which is a plate-like silicate mineral.

[0123] From the viewpoint of improving the rigidity, impact resistance, and dimensional stability of the molded body, the average particle diameter D50[L] of the filler is preferably 20.0 μm or less, more preferably 15.0 μm or less. The average particle diameter D50[L] of the filler is preferably 2.0 μm or more, more preferably 4.0 μm or more. The average particle diameter D50[L] of the filler is preferably 2.0 μm or more and 20.0 μm or less, more preferably 4.0 μm or more and 15.0 μm or less.

[0124] From the viewpoint of improving the rigidity, impact resistance, and dimensional stability of the molded body, the average particle diameter D50[S] of the filler is preferably 5.0 μm or less, more preferably 3.0 μm or less. The average particle diameter D50[S] of the filler is preferably 0.5 μm or more, more preferably 1.0 μm or more. The average particle diameter D50[S] of the filler is preferably 0.5 μm or more and 5.0 μm or less, more preferably 1.0 μm or more and 3.0 μm or less.

[0125] The ratio of the average particle diameter D50[L] to the average particle diameter D50[S] of the filler (D50[L] / D50[S]) is preferably 1.5 or more, more preferably 2.5 or more, from the viewpoint of improving the rigidity and dimensional stability of the molded body. D50[L] / D50[S] is preferably 10 or less, more preferably 8 or less. D50[L] / D50[S] is preferably 1.5 or more and 10 or less, more preferably 1.5 or more and 8 or less or 2.5 or more and 10 or less, and even more preferably 2.5 or more and 8 or less.

[0126] In this specification, "average particle diameter D50[L]" is determined based on volume-based particle diameter distribution measurement data measured by laser diffraction in accordance with the method specified in JIS R1629, and refers to the particle diameter when the cumulative number of particles from the smallest particle diameter reaches 50% in the particle diameter distribution measurement data (50% equivalent particle diameter). The particle diameter defined in this way is generally referred to as the "50% equivalent particle diameter" and is expressed as "D50".

[0127] The average particle diameter D50 [L] of the filler can be measured using a Microtrac particle size analyzer MT-3300EXII manufactured by Nikkiso Co., Ltd., after dispersing the particles under the following conditions according to the method specified in JIS R1629. Dispersion medium: ethanol Equipment: Homogenizer Output: 40W Processing time: 10 minutes

[0128] In this specification, the term "average particle diameter D50 [S]" is determined based on volume-based particle diameter distribution measurement data measured by centrifugal sedimentation in accordance with the method specified in JIS R1619, and refers to the particle diameter when the cumulative number of particles from the smaller particle diameter side reaches 50% in the particle diameter distribution measurement data (50% equivalent particle diameter).

[0129] The average particle diameter D50[S] of the filler can be measured using a centrifugal sedimentation particle size distribution analyzer SA-CP3 manufactured by Shimadzu Corporation, after dispersing the particles under the following conditions according to the method specified in JIS R1619. Dispersion medium: ethanol Equipment: Honda Electronics W-113MkII Output: 110W 24kHz Processing time: 10 minutes

[0130] The greater the ratio of the average particle diameter D50[L] to the average particle diameter D50[S] (D50[L] / D50[S]) of the filler, the more excellent the rigidity and dimensional stability of the molded body.

[0131] The content of the filler is preferably 1% by mass or more, more preferably 5% by mass or more, based on 100% by mass of the total mass of the propylene resin composition, and is preferably 50% by mass or less, more preferably 30% by mass or less, based on 100% by mass of the total mass of the propylene resin composition.

[0132] In one aspect, the propylene resin composition according to the present embodiment further contains a virgin heterophasic propylene polymer material (C), an ethylene-α-olefin copolymer (D), and an inorganic filler (E).

