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

Abstract

The objective is to provide a propylene-based resin composition, a molded article, and a method for producing a propylene-based resin composition, which can be obtained by obtaining a molded article that has relatively reduced odor, relatively high impact strength at low temperatures, and relatively high flexibility against tensile deformation at room temperature and retention rate against tensile deformation at high temperatures. [Solution] The propylene-based resin composition according to the present invention contains a propylene-based polymer (A) and a fragrance (B), The melt flow rate is between 0.3g / 10min and 200g / 10min. The fragrance (B) is a cyclic organic compound that does not contain nitrogen atoms and sulfur atoms. The content of the fragrance (B) is 0.01 ppm by mass or more and 1000 ppm by mass or less, relative to the propylene resin composition.

Description

[Technical Field]

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

[0002] Propylene resins are widely used in automotive parts, household electrical appliance casings, and other applications due to their excellent moldability, rigidity, and heat resistance. Furthermore, in recent years, there has been a growing demand for material recycling, which involves reusing waste plastics as raw materials for plastic products.

[0003] However, propylene resins contain residual components such as low molecular weight components generated during the polymerization process and components derived from polymerization catalysts. As a result, the resulting molded products have an unpleasant odor due to these residual components. In particular, recycled propylene resins recovered from the market contain additives such as processing aids, stabilizers, fibers, and fillers, which can also cause odors, resulting in molded products with an even more unpleasant odor.

[0004] To address the odor problem, for example, Patent Document 1 discloses a polyolefin resin composition comprising a polyolefin resin, a dibenzylidene sorbitol composition, and a fragrance, showing that the odor originating from the polyolefin resin is masked by the scent of the fragrance such as vanillin, resulting in improved odor. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 02 / 040587 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, molded articles containing a propylene-based resin composition that includes a propylene polymer and a fragrance have insufficient mechanical properties, particularly impact strength at low temperatures, flexibility against tensile deformation at room temperature, and retention rate against tensile deformation at high temperatures, and there is room for improvement.

[0007] The present invention has been made in view of these problems, and aims to provide a propylene-based resin composition, a molded article, and a method for producing a propylene-based resin composition that can be obtained by obtaining a molded article that has relatively reduced odor, relatively high impact strength at low temperatures, and relatively high flexibility against tensile deformation at room temperature and retention rate against tensile deformation at high temperatures. [Means for solving the problem]

[0008] The propylene-based resin composition according to the present invention contains a propylene-based polymer (A) and a fragrance (B), The melt flow rate is between 0.3g / 10min and 200g / 10min. The fragrance (B) is a cyclic organic compound that does not contain nitrogen atoms and sulfur atoms. The content of the fragrance (B) is 0.01 ppm by mass or more and 1000 ppm by mass or less, relative to the propylene resin composition.

[0009] The molded article according to the present invention contains the above-described propylene-based resin composition.

[0010] The method for producing a propylene resin composition according to the present invention is the method for producing a propylene resin composition described above. The process includes melting and kneading a propylene polymer (A) and a fragrance (B). The amount of fragrance (B) blended is 0.01 ppm by mass or more and 2000 ppm by mass or less relative to the propylene polymer (A). [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a propylene-based resin composition, a molded article, and a method for producing a propylene-based resin composition, which can be obtained in which odor is relatively reduced, impact strength at low temperatures is relatively high, and a molded article has relatively high flexibility against tensile deformation at room temperature and retention rate against tensile deformation at high temperatures. [Modes for carrying out the invention]

[0012] The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments.

[0013] [Propylene resin composition] The propylene-based resin composition according to this embodiment contains a propylene-based polymer (A) and a fragrance (B).

[0014] <Propylene-based polymer (A)> The propylene polymer (A) is a polymer containing 50% by mass or more monomer units derived from propylene. Examples of the propylene polymer (A) include propylene homopolymers, propylene random copolymers of propylene and monomers other than propylene, and heterophagic propylene polymerization materials. From the viewpoint of improving the rigidity and impact resistance of the molded article, the propylene resin composition according to this embodiment preferably contains a heterophagic propylene polymerization material as the propylene polymer (A). The propylene resin composition may contain only one type of propylene polymer (A) or two or more types.

[0015] The melt flow rate (MFR) of the propylene-based polymer (A) is preferably 0.1 g / 10 min or more and 300 g / 10 min or less, more preferably 1 g / 10 min or more and 100 g / 10 min or less, still more preferably 5 g / 10 min or more and 50 g / 10 min or less, and particularly preferably 10 g / 10 min or more and 50 g / 10 min or less, from the viewpoint of improving the molding processability of the propylene-based resin composition. The melt flow rate (MFR) of the propylene-based polymer (A) is measured by Method A under the conditions of a temperature of 230 °C and a load of 2.16 kg in accordance with the method specified in JIS K7210-1995.

[0016] In the propylene-based resin composition according to this embodiment, the propylene-based polymer (A) may be a recycled material. The recycled material means a polymer that is recycled through a recovery process after being once processed such as molding or after being used for some final application.

[0017] The content of the propylene-based polymer (A) is preferably 50.000% by mass or more, more preferably 75.000% by mass or more, and still more preferably 80.000% by mass or more, based on the propylene-based resin composition. Also, the content of the propylene-based polymer (A) is preferably 99.995% by mass or less, and more preferably 99.900% by mass or less, based on the propylene-based resin composition.

[0018] (Propylene homopolymer) The propylene-based resin composition according to this embodiment may contain a propylene homopolymer as the propylene-based polymer (A).

[0019] The isotactic pentad fraction of the propylene homopolymer is preferably 0.951 or higher, more preferably 0.961 or higher, even more preferably 0.965 or higher, and particularly preferably 0.970 or higher, from the viewpoint of improving rigidity. Furthermore, considering market availability, the isotactic pentad fraction of the propylene homopolymer is preferably 0.999 or lower, more preferably 0.995 or lower. In one embodiment, the isotactic pentad fraction of the propylene homopolymer is 0.951 or higher and 0.999 or lower.

[0020] In this specification, the isotactic pentad fraction refers to the isotactic fraction in pentad units. That is, the isotactic pentad fraction indicates the proportion of structures in which five monomer units derived from propylene are consecutively mesobonded, when viewed in pentad units.

[0021] The isotactic pentad fraction is, 13 This is a value measured by 13C-NMR spectroscopy. Specifically, 13 The ratio of the area of ​​the mmmm peak to the area of ​​the total absorption peak in the methyl carbon region obtained by 13C-NMR spectroscopy is defined as the isotactic pentad fraction. 13 A method for measuring isotactic pentad fractions using 1C-NMR spectroscopy is described, for example, in Macromolecules, 6, 925 (1973) by A. Zambelli et al. However, 13 The assignment of absorption peaks obtained by C-spectroscopy shall be based on the description in Macromolecules, 8, 687 (1975).

[0022] The isotactic pentad fraction of the propylene homopolymer can be adjusted to the above range by appropriately selecting the catalyst, donor, polymerization conditions, etc. Alternatively, propylene homopolymers with the desired isotactic pentad fraction can be obtained from commercially available products.

[0023] The aforementioned propylene homopolymer can be produced, for example, by carrying out a polymerization process in which propylene is polymerized using a polymerization catalyst.

