Propylene resin composition

Abstract

Provided is a propylene-based resin composition from which it is possible to form a molded article capable of achieving both high thermal stability and suppression of odor generation.　This propylene-based resin composition contains (A) a propylene-based polymer, (B) an inorganic filler, and (C) a hindered amine-based photostabilizer. When a molded article obtained by molding said propylene-based resin composition is heated for 15 minutes at 100°C, the concentration of amine compounds in volatile gas generated therefrom is 3-40 mass ppm.　

Description

Technical Field

[0001] The present invention relates to a propylene-based resin composition.

Background Art

[0002] A propylene-based resin composition containing a propylene-based polymer has good mechanical properties and is used in various applications. Molded articles of the propylene-based resin composition can be particularly preferably used, for example, as interior members in an instrument panel and a door trim of an automobile.

[0003] The interior of an automobile can be a closed space with a high temperature of, for example, 50°C or higher, especially in summer. Therefore, interior members of an automobile are required to be hardly deteriorated by heat, that is, to have high heat stability.

[0004] Further, especially when the propylene-based resin composition contains an inorganic filler such as talc, an odor may be generated from the interior member made of the molded article, which gives discomfort to a driver or a passenger. For the purpose of suppressing the generation of such an odor, an aspect in which zinc stearate is further blended with a propylene-based resin composition containing talc as an inorganic filler is known (see Non-Patent Document 1).

Prior Art Documents

Non-Patent Documents

[0005]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, while the propylene-based resin composition disclosed in Non-Patent Document 1 above can suppress odor generation, its thermal stability was not sufficient.

[0007] Therefore, there is a need for a propylene-based resin composition that can form interior components (molded articles) that achieve both high thermal stability and suppression of odor generation. [Means for solving the problem]

[0008] The inventors of this invention diligently conducted research to solve the above problems and have now completed this invention.

[0009] In other words, the present invention provides the following [1] to [6]. [1] (A) A propylene polymer and (B) Inorganic filler and (C) A propylene resin composition comprising a hindered amine-based light stabilizer, A propylene-based resin composition wherein the concentration of amine compounds in the volatile gas generated when a molded article, formed from the propylene-based resin composition under the following molding conditions X, is heated at 100°C for 15 minutes, is 3 to 40 ppm by mass. Molding conditions X: Molten resin temperature 200°C, mold temperature 40°C, filling pressure 15 MPa, holding pressure 4.3 MPa, holding time 40 s, molded body removal temperature ≤ 60°C, total cycle time 60 s [2] (B) The propylene resin composition according to [1], wherein the inorganic filler is talc. [3] (B) A propylene resin composition according to [1] or [2], wherein the inorganic filler comprises at least one selected from the group consisting of glass, calcium carbonate, and basic magnesium sulfate. [4] (D) Further comprising an olefin polymer, (D) The propylene resin composition according to any one of [1] to [3], wherein the olefin polymer is at least one polymer selected from the group consisting of ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, ethylene-(3-methyl-1-butene) copolymer, and copolymer of ethylene and an α-olefin having a cyclic structure. [5] The propylene resin composition according to any one of [1] to [4], wherein the content of (C) a hindered amine light stabilizer is 0.3 parts by mass or less when the total amount of (A) a propylene polymer and (B) an inorganic filler is 100 parts by mass. [6] (C) A propylene resin composition according to any one of [1] to [6], wherein the hindered amine light stabilizer is other than bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate. [7] A propylene resin composition according to any one of [1] to [6], wherein the concentration of the amine compound in the volatile gas is 3 to 30 ppm by mass. [8] (E) Further containing a metal-based additive, (E) A propylene resin composition according to any one of [1] to [7], wherein the metal additive is at least one compound selected from the group consisting of fatty acid zinc salts and fatty acid aluminum salts. [9] (E) The propylene resin composition according to [8], wherein the metal additive is zinc fatty acid.

[10] A molded article comprising a propylene resin composition described in any one of [1] to [9].