[0133] The propylene resin composition according to the present embodiment may contain other components in addition to those described above. Examples of the other components include thermoplastic resins (polystyrenes (e.g., polystyrene, poly(p-methylstyrene), poly(α-methylstyrene), AS (acrylonitrile / styrene copolymer) resin), ABS (acrylonitrile / butadiene / styrene copolymer) resin, AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin, ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin, polychloroprene, chlorinated rubber, polyvinyl chloride, polyvinylidene chloride, acrylic resin, ethylene / vinyl alcohol copolymer resin, fluororesin, polyacetal, grafted polyphenylene ether resin and polyphenylene sulfide resin, polyurethane, polyamide, polyester resin (e.g., polyethylene terephthalate, polybutylene terephthalate), poly Examples of suitable additives include carbonate, polysulfone, polyether ether ketone, polyethersulfone, aromatic polyester resin, polybutadiene, 1,2-polybutadiene, polyisoprene, styrene / butadiene copolymer, butadiene / acrylonitrile copolymer, natural rubber, etc.), epoxy resin, diallyl phthalate prepolymer, silicone resin, silicone rubber, epichlorohydrin rubber, acrylic rubber, and PLA resin (polylactic acid) produced by polymerizing plant-derived monomers extracted from biomaterials, neutralizing agents, antioxidants, UV absorbers, nucleating agents, lubricants, antistatic agents, antiblocking agents, processing aids, organic peroxides, colorants (inorganic pigments, organic pigments, pigment dispersants, etc.), foaming agents, foam nucleating agents, plasticizers, flame retardants, crosslinking agents, crosslinking aids, brightness enhancers, antibacterial agents, light diffusing agents, and light stabilizers. The other components may be virgin materials or recycled materials, may be contained in the raw materials used for recycling, or may be contained in the raw materials used for producing the propylene resin composition together with the recycled propylene polymer.

[0134] The propylene resin composition according to this embodiment is configured in the above manner, so that a molded article having a relatively low weld height can be obtained.

[0135] [Molded body] The molded article according to the present embodiment contains the above-described propylene resin composition. That is, the above-described propylene resin composition can be used as a material for forming a molded article by molding. The above-described propylene resin composition can be preferably used as an injection molding material. Hereinafter, an example of an injection-molded article produced using the propylene resin composition as an injection molding material will be described.

[0136] Injection-molded articles can be produced by injection molding, including, for example, general injection molding, injection foam molding, supercritical injection foam molding, ultra-high speed injection molding, injection compression molding, gas-assisted injection molding, sandwich molding, sandwich foam molding, and insert-outsert molding. The shape of the injection-molded article is not particularly limited.

[0137] The injection-molded article can be used, for example, for automotive materials, home appliance materials, containers, etc., and is preferably used for automotive interior and exterior applications. Examples of automotive interior and exterior parts include door trims, pillars, instrument panels, bumpers, etc.

[0138] The molded article according to this embodiment is configured in the above manner, and thus can be obtained as a molded article with a relatively low weld height.

[0139] [Method of manufacturing molded body] The method for producing a molded body according to this embodiment includes a step of mixing pellets containing a recycled propylene composition (A) with pellets containing a virgin heterophasic propylene polymerization material (B) to obtain a mixture (hereinafter also referred to as the "mixing step"), and a step of molding the mixture using a molding machine to obtain a molded body (hereinafter also referred to as the "molding step").

[0140] In the method for producing a molded article according to this embodiment, the recycled propylene composition (A) is the same as the recycled propylene composition (A) contained in the propylene resin composition according to this embodiment. Also, in the method for producing a molded article according to this embodiment, the virgin heterophasic propylene polymer material (B) is the same as the virgin heterophasic propylene polymer material (B) contained in the propylene resin composition according to this embodiment.

[0141] In one embodiment, in the mixing step, pellets containing the virgin heterophasic propylene polymerization material (C), pellets containing the ethylene-α-olefin copolymer (D), the inorganic filler (E), or any additive may be further mixed.

[0142] Various pellets can be obtained by melt-kneading polymer materials, etc. The melt-kneading can be carried out, for example, by pre-mixing the materials uniformly in a Henschel mixer or a tumbler, and then using an extruder such as a twin-screw kneading extruder.

[0143] The molding step is preferably carried out by the injection molding method described above. Examples of the molding machine include an injection molding machine.

[0144] The method for manufacturing a molded article according to this embodiment is configured in the above manner, and thus can manufacture a molded article having a relatively low weld height.