[0024] Examples of polymerization catalysts include Ziegler-type catalysts; Ziegler-Natta-type catalysts; catalysts containing compounds of Group 4 transition metals having a cyclopentadienyl ring and alkylaluminoxanes; catalysts containing compounds of Group 4 transition metals having a cyclopentadienyl ring, compounds that react with said transition metal compounds to form ionic complexes, and organoaluminum compounds; and catalysts modified by supporting catalyst components (compounds of Group 4 transition metals having a cyclopentadienyl ring, compounds that form ionic complexes, organoaluminum compounds, etc.) on inorganic particles (silica, clay minerals, etc.).

[0025] Examples of the polymerization catalyst include catalysts described in Japanese Patent Publication No. 61-218606, Japanese Patent Publication No. 5-194685, Japanese Patent Publication No. 7-216017, Japanese Patent Publication No. 9-316147, Japanese Patent Publication No. 10-212319, Japanese Patent Publication No. 2004-182981, Japanese Patent Publication No. 2010-168545, Japanese Patent Publication No. 2011-246699, and the like.

[0026] Furthermore, a polymer obtained by prepolymerizing propylene in the presence of the polymerization catalyst can also be used as the polymerization catalyst.

[0027] Polymerization methods include, for example, bulk polymerization, solution polymerization, and gas-phase polymerization. Here, bulk polymerization refers to a method in which polymerization is carried out using liquid olefins 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, and octane. Gas-phase polymerization refers to a method in which a monomer in a gaseous state is used as a medium to polymerize a monomer in a gaseous state within that medium.

[0028] Polymerization methods include, for example, batch, continuous, and combinations thereof. The polymerization method may also be a multi-stage system in which multiple polymerization reactors are connected in series.

[0029] From an industrial and economically superior viewpoint, the polymerization method is preferably a continuous gas-phase polymerization method, or a bulk-gas-phase polymerization method that sequentially performs bulk polymerization and gas-phase polymerization.

[0030] The various conditions in the polymerization process (polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, polymerization time, etc.) should be appropriately determined according to the molecular structure of the target polymer.

[0031] In the above-mentioned method for producing the propylene homopolymer, other steps may be performed before or after the polymerization step. For example, after the polymerization step, the polymer may be dried at a temperature below the melting point of the polymer, if necessary, in order to remove residual solvent contained in the polymer, ultra-low molecular weight oligomers produced as by-products during manufacturing, etc. Examples of drying methods include those described in Japanese Patent Publication No. 55-75410 and Japanese Patent No. 2565753.

[0032] (Propylene random copolymer) The propylene resin composition according to this embodiment may contain a propylene random copolymer as the propylene polymer (A).

[0033] The propylene random copolymer contains monomer units derived from propylene and monomer units derived from monomers other than propylene. The propylene random copolymer preferably contains 0.01% to 20% by mass of monomer units derived from monomers other than propylene, based on 100% by mass of the total mass of the copolymer.

[0034] 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.

[0035] 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.

[0036] Examples of the propylene random copolymer include propylene-ethylene random copolymer, propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer, propylene-ethylene-1-butene random copolymer, propylene-ethylene-1-hexene random copolymer, and propylene-ethylene-1-octene random copolymer.

[0037] If the propylene random copolymer contains monomer units derived from ethylene, the content thereof is preferably 5.0% by mass or less, more preferably 2.9% by mass or less, and even more preferably 2.5% by mass or less, based on 100% by mass of the total mass of the propylene random copolymer. The content of monomer units derived from ethylene may also be 0.1% by mass or more, based on 100% by mass of the total mass of the propylene random copolymer.

[0038] The propylene random copolymer can be produced, for example, by polymerizing propylene and monomers other than propylene according to the polymerization catalyst, polymerization method, polymerization scheme, and polymerization conditions that can be used in the production of the propylene homopolymer described above.

[0039] (Heterophagic propylene polymerization material) The propylene-based resin composition according to this embodiment may contain a heterophagic propylene polymerization material as the propylene-based polymer (A).

[0040] The heterophagic propylene polymerization material is a mixture comprising: Polymer I containing 97% by mass or more monomer units derived from propylene (provided that the total mass of Polymer I is 100% by mass); and Polymer II containing 50% by mass or more and 99% by mass or less monomer units derived from propylene, and 1% by mass or more and 50% by mass or less 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 (provided that the total mass of Polymer II is 100% by mass).

[0041] The heterophagic propylene polymerization material can be produced, for example, by carrying out a first polymerization step of polymer I and a second polymerization step of polymer II in the presence of polymer I. These polymerization steps can be carried out according to the polymerization catalyst, polymerization method, polymerization scheme, and polymerization conditions that can be used in the production of the propylene homopolymer described above.

[0042] The heterophagic propylene polymerization material may have a total composition of polymer I and polymer II, where the sum of polymer I and polymer II is 100% by mass relative to 100% by mass of the total mass of the heterophagic propylene polymerization material. That is, in one embodiment, the heterophagic propylene polymerization material comprises polymer I, which contains 97% by mass or more of monomer units derived from propylene; and polymer II, which contains 50% by mass or more and 99% by mass or less of monomer units derived from propylene; and 1% by mass or more and 50% by mass or less 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.

[0043] As described above, polymer I contains 97% by mass or more monomer units derived from propylene (provided the total mass of polymer I is 100% by mass). Polymer I may be, for example, a propylene homopolymer, or it may contain monomer units derived from monomers other than propylene. If polymer I contains monomer units derived from monomers other than propylene, the content may be, for example, 0.01% by mass or more and 3% by mass or less, relative to 100% by mass of the total mass of polymer I.

[0044] Examples of monomers other than propylene include ethylene and α-olefins having four or more carbon atoms. Examples of α-olefins having four 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.

[0045] 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.

[0046] Examples of polymer I containing monomer units derived from monomers 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.

[0047] 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.

[0048] 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, but may be, for example, 0.900 or more, 0.925 or more, 0.930 or more, 0.961 or more, 0.965 or more, 0.968 or more, or 0.970 or more.

[0049] The content of polymer I is 50% to 99% by mass, preferably 60% to 95% by mass, based on 100% by mass of the total mass of the heterophagic propylene polymerization material.

[0050] As described above, polymer II contains 50% to 99% by mass of monomer units derived from propylene, and 1% to 50% by mass 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 (provided the total mass of polymer II is 100% by mass). 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.

[0051] Polymer II contains 50% to 99% by mass of monomer units derived from propylene, preferably 55% to 95% by mass, more preferably 60% to 90% by mass, and particularly preferably 65% ​​to 85% by mass. Polymer II also contains 1% to 50% by mass of monomer units derived from ethylene and at least one α-olefin selected from the group consisting of α-olefins having 4 to 12 carbon atoms, preferably 5% to 45% by mass, more preferably 10% to 40% by mass, and particularly preferably 15% to 35% by mass.

[0052] 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.

[0053] 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, and propylene-1-decene copolymer. Among these, polymer II is preferably propylene-ethylene copolymer, propylene-1-butene copolymer, or propylene-ethylene-1-butene copolymer, and more preferably propylene-ethylene copolymer.

[0054] The content of polymer II is 1% by mass or more and 50% by mass or less, preferably 5% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 35% by mass or less, and particularly preferably 15% by mass or more and 30% by mass or less, based on 100% by mass of the total mass of the heterophagic propylene polymerization material.

[0055] In the heterophagic propylene polymerization material, the content of monomer units derived from ethylene and at least one α-olefin selected from the group consisting of 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, based on 100% by mass of the total mass of the heterophagic propylene polymerization material.