[11] A method for producing a molded article comprising the propylene resin composition according to claim 10, comprising steps (α') and (β'). Step (α'): A step of grinding a molded article containing the propylene resin composition described in any one of claims 1 to 9 to obtain a pulverized product. Step (β'): A step of molding the pulverized product to obtain a molded article containing the propylene resin composition described in any one of claims 1 to 9. [Effects of the Invention]

[0010] According to the present invention, a propylene-based resin composition capable of forming an interior member (molded body) that achieves both high thermal stability and suppression of odor generation can be provided.

Mode for Carrying Out the Invention

[0011] Hereinafter, embodiments of the present invention will be specifically described. The present invention is not limited to the specific embodiments shown below, and can be appropriately modified without departing from the object of the present invention.

[0012] In this specification, "AA~BB" means AA or more and BB or less. Here, AA and BB each represent a numerical value, and AA <BB. The unit of AA is the same as the unit described immediately after BB, unless otherwise specified.

[0013] In this specification, the term "monomer unit" means a structural unit having a structure obtained by polymerizing the monomer.

[0014] In this specification, the term "α-olefin" means an olefin having a carbon-carbon double bond at the terminal.

[0015] 1. Propylene-based resin composition The propylene-based resin composition according to the embodiment of the present invention is (A) a propylene-based polymer, (B) an inorganic filler, (C) a hindered amine-based light stabilizer, and is a propylene-based resin composition, when the molded body obtained by molding the propylene-based resin composition under the following molding conditions X is heated at 100°C for 15 minutes, the concentration of amine compounds in the volatile gas generated is 3 to 40 mass ppm. Molding conditions X: Melt resin temperature 200°C, mold temperature 40°C, filling pressure 15 MPa, holding pressure 4.3 MPa, holding time 40 s, molded body removal temperature ≤ 60°C, total cycle time 60 s Hereinafter, the components that can be included in the propylene-based resin composition of the present embodiment will be described.

[0016] (1) Component (A) Polypropylene-based polymer A polypropylene-based polymer is a polymer that contains more than 50% by mass of propylene units relative to all constituent units (100% by mass). The propylene units in the polypropylene-based polymer are usually 100% by mass or less. Examples of polypropylene-based polymers include propylene homopolymers; and copolymers of propylene and other monomers copolymerizable therewith. The copolymer may be a random copolymer or a block copolymer.

[0017] Examples of other monomers copolymerizable with propylene include olefins other than propylene (e.g., ethylene, olefins having 4 or more carbon atoms).

[0018] Olefins having 4 or more carbon atoms may be linear olefins or branched olefins. Olefins having 4 or more carbon atoms may have a cyclic structure, and for example, may be α-olefins having a cyclic structure such as vinylcyclopropane and vinylcyclobutane.

[0019] Examples of olefins other than propylene copolymerizable with propylene include α-olefins other than propylene (e.g., ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene). Olefins other than propylene copolymerizable with propylene are preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene, and more preferably ethylene, propylene, 1-butene, 1-hexene, and 1-octene.

[0020] The polypropylene-based resin composition of this embodiment may contain two or more component (A) polypropylene-based polymers as the component (A) polypropylene-based polymer. The propylene-based resin composition of this embodiment may contain a propylene homopolymer (component (A-2)) obtained by polymerizing only one type of propylene monomer as component (A) propylene polymer, or it may contain a propylene polymer obtained by polymerizing two or more types of monomers in any combination of proportions.

[0021] Examples of component (A) propylene polymers include component (A-2) propylene homopolymers and random copolymers of propylene and other monomers copolymerizable therewith (hereinafter also referred to as propylene random copolymers).

[0022] Examples of combinations of propylene polymers when two or more components (A) propylene polymers are included include combinations of two or more propylene homopolymers with different weight-average molecular weights, and combinations of polymer (I) and polymer (II) described below.

[0023] The propylene-based resin composition of this embodiment may contain, as component (A) propylene polymer, component (A-1) heterophagic propylene polymer material.

[0024] Here, component (A-1) heterophagic propylene polymer material refers to a material that contains two or more propylene polymers, in which these two or more propylene polymers are miscible and form separate phases from each other.