[0145] The present invention includes the following aspects. [1] A recycled propylene composition (A), and (B) a virgin heterophasic propylene polymerization material, The virgin heterophasic propylene polymerization material (B) has a weight average molecular weight of 200,000 or more and less than 500,000, and the ratio of [η]CXS to [η]CXIS is less than 6.0; A propylene resin composition, wherein the virgin heterophasic propylene polymer material (B) has a melt flow rate (MFR) of 5 g / 10 min or more. [2] The propylene resin composition according to [1], wherein the virgin heterophasic propylene polymer material (B) has a melt flow rate (MFR) of 100 g / 10 min or less. [3] The propylene resin composition according to [1] or [2], wherein the virgin heterophasic propylene polymerization material (B) has an [η]CXS of 5.00 dL / g or more and 9.00 dL / g or less. [4] The propylene resin composition according to any one of [1] to [3], wherein the virgin heterophasic propylene polymerization material (B) has an [η]CXIS of 0.50 dL / g or more and 2.00 dL / g or less. [5] The propylene resin composition according to any one of [1] to [4], wherein the ratio of [η]CXS to [η]CXIS in the virgin heterophasic propylene polymerization material (B) is 3.0 or more and less than 6.0. [6] The propylene resin composition according to any one of [1] to [5], wherein the amount of CXS in the virgin heterophasic propylene polymerization material (B) is 15% by mass or more and 30% by mass or less, relative to 100% by total mass of the virgin heterophasic propylene polymerization material (B). [7] The virgin heterophasic propylene polymerization material (B) has an [η]CXS of 5.00 dL / g or more and 9.00 dL / g or less; [η]CXIS of the virgin heterophasic propylene polymerization material (B) is 0.50 dL / g or more and 2.00 dL / g or less, the ratio of [η]CXS to [η]CXIS of the virgin heterophasic propylene polymerization material (B) is 3.0 or more and less than 6.0; The propylene resin composition according to [1] or [2], wherein the amount of CXS in the virgin heterophasic propylene polymer material (B) is 15% by mass or more and 30% by mass or less, relative to 100% by total mass of the virgin heterophasic propylene polymer material (B). [8] The propylene resin composition according to any one of [1] to [7], wherein at least a part of the recycled propylene composition (A) is derived from materials recovered from automobile parts. [9] Further, it contains virgin heterophasic propylene polymer material (C), The virgin heterophasic propylene polymer material (C) is A virgin heterophasic propylene polymer material (C1) having a weight average molecular weight of less than 200,000; A virgin heterophasic propylene polymer material (C2) having a weight average molecular weight of 500,000 or more, and At least one selected from the group consisting of virgin heterophasic propylene polymerization materials (C3) having a weight average molecular weight of 200,000 or more and less than 500,000 and a ratio of [η]CXS to [η]CXIS of 6.0 or more, The propylene resin composition according to any one of [1] to [8].

[10] With respect to 100% by mass of the total mass of the recycled propylene composition (A), the virgin heterophasic propylene polymerization material (B), and the virgin heterophasic propylene polymerization material (C), The content of the recycled propylene composition (A) is 20% by mass or more and 80% by mass or less, The content of the virgin heterophasic propylene polymerization material (B) is 1% by mass or more and 20% by mass or less, The propylene resin composition according to [9], wherein the content of the virgin heterophasic propylene polymer material (C) is 5% by mass or more and 79% by mass or less.

[11] The propylene resin composition according to any one of [1] to

[10] , further comprising an ethylene-α-olefin copolymer (D).

[12] The propylene resin composition according to any one of [1] to

[11] , further comprising an inorganic filler (E).

[13] The propylene resin composition according to any one of [1] to [8], further comprising a virgin heterophasic propylene polymerization material (C), an ethylene-α-olefin copolymer (D), and an inorganic filler (E).

[14] A molded article comprising the propylene resin composition according to any one of [1] to

[13] .