[0056] The content of xylene-insoluble components (CXIS components) in the heterophagic propylene polymerization material is preferably 50% to 99% by mass, and more preferably 60% to 95% by mass, based on 100% by mass of the total mass of the heterophagic propylene polymerization material.

[0057] The content of xylene-soluble components (CXS components) in the heterophagic propylene polymerization material is preferably 1% to 50% by mass, more preferably 5% to 40% by mass, and particularly preferably 10% to 30% by mass, based on 100% by mass of the total mass of the heterophagic propylene polymerization material.

[0058] In this specification, xylene-insoluble components (CXIS components) refer to components insoluble in p-xylene contained in the polymer, and are solids obtained by the following method: A method for precipitating solid material by dissolving approximately 2 g of polymer in boiling p-xylene for 2 hours to obtain a solution, and then cooling the solution to 20°C.

[0059] Furthermore, in this specification, xylene-soluble components (CXS components) refer to components in the polymer other than the "CXIS components".

[0060] In this embodiment, the CXIS component in the heterophagic propylene polymerization material is considered to be mainly composed of polymer I, and the CXS component in the heterophagic propylene polymerization material is considered to be mainly composed of polymer II.

[0061] Examples of heterophagic propylene polymerization materials include (propylene)-(propylene-ethylene) polymerization materials, (propylene)-(propylene-ethylene-1-butene) polymerization materials, (propylene)-(propylene-ethylene-1-hexene) polymerization materials, (propylene)-(propylene-ethylene-1-octene) polymerization materials, (propylene)-(propylene-1-butene) polymerization materials, (propylene)-(propylene-1-hexene) polymerization materials, (propylene)-(propylene-1-octene) polymerization materials, and (propylene)-(propylene-1-decene) polymerization materials. Polymerization material, (propylene-ethylene)-(propylene-ethylene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-hexene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-octene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-decene) polymerization material, (propylene-ethylene)-(propylene-1-butene) polymerization material, (propylene-ethylene)-(propylene-1-hexene) polymerization material, (propylene-ethylene (propylene-1-octene) polymerization material, (propylene-ethylene)-(propylene-1-decene) polymerization material, (propylene-1-butene)-(propylene-ethylene) polymerization material, (propylene-1-butene)-(propylene-ethylene-1-butene) polymerization material, (propylene-1-butene)-(propylene-ethylene-1-hexene) polymerization material, (propylene-1-butene)-(propylene-ethylene-1-octene) polymerization material, (propylene-1-butene)-(propylene-ethylene-1-decene) polymerization material, (propylene-1-butene)-( (Propylene-1-butene) polymerization material, (Propylene-1-butene)-(Propylene-1-hexene) polymerization material, (Propylene-1-butene)-(Propylene-1-octene) polymerization material, (Propylene-1-butene)-(Propylene-1-decene) polymerization material, (Propylene-1-hexene)-(Propylene-1-hexene) polymerization material, (Propylene-1-hexene)-(Propylene-1-octene) polymerization material, (Propylene-1-hexene)-(Propylene-1-decene) polymerization material, (Propylene-1-octene)-(Propylene-1-octene) polymerization material,Examples include (propylene-1-octene)-(propylene-1-decene) polymerization materials.

[0062] Here, the description "(propylene)-(propylene-ethylene) polymerization material" means "a heterophagous propylene polymerization material in which polymer I is a propylene homopolymer and polymer II is a propylene-ethylene copolymer." The same applies to other similar expressions.

[0063] The heterophagic propylene polymerization material is preferably a (propylene)-(propylene-ethylene) polymerization material, a (propylene)-(propylene-ethylene-1-butene) polymerization material, a (propylene-ethylene)-(propylene-ethylene) polymerization material, a (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization material, or a (propylene-1-butene)-(propylene-1-butene) polymerization material, and more preferably a (propylene)-(propylene-ethylene) polymerization material.

[0064] The intrinsic viscosity number ([η]I) of polymer I is preferably 0.1 dL / g or more and 4.0 dL / g or less, more preferably 0.5 dL / g or more and 3.0 dL / g or less, and even more preferably 0.7 dL / g or more and 2.0 dL / g or less.

[0065] The intrinsic viscosity number ([η]II) of polymer II is preferably 0.1 dL / g or more and 10.0 dL / g or less, more preferably 0.5 dL / g or more and 10.0 dL / g or less, and even more preferably 1.0 dL / g or more and 9.0 dL / g or less.

[0066] One method for measuring the intrinsic viscosity number ([η]I) of polymer I is to extract the polymerized polymer I from the reactor in which it is polymerized and measure the intrinsic viscosity number of the polymer.

[0067] The intrinsic viscosity number of polymer II ([η]II) can be calculated, for example, using the intrinsic viscosity number of the heterophagic propylene polymerization material ([η]Total), the intrinsic viscosity number of polymer I ([η]I), and the content of polymer II and polymer I, by the following formula (i).

[0068] [η]II=([η]Total-[η]I×XI) / XII ···(i) [η] Total: Intrinsic viscosity number (dL / g) of heterophagic propylene polymerization material [η]I: Intrinsic viscosity number of polymer I (dL / g) XI: Ratio of the mass of polymer I to the total mass of heterophagic propylene polymerization material (mass of polymer I / mass of heterophagic propylene polymerization material) XII: Ratio of the mass of polymer II to the total mass of heterophagic propylene polymerization material (mass of polymer II / mass of heterophagic propylene polymerization material)

[0069] Here, XI and XII can be determined from the mass balance during polymerization.

[0070] Furthermore, XII may be calculated by measuring the heat of fusion of polymer I and the heat of fusion of the heterophagic propylene polymerization material and using the following formula. XII = 1 - (ΔHf)T / (ΔHf)P (ΔHf)T: Heat of fusion of heterophagic propylene polymerization material (J / g) (ΔHf)P: Heat of fusion of polymer I (J / g)

[0071] The intrinsic viscosity number ([η]CXIS) of the CXIS component is preferably 0.1 dL / g or more and 4.0 dL / g or less, more preferably 0.5 dL / g or more and 3.0 dL / g or less, and even more preferably 0.7 dL / g or more and 2.0 dL / g or less.

[0072] The intrinsic viscosity number ([η]CXS) of the CXS component is preferably 0.1 dL / g or more and 10.0 dL / g or less, more preferably 0.5 dL / g or more and 10.0 dL / g or less, and even more preferably 1.0 dL / g or more and 9.0 dL / g or less.

[0073] In this specification, the intrinsic viscosity number (unit: dL / g) is a value measured at a temperature of 135°C using tetralin as the solvent by the following method.

[0074] The reduced viscosity is measured at three points using an Ubbelohde viscometer at concentrations of 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 number is determined by extrapolation, where the concentration is extrapolated to zero. The method for calculating the intrinsic viscosity number by extrapolation is described, for example, on page 491 of "Polymer Solutions, Polymer Experiments 11" (Kyoritsu Shuppan Co., Ltd., 1982).

[0075] In one embodiment, the propylene-based resin composition according to this embodiment comprises a heterophagic propylene polymerization material comprising: polymer I containing 97% by mass or more monomer units derived from propylene; polymer II containing 50% by mass or more and 99% by mass or less monomer units derived from propylene, and 1% by mass or more and 50% by mass or less 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; wherein the content of polymer II is 1% by mass or more and 50% by mass or less relative to the heterophagic propylene polymerization material; and the intrinsic viscosity number of polymer II is 0.1 dL / g or more and 10.0 dL / g or less.