[0025] Examples of component (A-1) heterophagic propylene polymer materials include the following combinations of polymer (I) and polymer (II).

[0026] Here, polymer (I) is a polymer having propylene units in an amount greater than 80% by mass and less than or equal to 100% by mass relative to the total amount of constituent units.

[0027] Furthermore, polymer (II) is a copolymer of propylene units and at least one monomer unit selected from the group consisting of ethylene units and α-olefin units having 4 or more carbon atoms. Polymer (II) is preferably a polymer having propylene units in an amount greater than 0% by mass and less than 90% by mass relative to the total amount of constituent units, and more preferably a polymer having propylene units greater than 0% by mass and less than 80% by mass.

[0028] Polymer (I) may be a propylene homopolymer or a copolymer of propylene and another monomer. Polymers (I) and (II) may each consist of only one polymer or contain two or more polymers.

[0029] From the viewpoint of improving the rigidity and impact resistance of molded articles formed from propylene resin compositions, it is preferable that the propylene polymer includes one or more selected from the group consisting of propylene homopolymers and heterophagic propylene polymer materials.

[0030] Propylene polymers are used to improve the rigidity of molded articles made from propylene resin compositions. 13 The isotactic pentad fraction (also called the [mmmm] fraction), measured by 13C-NMR, is preferably 0.97 or higher, and more preferably 0.98 or higher. The closer the isotactic pentad fraction of a propylene polymer is to 1, the higher the stereoregularity of the molecular structure of the propylene polymer and the higher the crystallinity of the propylene polymer. If the propylene polymer is a copolymer, the isotactic pentad fraction can be measured for the chain of propylene units in the copolymer.

[0031] From the viewpoint of improving the processability of the propylene-based resin composition during molding, the propylene-based polymer has a melt flow rate (MFR) measured in accordance with JIS K7210-1:2014 and K7210-2:2014 under conditions of 230°C and a load of 2.16 kgf, preferably 1 g / 10 min or more, more preferably 3 g / 10 min or more, preferably 500 g / 10 min or less, and even more preferably 3 g / 10 min to 300 g / 10 min.

[0032] Propylene polymers can be produced, for example, by the following polymerization method using a polymerization catalyst.

[0033] Examples of polymerization catalysts include Ziegler-type catalyst systems; Ziegler-Natta-type catalyst systems; catalyst systems containing transition metal compounds of Group 4 of the periodic table having a cyclopentadienyl ring and alkylaluminoxanes; catalyst systems containing transition metal compounds of Group 4 of the periodic table having a cyclopentadienyl ring, compounds that react with them to form ionic complexes, and organoaluminum compounds; and catalyst systems in which catalyst components (e.g., transition metal compounds of Group 4 of the periodic table having a cyclopentadienyl ring, compounds that form ionic complexes, organoaluminum compounds, etc.) are supported on inorganic particles (e.g., silica, clay minerals, etc.) and modified. Alternatively, prepolymerization catalysts prepared by prepolymerizing monomers such as ethylene or α-olefins in the presence of such catalyst systems may be used. An example of a Ziegler-Natta-type catalyst system is a catalyst system that uses a combination of a titanium-containing solid transition metal component and an organometallic component.

[0034] Examples of such catalyst systems include those 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, and Japanese Patent Publication No. 2004-182981.

[0035] 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 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, or 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.

[0036] Examples of polymerization methods include batch, continuous, and combinations thereof. The polymerization method may also be a multi-stage method using multiple polymerization reactors connected in series.

[0037] Various conditions in the polymerization method (polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, polymerization time, etc.) can be appropriately determined according to the target propylene polymer.

[0038] In the production of propylene polymers, in order to remove residual solvents contained in the obtained propylene polymer and ultra-low molecular weight oligomers produced as by-products during production, the obtained propylene polymer may be held at a temperature at which the residual solvents and other impurities such as oligomers can volatilize, and at a temperature lower than the melting point of the propylene polymer. Examples of methods for removing such residual solvents and other impurities such as oligomers include the methods described in Japanese Patent Publication No. 55-75410 and Japanese Patent No. 2565753.