[15] A step of mixing pellets containing a recycled propylene composition (A) with pellets containing a virgin heterophasic propylene polymerization material (B) to obtain a mixture; and molding the mixture using a molding machine to obtain a molded body, The virgin heterophasic propylene polymerization material (B) has a weight average molecular weight of 200,000 or more and less than 500,000, and the ratio of [η]CXS to [η]CXIS is less than 6.0; The method for producing a molded article, wherein the virgin heterophasic propylene polymer material (B) has a melt flow rate (MFR) of 5 g / 10 min or more.

[0146] The propylene resin composition, the molded article, and the method for manufacturing the molded article are not limited to the above-described embodiments, and various modifications are possible without departing from the spirit of the present invention. In addition, the configurations, methods, etc. of embodiments other than those described above may be arbitrarily adopted and combined, and the configurations, methods, etc. of one embodiment described above may be applied to the configurations, methods, etc. of the other embodiments described above. [Example]

[0147] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0148] In the examples and comparative examples, the following raw materials were used.

[0149] As the recycled propylene composition (A), the following recycled propylene compositions (A-1) to (A-4) were prepared.

[0150] (A-1): Recycled propylene composition derived from automobile bumpers collected from the market Melt flow rate (MFR) (230°C, 2.16 kg load): 42 g / 10 min Ash content: 18.1% by mass CXIS amount: 70.0% by mass CXS amount: 30.0% by mass

[0151] (A-2): Recycled propylene composition derived from automobile bumpers collected from the market Melt flow rate (MFR) (230°C, 2.16 kg load): 45 g / 10 min Ash content: 11.4% by mass CXIS amount: 68.8% by mass CXS amount: 31.2% by mass

[0152] (A-3): Recycled propylene composition derived from automobile pillars collected from the market Melt flow rate (MFR) (230°C, 2.16 kg load): 33 g / 10 min Ash content: 3.1% by mass CXIS amount: 83.1% by mass CXS amount: 16.9% by mass

[0153] (A-4): Recycled propylene composition derived from automobile interior materials collected from the market Melt flow rate (MFR) (230°C, 2.16 kg load): 30 g / 10 min Ash content: 5.6% by mass CXIS amount: 76.3% by mass CXS amount: 23.7% by mass

[0154] As the virgin heterophasic propylene polymer material (B), the following virgin heterophasic propylene polymer materials (B-1) to (B-3) were prepared.

[0155] (B-1): Virgin heterophasic propylene polymer material Polymiray "EP5091" MFR (230℃, 2.16kg load): 30g / 10 minutes [η]CXIS:1.15dL / g [η]CXS:6.55dL / g [η]CXS / [η]CXIS:5.7 CXIS amount: 82.5% by mass CXS content: 17.5% by mass Weight average molecular weight: 258029

[0156] (B-2): バージンヘテロファジックプロピレン laminated material Made by ポリミレイ Corporation "EP5175" MFR (230℃, 2.16kg load): 12g / 10 minutes [η]CXIS:1.19dL / g [η]CXS:6.68dL / g [η]CXS / [η]CXIS:5.6 CXIS amount: 72.4% by mass CXS content: 27.6% by mass Weight average molecular weight: 407124

[0157] (B-3): バージンヘテロファジックプロピレン laminated material "X1956A" manufactured by Lyondell Basell MFR (230℃, 2.16kg load): 1g / 10 minutes [η]CXIS:2.55dL / g [η]CXS:7.20dL / g [η]CXS / [η]CXIS:2.8 CXIS amount: 76.3% by mass CXS content: 23.7% by mass Weight average molecular weight: 680250

[0158] The following virgin heterophasic propylene polymerization materials (C-1) to (C-3) were prepared as virgin heterophasic propylene polymerization materials (C). Specifically, the virgin heterophasic propylene polymerization materials (C-1) to (C-3) were produced by gas-phase polymerization in the presence of a polymerization catalyst obtained by the method described in Example 1 of JP-A-2004-182981. The physical properties of the obtained components (C-1) to (C-3) are as follows:

[0159] (C-1): Virgin heterophasic propylene polymer material Melt flow rate (MFR) (230°C, 2.16 kg load): 27.5 g / 10 min [η]CXIS: 1.19 dL / g [η]CXS: 2.93 dL / g [η]CXS / [η]CXIS:2.6 CXIS amount: 84.1% by mass CXS amount: 15.9% by mass Weight average molecular weight: 189176