[0076] <Fragrance (B)> Fragrance (B) is a cyclic organic compound that does not contain nitrogen atoms or sulfur atoms, from the viewpoint of reducing odor. The cyclic organic compound preferably contains an oxygen atom. Furthermore, from the viewpoint of reducing odor, the cyclic organic compound is preferably a five-membered ring organic compound or a six-membered ring organic compound. The cyclic organic compound may also be a cyclic hydrocarbon compound.

[0077] Examples of such fragrances (B) include vanillin, 4,5-dimethyl-3-hydroxy-2(5H)-furanone, δ-dodecanolactone, cinnamaldehyde, sclareol, 4-methyl-2-phenyl-1,3-dioxolane, α-methylcinnamaldehyde, trans-cinnamaldehyde, benzoyl ethyl acetate, α-angelicalactone, 2',4'-dimethylacetophenone, γ-octanolactone, 2-ethoxynaphthalene, γ-hexanolactone, 2-acetylfuran, hydrocinnamic acid, 5-(hydroxymethyl)furfural, γ-nonanolactone, δ-undecanolactone, and γ-valerolactone. Among these, fragrance (B) is preferably at least one selected from the group consisting of vanillin, α-angelicalactone, trans-cinnamaldehyde, γ-valerolactone, ethyl benzoyl acetate, and hydrocinnamic acid, from the viewpoint of obtaining a molded article that has reduced odor, high impact strength at low temperatures, and high flexibility against tensile deformation at room temperature and high retention rate against tensile deformation at high temperatures, and more preferably at least one selected from the group consisting of vanillin, α-angelicalactone, trans-cinnamaldehyde, and γ-valerolactone. The propylene resin composition may contain only one type of fragrance (B) or two or more types.

[0078] The boiling point of the fragrance (B) at 1 atmosphere is preferably 150°C or higher, and more preferably 180°C to 350°C, from the viewpoint of suppressing volatilization and decomposition during molding.

[0079] The content of the fragrance (B) is, from the viewpoint of obtaining a molded article that has reduced odor, high impact strength at low temperatures, and high flexibility against tensile deformation at room temperature and retention rate against tensile deformation at high temperatures, 0.01 ppm by mass or more and 1000 ppm by mass or less relative to the propylene resin composition, preferably 0.1 ppm by mass or more and 500 ppm by mass or less, more preferably 0.5 ppm by mass or more and 300 ppm by mass or less, particularly preferably 1 ppm by mass or more and 150 ppm by mass or less, and especially preferably 5 ppm by mass or more and 80 ppm by mass or less.

[0080] The content of the aforementioned fragrance (B) is obtained by gas chromatography (GC) measurement. Specifically, a flash GC nosepiece Heracles NEO (AlphaMoss) is used as the instrument, and a metal capillary column MXT-5 (10m, 0.18mm ID, 0.4μm) is used as the column. A FID is used as the detector. Hydrogen is used as the carrier gas.

[0081] 8 g of the propylene resin composition to be used for measurement is weighed using a scale and sealed in a 20 mL vial. The vial is heated at 100°C for 30 minutes, and 5000 μL of the sample gas that has evaporated into the vial is collected using a headspace autosampler and measured by GC. The trap temperature at this time is 20°C, the split rate is 10 mL / min, and the trap time is 30 seconds.

[0082] For GC measurement, the inlet temperature and detector temperature are set to 250°C. The column oven temperature is held at 40°C for 10 seconds, then increased from 40°C to 100°C at a rate of 1°C / second, then increased from 100°C to 250°C at a rate of 1.5°C / second, and held at 250°C for 10 seconds.

[0083] For the quantitative determination of fragrances, a single-check curve for alkanes (product name: Headspace injection solution (C6C16), 11 composes, manufacturer: RESTEK, product number: 563121) is used, and the volatile components of each are converted to their respective alkane values. 10 μL of alkane is collected in a 20 mL vial, heated at 100°C for 30 minutes, and 5000 μL of the volatile sample gas collected in the vial is measured by GC. The measurement conditions are the same as above. After measurement, the area value obtained by summing the area intensities of the 11 peaks detected from the alkane is used as a reference, and the area intensity of the peak corresponding to the fragrance is used for quantitative determination. The analytical method was based on JIS K 0114.

[0084] <Ethylene-α-olefin copolymer (C)> The propylene-based resin composition according to this embodiment may further contain an ethylene-α-olefin copolymer (C). The ethylene-α-olefin copolymer (C) is a copolymer containing monomer units derived from ethylene and monomer units derived from α-olefins having 4 or more carbon atoms, and substantially does not contain monomer units derived from propylene. The propylene-based resin composition may contain only one type of the ethylene-α-olefin copolymer (C), or it may contain two or more types.

[0085] The ethylene-α-olefin copolymer (C) may have a total content of monomer units derived from ethylene and monomer units derived from α-olefins having 4 or more carbon atoms, which may be 100% by mass, based on 100% by mass of the total mass of the copolymer.

[0086] 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, 1-decene, and the like. The α-olefin having 4 to 12 carbon atoms is preferably 1-butene, 1-hexene, or 1-octene. The α-olefin having 4 to 12 carbon atoms may be an α-olefin having a cyclic structure such as vinylcyclopropane or vinylcyclobutane.

[0087] Examples of the ethylene-α-olefin copolymer (C) include an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, an ethylene-1-decene copolymer, an ethylene-(3-methyl-1-butene) copolymer, a copolymer of ethylene and an α-olefin having a cyclic structure, and the like.

[0088] In the ethylene-α-olefin copolymer (C), the content of the monomer unit derived from the α-olefin 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 still more preferably 24% by mass or more and 49% by mass or less, based on 100% by mass of the total mass of the ethylene-α-olefin copolymer.

[0089] The density of the ethylene-α-olefin copolymer (C) is preferably 0.850 g / cm 3 or more and 0.890 g / cm 3 or less, more preferably 0.850 g / cm 3 or more and 0.880 g / cm 3 or less, and still more preferably 0.850 g / cm 3 or more and 0.870 g / cm 3 or less, from the viewpoint of the impact resistance of the molded body.

[0090] The melt flow rate of the ethylene-α-olefin copolymer (C) is preferably 0.1 g / 10 min or more and 80 g / 10 min or less. The melt flow rate of the ethylene-α-olefin copolymer can be measured by Method A, under the conditions of a temperature of 190°C and a load of 2.16 kg, in accordance with the method specified in JIS K7210-1995.

[0091] The content of ethylene-α-olefin copolymer (C) is preferably 1% by mass or more, and more preferably 5% by mass or more, relative to the propylene resin composition. Furthermore, the content of ethylene-α-olefin copolymer (C) is preferably 40% by mass or less, and more preferably 30% by mass or less, relative to the propylene resin composition.

[0092] Ethylene-α-olefin copolymer (C) can be produced by polymerizing ethylene and α-olefins having 4 or more carbon atoms using a polymerization catalyst.

[0093] Examples of polymerization catalysts include homogeneous catalysts such as metallocene catalysts and Ziegler-Natta type catalysts.

[0094] Examples of homogeneous catalysts include catalysts containing compounds of Group 4 transition metals having a cyclopentadienyl ring and alkylaluminoxanes; catalysts containing compounds of Group 4 transition metals having a cyclopentadienyl ring, compounds that react with the transition metal compounds to form ionic complexes, and organoaluminum compounds; and catalysts modified by supporting catalyst components (compounds of Group 4 transition metals having a cyclopentadienyl ring, compounds that form ionic complexes, organoaluminum compounds, etc.) on inorganic particles (silica, clay minerals, etc.).