[0039] The component (A-2) propylene homopolymer has an intrinsic viscosity number [η] of preferably 0.1 to 5 dL / g, more preferably 0.5 to 5 dL / g, and even more preferably 0.7 to 4 dL / g, from the viewpoint of improving the fluidity of the propylene resin composition when melted and the toughness of the molded article formed from the propylene resin composition. Here, the intrinsic viscosity number [η] is a value measured at 135°C using tetralin as the solvent.

[0040] Furthermore, the molecular weight distribution Mw / Mn of the propylene homopolymer is preferably 2 or more and less than 10, more preferably 3 to 8, and even more preferably 3 to 7, from the viewpoint of improving the fluidity of the resin composition during melting and the toughness of the molded article containing the resin composition. Here, Mw represents the weight-average molecular weight and Mn represents the number-average molecular weight. The molecular weight distribution is a value measured by gel permeation chromatography (also known as GPC).

[0041] Examples of propylene-based random copolymers include random copolymers containing propylene units and ethylene units (hereinafter also referred to as random polymer (1)); random copolymers containing propylene units and α-olefin units having 4 or more carbon atoms (hereinafter also referred to as random polymer (2)); and random copolymers containing propylene units, ethylene units, and α-olefin units having 4 or more carbon atoms (hereinafter also referred to as random polymer (3)).

[0042] α-olefins having 4 or more carbon atoms that can constitute a propylene-based random copolymer are preferably α-olefins having 4 to 10 carbon atoms. Examples of α-olefins having 4 to 10 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene, with 1-butene, 1-hexene, and 1-octene being preferred.

[0043] Examples of random copolymers (2) include propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer, and propylene-1-decene random copolymer.

[0044] Examples of random copolymers (3) include propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, and propylene-ethylene-1-decene copolymer.

[0045] The ethylene unit content in the random copolymer (1) is preferably 0.1 to 40% by mass.

[0046] The content of α-olefin units having 4 or more carbon atoms in the random copolymer (2) is preferably 0.1 to 40% by mass, more preferably 0.1 to 30% by mass, and even more preferably 2 to 15% by mass.

[0047] The total content of ethylene units and α-olefin units having 4 or more carbon atoms in the random copolymer (3) is preferably 0.1 to 40% by mass, more preferably 0.1 to 30% by mass, and even more preferably 2 to 15% by mass.

[0048] The propylene unit content in these random copolymers (1) to (3) is preferably 60 to 99.9% by mass, respectively.

[0049] As previously explained, polymer (I) in component (A-1) heterophagic propylene polymer material is a polymer containing propylene units in an amount exceeding 80% by mass and not exceeding 100% by mass relative to the total amount of constituent units. The total content of monomer units other than propylene units in polymer (I) is usually 0% by mass or more and less than 20% by mass, when the mass of polymer (I) is taken as 100% by mass, and may be 0% by mass or 0.01% by mass or more.

[0050] Examples of monomer units other than propylene units that polymer (I) may have include ethylene units and α-olefin units having 4 or more carbon atoms. The α-olefin having 4 or more carbon atoms that can constitute polymer (I) is preferably an α-olefin having 4 to 10 carbon atoms, more preferably 1-butene, 1-hexene, and 1-octene, and even more preferably 1-butene.

[0051] Examples of polymers (I) include propylene homopolymer, 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] Among these, propylene homopolymer, propylene-ethylene copolymer, propylene-1-butene copolymer, and propylene-ethylene-1-butene copolymer are preferred as polymer (I), and propylene homopolymer is more preferred from the viewpoint of rigidity of the molded article formed from the propylene resin composition.

[0053] As previously explained, polymer (II) is a copolymer of a propylene unit and at least one monomer unit selected from the group consisting of ethylene units and α-olefin units having 4 or more carbon atoms.

[0054] The total content of ethylene units and α-olefin units having 4 or more carbon atoms in polymer (II) is preferably 20 to 80% by mass, and more preferably 20 to 60% by mass, when the mass of polymer (II) is 100% by mass.