[0160] (C-2): Virgin heterophasic propylene polymer material Melt flow rate (MFR) (230°C, 2.16 kg load): 38 g / 10 min [η]CXIS:1.03dL / g [η]CXS: 2.07 dL / g [η]CXS / [η]CXIS:2.0 CXIS amount: 69.5% by mass CXS amount: 30.5% by mass Weight average molecular weight: 161568

[0161] (C-3): Virgin heterophasic propylene polymer material Melt flow rate (MFR) (230°C, 2.16 kg load): 13 g / 10 min [η]CXIS: 1.34 dL / g [η]CXS: 6.04 dL / g [η]CXS / [η]CXIS:4.5 CXIS amount: 77.1% by mass CXS amount: 22.9% by mass Weight average molecular weight: 609840

[0162] As the ethylene-α-olefin copolymer (D), the following ethylene-α-olefin copolymer (D-1) was prepared.

[0163] (D-1): Ethylene-1-octene random copolymer Dow Chemical Company "EG8200" Density: 0.870g / cm 3 Melt flow rate (MFR) (190°C, 2.16 kg load): 5.0 g / 10 min

[0164] As the inorganic filler (E), the following inorganic filler (E-1) was prepared.

[0165] (E-1): Talc Hayashi Kasei “MW UPN TT-H” Average particle size D50 [L] (laser diffraction method, 50% equivalent particle size): 4.90 μm Average particle size D50 [S] (centrifugal sedimentation method, 50% equivalent particle size): 2.28 μm

[0166] As other optional and suitable additives, the following components were used.

[0167] The following antioxidants (F-1), (F-2), and (F-3) were prepared.

[0168] (F-1): Sumitomo Chemical Co., Ltd. "Sumilizer GA80 (phenolic antioxidant)" (F-2): Sumitomo Chemical's "Sumilizer GP (phosphorus antioxidant)" (F-3): Songwon "Songnox 6260 (phosphorus antioxidant)"

[0169] The following neutralizer (F-4) was prepared.

[0170] (F-4): Calcium stearate manufactured by Sakai Chemical Industry Co., Ltd.

[0171] The following ultraviolet absorber (F-5) was prepared.

[0172] (F-5): BASF "Uvinal 5050H"

[0173] The following light stabilizer (F-6) was prepared.

[0174] (F-6): BASF "Tinuvin 770DF"

[0175] The following lubricant (F-7) was prepared.

[0176] (F-7): NOF Corp. "Alflo H-50P"

[0177] Each physical property was calculated by the following method.

[0178] (1) Ash content (unit: mass%) The crucible was heated at 600 ° C. for 60 minutes using an electric furnace, removed and cooled in a desiccator for 1 hour, and then weighed on a precision balance. 10 g of recycled propylene composition (A) was weighed into the crucible and heated at 600 ° C. for 60 minutes using an electric furnace to completely incinerate it. The crucible was then cooled in a desiccator for 1 hour, after which the weight of the ash was measured to the nearest 0.1 mg using a precision balance, and the ash content (mass%) relative to the recycled propylene composition (A) was calculated.

[0179] (2) Melt flow rate (MFR, unit: g / 10 min) The melt flow rate (MFR) was measured by Method A according to the method specified in JIS K7210-1995, under conditions of a temperature of 230°C or 190°C and a load of 2.16 kg.

[0180] (3) Intrinsic viscosity (unit: dL / g) The intrinsic viscosity is a value measured at a temperature of 135°C using tetralin as a solvent by the following method.

[0181] Using an Ubbelohde viscometer, reduced viscosities were measured at three concentrations: 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL. The reduced viscosities were plotted against the concentrations, and the intrinsic viscosity was calculated by extrapolation, extrapolating the concentration to zero. The method for calculating intrinsic viscosity using extrapolation is described, for example, on page 491 of "Polymer Solutions, Polymer Experiments 11" (published by Kyoritsu Shuppan Co., Ltd. in 1982).