[0095] Examples of Ziegler-Natta type catalysts include catalysts that combine a titanium-containing solid transition metal component with an organometallic component.

[0096] Commercially available ethylene-α-olefin copolymers (C) may be used. Examples of commercially available ethylene-α-olefin copolymers (C) include Engage® manufactured by Dow Chemical Japan Ltd., Tuffmer® manufactured by Mitsui Chemicals, Inc., Neozex® and Ultzex® manufactured by Prime Polymer Co., Ltd., and Excellen FX®, Sumikasen®, and Esprene SPO® manufactured by Sumitomo Chemical Co., Ltd.

[0097] Ethylene-α-olefin copolymer (C) can also be contained in the xylene-soluble component (CXS component) of a propylene-based resin composition. In this case, the propylene-based resin composition itself is dissolved with p-xylene, fillers, pigment components, etc. are removed by filtration, and then the xylene-soluble component (CXS) and xylene-insoluble component (CXIS) are separated in the same manner as the heterophagic propylene polymerization material described above. In this case, ethylene-α-olefin copolymer (C) is usually contained in the xylene-soluble component (CXS).

[0098] When the propylene-based resin composition according to this embodiment contains an ethylene-α-olefin copolymer (C), the content of xylene-soluble components (CXS components) in the propylene-based resin composition is preferably 1% to 50% by mass, more preferably 5% to 40% by mass, even more preferably 8% to 35% by mass, particularly preferably 10% to 32% by mass, and especially preferably 15% to 28% by mass, based on 100% by mass of the total mass of the propylene-based resin composition.

[0099] When the propylene-based resin composition according to this embodiment contains an ethylene-α-olefin copolymer (C), the intrinsic viscosity number ([η]CXS) of the CXS component is preferably 0.1 dL / g or more and 10.0 dL / g or less, more preferably 0.5 dL / g or more and 8.0 dL / g or less, even more preferably 1.0 dL / g or more and 6.0 dL / g or less, and particularly preferably 1.5 dL / g or more and 4.0 dL / g or less.

[0100] <Other ingredients> The propylene-based resin composition according to this embodiment may contain other components besides those listed above. Other components include, for example, fillers, 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 resins, ethylene / vinyl alcohol copolymer resins, fluororesins, polyacetals, grafted polyphenylene ether resins and polyphenylene sulfide resins, polyurethanes, polyamides, polyester resins (e.g., polyethylene terephthalate, polybutylene terephthalate), and poly Examples include carbonates, polysulfones, polyetheretherketones, polyethersulfones, aromatic polyester resins, polybutadiene, 1,2-polybutadiene, polyisoprene, styrene / butadiene copolymers, butadiene / acrylonitrile copolymers, natural rubber, etc.), epoxy resins, diallyl phthalate prepolymers, silicone resins, silicone rubber, epichlorohydrin rubber, acrylic rubber, and PLA resins (polylactic acid) produced by polymerizing plant-derived monomers extracted from bio-raw materials. Other examples include 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, foaming nucleating agents, plasticizers, flame retardants, crosslinking agents, crosslinking aids, brightness enhancers, antibacterial agents, light diffusing agents, light stabilizers, and weathering agents.

[0101] Examples of the fillers include inorganic fillers and organic fillers. Examples of the inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloons, aluminum hydroxide, magnesium hydroxide, dolomite, calcium sulfate, potassium titanate, barium sulfate, talc, clay, mica, glass flakes, glass beads, glass fibers, aluminum silicate, calcium silicate, montmorillonite, bentonite, molybdenum sulfide, graphite, calcium carbonate, metal powders (aluminum, copper, iron, lead, etc.), and silica. Examples of the organic fillers include polyester, aromatic polyamide, cellulose, and vinylon. The propylene resin composition may contain only one type of filler, or it may contain two or more types.

[0102] The melt flow rate of the propylene-based resin composition according to this embodiment is 0.3 g / 10 min to 200 g / 10 min, preferably 0.4 g / 10 min to 90 g / 10 min, and more preferably 1 g / 10 min to 60 g / 10 min, from the viewpoint of obtaining a molded article with reduced odor, high impact strength at low temperatures, and high flexibility against tensile deformation at room temperature and retention rate against tensile deformation at high temperatures. The melt flow rate (MFR) of the propylene-based resin composition is calculated theoretically based on the following formula. M[R] = 10^{(Propylene polymer (A) content) × Log10M[A] + (Resin material content) × Log10M[P] + (Fragrance content) × Log10M[PF]} In the formula, M[R] represents the MFR of the propylene resin composition, M[A] represents the MFR of the propylene polymer (A), M[P] represents the MFR of the resin material, and M[PF] represents the MFR of the fragrance. Also, M[PF] is set to 1g / 10min. The resin material is the component of the propylene resin composition excluding the fragrance (including the masterbatch).

[0103] The density of the propylene-based resin composition according to this embodiment is preferably 1.30 g / cm³. 3 The following, and more preferably 1.20 g / cm³ 3The following, and more preferably 1.10 g / cm³ 3 The following applies. Furthermore, the density of the propylene-based resin composition is preferably 0.80 g / cm³. 3 The above, more preferably 0.85 g / cm³ 3 The above is preferable, and more preferably 0.90 g / cm³ 3 This concludes the procedure. The density of the propylene resin composition is measured according to the method specified in Method A of JIS K7112-1980. The sample is subjected to annealing as described in JIS K6760-1995.

[0104] The propylene-based resin composition according to this embodiment contains a propylene-based polymer (A) and a fragrance (B), has a melt flow rate of 0.3 g / 10 min to 200 g / 10 min, the fragrance (B) is a cyclic organic compound that does not contain nitrogen atoms or sulfur atoms, and the content of the fragrance (B) is 0.01 ppm by mass to 1000 ppm by mass relative to the propylene-based resin composition. As a result, a molded article can be obtained in which odor is relatively reduced, impact strength at low temperatures is relatively high, and flexibility against tensile deformation at room temperature and retention rate against tensile deformation at high temperatures are relatively high.

[0105] [Method for producing propylene resin compositions] The method for producing the propylene-based resin composition according to this embodiment is the method for producing the propylene-based resin composition described above, and includes the step of melt-kneading a propylene-based polymer (A) and a fragrance (B).

[0106] The amount of fragrance (B) blended is, from the viewpoint of obtaining a molded article that reduces odor, has high impact strength at low temperatures, and has high flexibility against tensile deformation at room temperature and high retention rate against tensile deformation at high temperatures, 0.01 ppm by mass or more and 2000 ppm by mass or less relative to the propylene polymer (A), preferably 0.02 ppm by mass or more and 1000 ppm by mass or less, more preferably 0.05 ppm by mass or more and 750 ppm by mass or less, particularly preferably 0.1 ppm by mass or more and 100 ppm by mass or less, and especially preferably 1 ppm by mass or more and 70 ppm by mass or less.

[0107] The propylene-based resin composition according to this embodiment may be obtained by melt-kneading a propylene-based polymer (A), a fragrance (B), and, if necessary, an ethylene-α-olefin copolymer (C) and other components. The fragrance (B) may be obtained by adding the fragrance (B) to a small amount of the propylene-based polymer (A), and then kneading the resulting masterbatch with the propylene-based polymer (A).

[0108] The temperature during melting and kneading may be 180°C or higher, 180°C to 300°C, or 180°C to 250°C.

[0109] For melt mixing, a Banbury mixer, a single-screw extruder, a twin-screw co-rotating extruder, etc., can be used.

[0110] The order in which each raw material component is mixed is not particularly limited. For example, all components may be mixed together at once, or some components may be mixed first, and then the resulting mixture may be mixed with the other components.

[0111] The method for producing the propylene resin composition according to this embodiment may include other optional steps. Optional steps include, for example, crushing, purification, and molding into pellet form. Purification steps include, for example, washing with water, aqueous and / or oily chemicals, microbial treatment, magnetic separation, and specific gravity separation. Molding steps are not particularly limited and include, for example, injection molding.

[0112] The shape of the propylene-based resin composition obtained in this way is not particularly limited and may be in the form of strands, sheets, plates, or pellets. A pelletized propylene-based resin composition can be produced, for example, by forming a strand-shaped resin composition and then cutting it to an appropriate length.

[0113] From the viewpoint of improving the moldability of the propylene resin composition and the production stability when manufacturing the molded product, the shape of the propylene resin composition before molding is preferably in the form of pellets with a length of about 1 to 50 mm.

[0114] [Molded body] The molded article according to this embodiment includes the propylene-based resin composition described above. That is, the propylene-based resin composition described above can be used as a material for molding to form a molded article. Preferably, the propylene-based resin composition can be used as an injection molding material. An example of an injection-molded article manufactured using the propylene-based resin composition as an injection molding material will be described below.

[0115] Injection-molded articles can be manufactured by injection molding. Examples of injection molding methods include 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.

[0116] Injection-molded products can be used, for example, in automotive materials, home appliance materials, containers, and the like.

[0117] The molded article according to this embodiment, by containing the above-mentioned propylene-based resin composition, has a relatively reduced odor, relatively high impact strength at low temperatures, and relatively high flexibility against tensile deformation at room temperature and retention rate against tensile deformation at high temperatures.

[0118] The present invention includes the following embodiments. [1] Contains a propylene polymer (A) and a fragrance (B), The melt flow rate is between 0.3g / 10min and 200g / 10min. The fragrance (B) is a cyclic organic compound that does not contain nitrogen atoms and sulfur atoms. A propylene resin composition in which the content of the fragrance (B) is 0.01 ppm by mass or more and 1000 ppm by mass or less, relative to the propylene resin composition. [2] The propylene resin composition according to [1], wherein the melt flow rate is 0.4 g / 10 min or more and 90 g / 10 min or less. [3] The propylene polymer (A) contains a propylene homopolymer, The propylene-based resin composition according to [1] or [2], wherein the isotactic pentad fraction of the propylene homopolymer is 0.951 or more and 0.999 or less. [4] The propylene polymer (A) contains a propylene random copolymer, The propylene resin composition according to any one of [1] to [3], wherein, if the propylene random copolymer contains monomer units derived from ethylene, the content thereof is 2.9% by mass or less based on 100% by mass of the total mass of the propylene random copolymer. [5] The propylene polymer (A) contains a heterophagic propylene polymerization material, The heterophagic propylene polymerization material comprises polymer I, which contains 97% by mass or more monomer units derived from propylene; and polymer II, which contains 50% by mass or more and 99% by mass or less monomer units derived from propylene, and 1% by mass or more and 50% by mass or less 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. The content of polymer II is 1% by mass or more and 50% by mass or less, based on 100% by mass of the total mass of the heterophagic propylene polymerization material. The propylene resin composition according to any one of [1] to [4], wherein the intrinsic viscosity number of the polymer II is 0.1 dL / g or more and 10.0 dL / g or less. [6] The propylene resin composition according to any one of [1] to [5], wherein the cyclic organic compound contains an oxygen atom. [7] The propylene resin composition according to any one of [1] to [6], wherein the cyclic organic compound is a five-membered ring organic compound or a six-membered ring organic compound. [8] The propylene resin composition according to any one of [1] to [7], wherein the fragrance (B) is at least one selected from the group consisting of vanillin, α-angelicalactone, trans-cinnamaldehyde, and γ-valerolactone. [9] The propylene-based resin composition according to any one of [1] to [8], wherein the propylene-based polymer (A) is made from recycled material. A molded article comprising a propylene-based resin composition described in any one of

[10] [1] to [9]. A method for producing a propylene resin composition described in any one of

[11] [1] to [9], The process includes melting and kneading a propylene polymer (A) and a fragrance (B). A method for producing a propylene resin composition, wherein the amount of fragrance (B) blended is 0.01 ppm by mass or more and 2000 ppm by mass or less relative to the propylene polymer (A). [Examples]

[0119] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples.

[0120] In the following explanation, "%" and "parts" used to express quantities refer to mass unless otherwise specified. Furthermore, the operations described below were performed under normal temperature (23°C) and atmospheric pressure (0.1013 MPa (absolute)) conditions unless otherwise specified.

[0121] [Method for measuring physical properties] (1) Melt flow rate (MFR, unit: g / 10 min) The MFRs of propylene polymers (A) and resin materials were measured in accordance with Method A as specified in JIS K7210-1:2014 and K7210-2:2014, under conditions of a temperature of 230°C and a load of 2.16 kgf. However, the MFR of ethylene-α-olefin copolymer (C) was measured under conditions of a temperature of 190°C and a load of 2.16 kgf.

[0122] The MFR (M[R]) of the propylene resin composition was calculated theoretically based on the following formula. M[R] = 10^{(Propylene polymer (A) content) × Log10M[A] + (Resin material content) × Log10M[P] + (Fragrance content) × Log10M[PF]} The MFR of the propylene resin composition is denoted as M[R], the MFR of the propylene polymer (A) as M[A], the MFR of the resin material as M[P], and the MFR of the fragrance as M[PF]. Furthermore, M[PF] was set to 1g / 10min.

[0123] (2) Intrinsic viscosity number ([η], unit: dL / g) Using an Ubbelohde viscometer, the reduced viscosity was measured for multiple concentrations, and the intrinsic viscosity was determined by plotting the reduced viscosity against the concentration and extrapolating the concentration to zero. More specifically, using the method described on page 491 of "Polymer Solutions, Polymer Experiments 11" (Kyoritsu Shuppan Co., Ltd., 1982), the reduced viscosity was measured at three points with concentrations of 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL, and the intrinsic viscosity was determined by plotting the reduced viscosity against the concentration and extrapolating the concentration to zero.

[0124] (3) Density The density was measured according to the method specified in Method A of JIS K7112-1980. The sample was also subjected to annealing as described in JIS K6760-1995.

[0125] [Components used in the examples and comparative examples] The components used in the examples and comparative examples are shown below.