[0182] (4) CXIS and CXS amounts A 4 g sample was weighed and refluxed in boiling xylene for 5 hours using a cylindrical filter paper and a Soxhlet extraction tube. The extract was then concentrated under reduced pressure using a rotary evaporator to obtain a polymer component. The resulting polymer component was weighed (hereinafter, the "weight of polymer component" will be referred to as "a"). 2 g of polymer component a was weighed and dissolved in boiling xylene by heating for 2 hours. After cooling to 20°C, the solution was filtered using filter paper. The filtrate was concentrated under reduced pressure using a rotary evaporator to obtain a CXS component. The resulting CXS component was weighed (hereinafter, the "weight of CXS component" will be referred to as "b"). The amounts of CXIS and CXS in the sample were calculated using the values ​​a and b according to the following formula. The solid remaining on the filter paper was vacuum dried to obtain the CXIS component. The resulting CXIS component was used to evaluate the molecular weight distribution. CXS amount (mass%)=(b / a)×100 CXIS amount (mass%) = 100-CXS amount (mass%)

[0183] (5): Weight average molecular weight The weight average molecular weight (Mw) of the virgin heterophasic propylene polymer material was measured using gel permeation chromatography (GPC) under the following conditions. Equipment: Tosoh Corporation HLC-8121 GPC / HT Separation column: Tosoh Corporation GMHHR-H(S)HT (3 columns) Measurement temperature: 140℃ Carrier: Orthodichlorobenzene Flow rate: 1.0mL / min Sample concentration: approximately 1 mg / mL Sample injection volume: 400 μL Detector: Differential refraction Calibration curve creation method: Standard polystyrene is used

[0184] (6): Average particle diameter D50[L] The average particle diameter D50 [L] of talc was measured using a Microtrac particle size analyzer MT-3300EXII manufactured by Nikkiso Co., Ltd., after dispersing the particles under the following conditions according to the method specified in JIS R1629. Dispersion medium: ethanol Equipment: Homogenizer Output: 40W Processing time: 10 minutes

[0185] (7): Average particle diameter D50[S] The average particle diameter D50[S] was measured using a centrifugal sedimentation particle size distribution analyzer SA-CP3 manufactured by Shimadzu Corporation after dispersing the particles under the following conditions according to the method specified in JIS R1619. Dispersion medium: ethanol Equipment: Honda Electronics W-113MkII Output: 110W 24kHz Processing time: 10 minutes

[0186] <Examples 1 to 16 and Comparative Examples 1 and 2> A propylene resin composition was prepared by the following method.

[0187] The raw materials and additives having the compositions shown in Tables 1 and 2 were weighed out in the following amounts relative to 100% by mass of the total mass of components (A) to (E): 0.05% by mass of Sumilizer GA80, 0.05% by mass of Sumilizer GP, 0.1% by mass of Songnox 6260, 0.05% by mass of calcium stearate, 0.2% by mass of Uvinal 5050H, 0.1% by mass of Tinuvin 770DF, and 0.05% by mass of Alflow H-50P. All components were uniformly pre-mixed in a Henschel mixer or a tumbler, and then melt-kneaded using a twin-screw kneading extruder (TEX44αII-49BW-3V, manufactured by The Japan Steel Works, Ltd.) to obtain a pellet-shaped propylene resin composition.

[0188] The melt-kneading conditions were a cylinder temperature of 200°C, a screw rotation speed of 180 rpm, two screen meshes of 100 mesh and 40 mesh stacked together, and an extrusion rate of 60 kg / hr.

[0189] The obtained resin composition was injection molded under the following conditions to produce an injection-molded article for evaluation: The resin composition was melted in an injection molding machine and supplied from the gate into the mold cavity by the injection molding machine. Injection molding machine: SE180D manufactured by Sumitomo Heavy Industries, Ltd. (mold clamping force 180 tons, cylinder diameter 50 mm) Mold cavity shape: 100mm (width) x 400mm (length) x 3mm (thickness) Gate: 2 fan gates on both ends of the 100mm side Cylinder temperature: 220℃ Mold temperature: 50℃ Injection speed: 23mm / sec Cooling time: 30 seconds

[0190] (Evaluation of flow mark occurrence location) The behavior (flow) of the molten resin during melt processing remains on the molded product, making it obvious that it is a "flow mark." This was evaluated visually. Starting from the end of the molded product on the gate side, the distance to the point where the first flow mark appeared was measured. The closer the flow mark was to the gate (smaller the measurement value), the worse the appearance of the injection-molded product surface; the farther the flow mark was to the gate (larger the measurement value), the better the appearance.