[0126] (1) Propylene polymer (A) <Heterophagic propylene polymerization material (A-1)> Using a polymerization catalyst obtained by the method described in Example 1 of Japanese Patent Publication No. 2004-182981, a heterophagic propylene polymerization material (A-1) was produced as a propylene-based polymer (A) by liquid-phase polymerization, containing 79% by mass of (a) propylene homopolymer component as polymer I and 21% by mass of (b) propylene-ethylene copolymer component as polymer II (where the total mass of the heterophagic propylene polymerization material is 100% by mass). The physical properties were as follows. • Melt flow rate (230℃, load 2.16kgf): 55g / 10min (a) Propylene homopolymer component Intrinsic viscosity: 0.90dL / g Isotactic pentad fraction: 0.984 (b) Propylene-ethylene copolymer component Intrinsic viscosity: 6.0dL / g Ethylene-derived monomer unit content: 32% by mass

[0127] <Heterophagic propylene polymerization material (A-2)> Using a polymerization catalyst obtained by the method described in Example 1 of Japanese Patent Publication No. 2004-182981, a heterophagic propylene polymerization material (A-2) was produced as a propylene-based polymer (A) by liquid-phase polymerization, containing 71% by mass of (a) a propylene homopolymer component as polymer I and 29% by mass of (b) a propylene-ethylene copolymer component as polymer II (where the total mass of the heterophagic propylene polymerization material is 100% by mass). The physical properties were as follows. • Melt flow rate (230℃, load 2.16kgf): 10g / 10min (a) Propylene homopolymer component Intrinsic viscosity: 1.20dL / g Isotactic pentad fraction: 0.980 (b) Propylene-ethylene copolymer component Intrinsic viscosity: 2.7dL / g Ethylene-derived monomer unit content: 37% by mass

[0128] (2)Fragrance (B) • Vanillin: CAS No. 121-33-5, manufactured by TCI Corporation. • trans-cinnamaldehyde: CAS No. 14371-10-9, manufactured by Sigma-Aldrich. • γ-Valerolactone: CAS No. 108-29-2, manufactured by TCI Corporation. • α-Angelicalactone: CAS No. 591-12-8, manufactured by TCI Corporation. Methyl myristate: CAS No. 124-10-7, manufactured by TCI, "Methyl Myristate" • Leaf alcohol: CAS No. 928-96-1, manufactured by TCI, "cis-3-Hexen-1-ol" • 2-Methylthiazoline: CAS No. 2346-00-1, manufactured by TCI.

[0129] (3) Ethylene-α-olefin copolymer (C) <Ethylene-α-olefin copolymer (C-1)> Dow Chemical Japan's "Engage® 8200" (ethylene-1-octene copolymer) was used. The physical properties were as follows: • Ethylene-derived monomer content: 63% by mass (1-octene-derived monomer content: 37% by mass) • Melt flow rate (190℃, load 2.16kgf): 5g / 10min ·Density: 0.870g / cm 3

[0130] (4) Filling material Talc (D-1): CAS No. 14807-96-6

[0131] (5) Other additives (5-1) Neutralizing agent • Neutralizing agent 1: CAS No. 1592-23-0, "Calcium Stearate" manufactured by Sakai Chemical Industry Co., Ltd.

[0132] (5-2) Antioxidants • Antioxidant 1: CAS No. 90498-90-1, "SumiLizer GA80" manufactured by Sumitomo Chemical Co., Ltd. • Antioxidant 2: CAS No. 26741-53-7, Songnox6260 manufactured by Songwon Co., Ltd. • Antioxidant 3: CAS No. 6683-19-8, BASF "Irganox 1010" • Antioxidant 4: CAS No. 31570-04-4, BASF "Irgafos 168"

[0133] (5-3) Weather-resistant agent • Weather-resistant agent 1: CAS No. 91788-83-9, ADEKA "LA52"

[0134] [Example 1] A heterophagic propylene polymerization material (A-1): 66% by mass, ethylene-α-olefin copolymer (C-1): 18% by mass, and talc (D-1): 16% by mass were uniformly mixed with 100 parts by mass of the total polymer and filler, along with 1:0.05 parts by mass of neutralizing agent, 1:0.05 parts by mass of antioxidant, 2:0.05 parts by mass of antioxidant, and 1:0.05 parts by mass of weather-resistant agent. The mixture was then fed into a twin-screw kneader (twin-screw extruder) (TEX44αII, manufactured by Japan Steel Works) from the upstream raw material inlet and melt-kneaded to obtain a resin material. The melt-kneading conditions were a cylinder temperature of 200°C, a discharge rate of 50 kg / hour, a screw rotation speed of 200 rpm, and an oxygen concentration of 2% in the feed hopper. The oxygen concentration in the feed hopper was measured by inserting a sensor from a portable oxygen concentration meter into the purge resin inlet attached to the feed hopper. Furthermore, the condition of an oxygen concentration of 2% was achieved by circulating nitrogen gas to the feed hopper section. The MFR of the resin material was 35 g / 10 min.

[0135] Furthermore, 100 parts by mass of heterophagic propylene polymerization material (A-1), 0.05 parts by mass of antioxidant 3, 0.05 parts by mass of antioxidant 4, and 0.084 parts by mass of vanillin were uniformly mixed. The mixture was then introduced into a twin-screw kneader (twin-screw extruder) (TEX44αII, manufactured by Japan Steel Works) from the upstream raw material inlet and melt-kneaded, and melt-kneaded under the same conditions to obtain a fragrance masterbatch.

[0136] 100 parts by mass of the resin material and 6 parts by mass of the fragrance masterbatch were mixed to obtain the propylene-based resin composition of Example 1.

[0137] [Examples 2-4, Comparative Examples 2-4] The propylene resin compositions of Examples 2-4 and Comparative Examples 2-4 were obtained in the same manner as in Example 1, except that the fragrances shown in Table 1 were used instead of vanillin.

[0138] [Comparative Example 1] A propylene-based resin composition of Comparative Example 1 was obtained in the same manner as in Example 1, except that a masterbatch without fragrance was prepared and mixed with the resin material.

[0139] [Example 5] The propylene-based resin composition of Example 5 was obtained in the same manner as in Example 1, except that 100 parts by mass of the resin material and 0.1 parts by mass of the fragrance masterbatch were mixed.

[0140] [Example 6] The propylene-based resin composition of Example 6 was obtained in the same manner as in Example 1, except that 100 parts by mass of the resin material and 12 parts by mass of the fragrance masterbatch were mixed.

[0141] [Example 7] The propylene-based resin composition of Example 7 was obtained in the same manner as in Example 1, except that the resin material was obtained using heterophagic propylene polymerization material (A-2) instead of heterophagic propylene polymerization material (A-1).

[0142] [Example 8] The propylene-based resin composition of Example 8 was obtained in the same manner as in Example 2, except that the resin material was obtained using heterophagic propylene polymerization material (A-2) instead of heterophagic propylene polymerization material (A-1).

[0143] [Comparative Example 5] A propylene-based resin composition for Comparative Example 5 was obtained in the same manner as in Example 7, except that a fragrance masterbatch was not mixed in.

[0144] [Example 9] The fragrance masterbatch obtained in Example 1 was used as the propylene-based resin composition in Example 9.

[0145] [Comparative Example 6] A masterbatch was obtained in the same manner as in Example 1, except that no fragrance was mixed in, to obtain the propylene-based resin composition of Comparative Example 6.

[0146] (Measurement of fragrance content) The fragrance content was measured using gas chromatography (GC).

[0147] Specifically, a flash GC nosepiece Heracles NEO (manufactured by AlphaMoss) was used as the instrument, and a metal capillary column MXT-5 (10m, 0.18mm ID, 0.4μm) was used as the column.

[0148] A FID detector was used. Hydrogen was used as the carrier gas.

[0149] Eight g of each propylene resin composition used for measurement was weighed using a scale and sealed in a 20 mL vial. The vial was heated at 100°C for 30 minutes, and 5000 μL of the volatile sample gas in the vial was collected using a headspace autosampler and measured by GC. The trap temperature was 20°C, the split rate was 10 mL / min, and the trap time was 30 seconds.