[0191] (Evaluation of average weld height) The surface roughness in the direction perpendicular to the welds generated on the surface of the obtained molded article was measured under the following conditions. The average value of the measurements at four locations was calculated, and this average value was used as the weld height value. A higher weld height indicates a poorer appearance (more noticeable) of the injection-molded article surface, while a lower weld height indicates a better appearance (less noticeable). Surface roughness meter: Tokyo Seimitsu Surfcom 480A Stylus tip: 2 μmR Measurement length: 20 mm Measurement speed: 0.3mm / sec Cutoff: None Measurement position: 10, 20, 50, 70 mm from the gate

[0192] (Evaluation of the number of flat particles) The surface of the obtained molded article was visually observed, and the number of visible foreign matter was counted as 100. The area where the 100 foreign matter particles were present was calculated, and the area was used to calculate the area of ​​400 cm of the molded article. 2 The number of foreign objects per unit area was calculated. Number of foreign objects in the molded body (pieces / 400cm 2 ) = 100 pieces x (400cm 2 / cm area where 100 foreign particles exist 2 )

[0193] [Table 1]

[0194] [Table 2]

[0195] As can be seen from the results in Tables 1 and 2, the propylene resin compositions of Examples 1 to 16, which satisfy all of the constituent requirements of the present invention, can provide propylene resin compositions, molded articles, and methods for producing molded articles that can produce molded articles with relatively low weld heights while recycling polypropylene. Furthermore, the propylene resin compositions of Examples 1 to 16 can produce molded articles with relatively beautiful appearances, based on the evaluation results of the flow mark occurrence positions and the number of flat bumps.

Claims

1. A recycled propylene composition (A), a virgin heterophasic propylene polymer material (B); and (C) a virgin heterophasic propylene polymerization material, The amount of CXS in the recycled propylene composition (A) is 16.9% by mass or more and 31.2% by mass or less, based on 100% by total mass of the recycled propylene composition (A), In the recycled propylene composition (A), the ash content is 3.1 mass% or more and 18.1 mass% or less, based on 100 mass% of the total mass of the recycled propylene composition (A), The melt flow rate (MFR) of the recycled propylene composition (A) is 10 g / 10 min or more and 50 g / 10 min or less, the virgin heterophasic propylene polymer material (B) has a weight average molecular weight of 200,000 or more and less than 500,000, and a ratio of [η]CXS to [η]CXIS is 5.50 or more and 5.98 or less; the [η]CXS of the virgin heterophasic propylene polymerization material (B) is 6.55 dL / g or more and 6.88 dL / g or less; the [η]CXIS of the virgin heterophasic propylene polymerization material (B) is 1.15 dL / g or more and 1.19 dL / g or less; the amount of CXS in the virgin heterophasic propylene polymer material (B) is 17.5% by mass or more and 27.6% by mass or less, based on 100% by total mass of the virgin heterophasic propylene polymer material (B); the virgin heterophasic propylene polymer material (B) has a melt flow rate (MFR) of 12 g / 10 min or more and 30 g / 10 min or less; The virgin heterophasic propylene polymer material (C) is A virgin heterophasic propylene polymer material (C1) having a weight average molecular weight of 100,000 or more and less than 200,000, or a virgin heterophasic propylene polymer material (C2) having a weight-average molecular weight of 500,000 or more and 1,000,000 or less; the [η]CXS of the virgin heterophasic propylene polymerization material (C) is 2.07 dL / g or more and 6.04 dL / g or less; the [η]CXIS of the virgin heterophasic propylene polymerization material (C) is 1.03 dL / g or more and 1.34 dL / g or less; the amount of CXS in the virgin heterophasic propylene polymer material (C) is 15.9 mass% or more and 30.5 mass% or less, based on 100% by total mass of the virgin heterophasic propylene polymer material (C); the virgin heterophasic propylene polymer material (C) has a melt flow rate (MFR) of 10 g / 10 min or more and 50 g / 10 min or less; Based on 100% by mass of the total mass of the propylene resin composition, The content of the recycled propylene composition (A) is 30% by mass or more and 50% by mass or less, The content of the virgin heterophasic propylene polymer material (B) is 5% by mass or more and 15% by mass or less, A propylene resin composition, wherein the content of the virgin heterophasic propylene polymer material (C) is 36% by mass or more and 60% by mass or less.

2. The propylene resin composition according to claim 1, wherein at least a portion of the recycled propylene composition (A) is derived from materials recovered from automobile parts.

3. The propylene resin composition according to claim 1, further comprising an ethylene-α-olefin copolymer (D).

4. The propylene resin composition according to claim 1, further comprising an inorganic filler (E).

5. The propylene resin composition according to claim 1, further comprising an ethylene-α-olefin copolymer (D) and an inorganic filler (E).

6. A molded article comprising the propylene resin composition according to any one of claims 1 to 5.

7. A step of mixing pellets containing the recycled propylene composition (A), pellets containing the virgin heterophasic propylene polymer material (B), and pellets containing the virgin heterophasic propylene polymer material (C) to obtain a propylene resin composition; and a step of molding the propylene resin composition using a molding machine to obtain a molded product, The amount of CXS in the recycled propylene composition (A) is 16.9% by mass or more and 31.2% by mass or less, based on 100% by total mass of the recycled propylene composition (A), In the recycled propylene composition (A), the ash content is 3.1 mass% or more and 18.1 mass% or less, based on 100 mass% of the total mass of the recycled propylene composition (A), The melt flow rate (MFR) of the recycled propylene composition (A) is 10 g / 10 min or more and 50 g / 10 min or less, the virgin heterophasic propylene polymer material (B) has a weight average molecular weight of 200,000 or more and less than 500,000, and a ratio of [η]CXS to [η]CXIS is 5.50 or more and 5.98 or less; the [η]CXS of the virgin heterophasic propylene polymerization material (B) is 6.55 dL / g or more and 6.88 dL / g or less; the [η]CXIS of the virgin heterophasic propylene polymerization material (B) is 1.15 dL / g or more and 1.19 dL / g or less; the amount of CXS in the virgin heterophasic propylene polymer material (B) is 17.5% by mass or more and 27.6% by mass or less, based on 100% by total mass of the virgin heterophasic propylene polymer material (B); the virgin heterophasic propylene polymer material (B) has a melt flow rate (MFR) of 12 g / 10 min or more and 30 g / 10 min or less; The virgin heterophasic propylene polymer material (C) is A virgin heterophasic propylene polymer material (C1) having a weight average molecular weight of 100,000 or more and less than 200,000, or a virgin heterophasic propylene polymer material (C2) having a weight-average molecular weight of 500,000 or more and 1,000,000 or less; the [η]CXS of the virgin heterophasic propylene polymerization material (C) is 2.07 dL / g or more and 6.04 dL / g or less; the [η]CXIS of the virgin heterophasic propylene polymerization material (C) is 1.03 dL / g or more and 1.34 dL / g or less; the amount of CXS in the virgin heterophasic propylene polymer material (C) is 15.9 mass% or more and 30.5 mass% or less, based on 100% by total mass of the virgin heterophasic propylene polymer material (C); the virgin heterophasic propylene polymer material (C) has a melt flow rate (MFR) of 10 g / 10 min or more and 50 g / 10 min or less; Based on 100% by mass of the total mass of the propylene resin composition, The content of the recycled propylene composition (A) is 30% by mass or more and 50% by mass or less, The content of the virgin heterophasic propylene polymer material (B) is 5% by mass or more and 15% by mass or less, The method for producing a molded article, wherein the content of the virgin heterophasic propylene polymerization material (C) is 36% by mass or more and 60% by mass or less.

Images