[0150] For the GC measurement conditions, the inlet temperature was set to 250°C and the detector temperature to 250°C. The column oven temperature was held at 40°C for 10 seconds, then increased from 40°C to 100°C at a rate of 1°C / second, then increased from 100°C to 250°C at a rate of 1.5°C / second, and held at 250°C for 10 seconds.

[0151] For the quantitative determination of the fragrance, a single-check quantity curve for the fragrance was created using each propylene resin composition adjusted to a fragrance concentration of 830 ppm, and the fragrance was quantified using the area intensity of the peak corresponding to the fragrance. The GC measurement conditions were the same as described above.

[0152] (Method for determining the intrinsic viscosity number of the CXS component in resin materials) Four grams of the aforementioned resin material were dissolved in hot xylene at 150°C over two hours, and talc, an unwanted xylene component, was removed by filtration using cylindrical filter paper. The resulting xylene solution was then cooled to 20°C, causing the polymer to precipitate. The precipitated polymer was filtered off, and ethanol was added to the remaining xylene solution, causing the polymer to precipitate again. After filtering and drying, the mass was measured to be 0.63 g. This polymer was designated as the xylene-soluble component (CXS component), and its intrinsic viscosity was measured using the method described in "(2) Intrinsic Viscosity" above. The intrinsic viscosity was found to be 2.0 dL / g. The precipitated and filtered polymer component was designated as the xylene-insoluble component (CXIS component).

[0153] Similarly, for the heterophagic propylene polymerization material (A-1), the above method was used except for the step of removing talc, and the intrinsic viscosity number of the CXS component of the heterophagic propylene polymerization material (A-1) was measured, yielding a value of 5.9 dL / g. The intrinsic viscosity of the CXIS component was 0.99.

[0154] Similarly, for heterophagic propylene polymerization material (A-2), the above method was used except for the step of removing talc, and the intrinsic viscosity number of the CXS component of heterophagic propylene polymerization material (A-2) was measured, yielding a value of 5.9 dL / g. The intrinsic viscosity of the CXIS component was 1.30.

[0155] [evaluation] (Odor measurement) Each propylene-based resin composition was supplied to an injection molding machine (Meiki Seisakusho's "M70 type injection molding machine"), and a flat plate with a length of 60 mm, a width of 60 mm, and a thickness of 2.0 mm was molded at a molten resin temperature of 200°C, a mold temperature of 40°C, a filling pressure of 15 MPa, a holding pressure of 4.3 MPa, a holding time of 40 seconds, a total cycle time of 60 seconds, and a molded product removal temperature of 60°C or less. Subsequently, the flat plate was cut to a size of 60 mm in length, 30 mm in width, and 2.0 mm in thickness.

[0156] Next, the three cut flat plates were placed in a 0.5L odorless glass bottle, the lid was closed, and the bottle was heated in an oven at 80°C for 2 hours. After that, the glass bottle was left to stand at 60°C for a while. Then, a panelist conducted an odor test on the flat plates inside the glass bottle.

[0157] Specifically, one panelist scored the odors in 0.1-point increments based on the following scoring criteria.

[0158] 1 point: I don't smell anything. 2 points: I can smell it, but it's not unpleasant. 3 points: The smell is clearly noticeable, but not yet unpleasant. 4 points: It has an unpleasant odor. 5 points: It has a very unpleasant smell. 6 points: The smell is unbearable.

[0159] The quality of the odors perceived by the panelists was also recorded. The results are shown in Table 1. Note that a lower odor score indicates less odor, and a score of 3.0 or lower is considered acceptable.

[0160] (Tensile modulus of elasticity) Each propylene-based resin composition was supplied to an injection molding machine (M70 injection molding machine manufactured by Meiki Seisakusho), and dumbbell-shaped test specimens were molded under the following conditions: molten resin temperature 200°C, mold temperature 40°C, filling pressure 15 MPa, holding pressure 4.3 MPa, holding time 40 seconds, total cycle time 60 seconds, and molded product removal temperature 60°C or lower. Two days after molding, the tensile modulus was measured at 23°C and 80°C using the dumbbell-shaped test specimens under conditions of 23°C and 50% Rh, in accordance with JIS K7161-2:2014. The test speed was 1.0 mm / min. The ratio of the tensile modulus at 80°C to the tensile modulus at 23°C was calculated and used as the retention rate. The results are shown in Table 1.

[0161] (Charpy impact strength) The dumbbell-shaped test specimen described above was cut to a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. A V-notch was then applied to the surface formed by the 80 mm length and 4 mm thickness. The Charpy impact strength was then measured at -30°C in accordance with JIS K 7111-1. Since the specimen is susceptible to slight scratches and voids from the molding process, only values ​​above the lower limit of the tolerance range were used.

[0162] [Table 1]

[0163] As can be seen from the results in Table 1, molded articles containing the propylene resin compositions of each example that satisfy all the constituent requirements of the present invention have relatively reduced odor, relatively high impact strength at low temperatures, and relatively high flexibility against tensile deformation at room temperature and retention rate against tensile deformation at high temperatures.

Claims

1. It contains a propylene polymer (A) and a fragrance (B), The melt flow rate is 0.3 g / 10 min or more and 200 g / 10 min or less. The fragrance (B) is a cyclic organic compound that does not contain nitrogen atoms and sulfur atoms. The content of the fragrance (B) is 0.01 ppm by mass or more and 1000 ppm by mass or less, relative to the propylene resin composition. The propylene polymer (A) contains a heterophagic propylene polymerization material. The heterophagic propylene polymerization material comprises polymer I, which contains 97% by mass or more monomer units derived from propylene; and polymer II, which contains 50% by mass or more and 99% by mass or less monomer units derived from propylene, and 1% by mass or more and 50% by mass or less 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. The content of polymer II is 1% by mass or more and 50% by mass or less, based on 100% by mass of the total mass of the heterophagic propylene polymerization material. A propylene-based resin composition wherein the intrinsic viscosity number of polymer II is 0.1 dL / g or more and 10.0 dL / g or less.

2. The propylene-based resin composition according to claim 1, wherein the melt flow rate is 0.4 g / 10 min or more and 90 g / 10 min or less.

3. The propylene polymer (A) contains a propylene homopolymer, The propylene-based resin composition according to claim 1, wherein the isotactic pentad fraction of the propylene homopolymer is 0.951 or more and 0.999 or less.

4. The propylene polymer (A) contains a propylene random copolymer, The propylene-based resin composition according to claim 1, wherein, if the propylene random copolymer contains monomer units derived from ethylene, the content thereof is 2.9% by mass or less based on 100% by mass of the total mass of the propylene random copolymer.

5. The propylene-based resin composition according to claim 1, wherein the cyclic organic compound contains an oxygen atom.

6. The propylene-based resin composition according to claim 1, wherein the cyclic organic compound is a five-membered ring organic compound or a six-membered ring organic compound.

7. The propylene resin composition according to claim 1, wherein the fragrance (B) is at least one selected from the group consisting of vanillin, α-angelicalactone, trans-cinnamaldehyde, and γ-valerolactone.

8. The propylene-based resin composition according to claim 1, wherein the propylene-based polymer (A) is a recycled material.

9. A molded article comprising the propylene resin composition according to any one of claims 1 to 8.

10. A method for producing a propylene resin composition according to any one of claims 1 to 8, The process includes melting and kneading a propylene polymer (A) and a fragrance (B). A method for producing a propylene resin composition, wherein the amount of fragrance (B) blended is 0.01 ppm by mass or more and 2000 ppm by mass or less relative to the propylene polymer (A).

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