[0055] The α-olefins that can constitute polymer (II) and have four or more carbon atoms are preferably α-olefins with 4 to 10 carbon atoms, and examples similar to those of α-olefins that can constitute polymer (I) can be given.

[0056] 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. Polymer (II) is preferably propylene-ethylene copolymer, propylene-1-butene copolymer, and propylene-ethylene-1-butene copolymer, and more preferably propylene-ethylene copolymer.

[0057] The content of polymer (II) in component (A-1) heterophagic propylene polymer material is preferably 1 to 50% by mass, more preferably 1 to 45% by mass, even more preferably 5 to 40% by mass, and particularly preferably 8 to 32% by mass, when the total mass of polymer (I) and polymer (II) is taken as 100% by mass.

[0058] Examples of component (A-1) heterophagic propylene polymer materials include combinations of polymer (I) being a propylene homopolymer, a propylene homopolymer and a (propylene-ethylene) copolymer, a propylene homopolymer and a (propylene-ethylene-1-butene) copolymer, a propylene homopolymer and a (propylene-ethylene-1-hexene) copolymer, a propylene homopolymer and a (propylene-ethylene-1-octene) copolymer, a propylene homopolymer and a (propylene-1-butene) copolymer, a propylene homopolymer and a (propylene-1-hexene) copolymer, a propylene homopolymer and a (propylene-1-octene) copolymer, and a propylene homopolymer and a (propylene-1-decene) copolymer.

[0059] Furthermore, the heterophagic propylene polymer material may be a combination in which polymer (I) is a polymer containing propylene units and monomer units other than propylene units. If we describe the types of polymer (I) first and the types of polymer (II) second, specific examples of such heterophagic propylene polymer materials include a combination of (propylene-ethylene) copolymer and (propylene-ethylene) copolymer, a combination of (propylene-ethylene) copolymer and (propylene-ethylene-1-butene) copolymer, a combination of (propylene-ethylene) copolymer and (propylene-ethylene-1-hexene) copolymer, and a combination of (propylene-ethylene) copolymer and (propylene-ethylene-1 Combinations with (octene) copolymer, combinations of (propylene-ethylene) copolymer and (propylene-ethylene-1-decene) copolymer, combinations of (propylene-ethylene) copolymer and (propylene-1-butene) copolymer, combinations of (propylene-ethylene) copolymer and (propylene-1-hexene) copolymer, combinations of (propylene-ethylene) copolymer and (propylene-1-octene) copolymer, combinations of (propylene-ethylene) copolymer and (propylene-1-decene) copolymer Combinations, combinations of (propylene-1-butene) copolymer and (propylene-ethylene) copolymer, combinations of (propylene-1-butene) copolymer and (propylene-ethylene-1-butene) copolymer, combinations of (propylene-1-butene) copolymer and (propylene-ethylene-1-hexene) copolymer, combinations of (propylene-1-butene) copolymer and (propylene-ethylene-1-octene) copolymer, combinations of (propylene-1-butene) copolymer and (propylene-ethylene-1-decene) copolymer Combinations with polymers, combinations of (propylene-1-butene) copolymer and (propylene-1-butene) copolymer, combinations of (propylene-1-butene) copolymer and (propylene-1-hexene) copolymer, combinations of (propylene-1-butene) copolymer and (propylene-1-octene) copolymer, combinations of (propylene-1-butene) copolymer and (propylene-1-decene) copolymer, combinations of (propylene-1-hexene) copolymer and (propylene-1-hexene) copolymer,Examples include combinations of (propylene-1-hexene) copolymer and (propylene-1-octene) copolymer, combinations of (propylene-1-hexene) copolymer and (propylene-1-decene) copolymer, combinations of (propylene-1-octene) copolymer and (propylene-1-octene) copolymer, and combinations of (propylene-1-octene) copolymer and (propylene-1-decene) copolymer.

[0060] The component (A-1) heterophagic propylene polymer material that can be included in the propylene-based resin composition of this embodiment is preferably a combination of propylene homopolymer and (propylene-ethylene) copolymer, a combination of propylene homopolymer and (propylene-ethylene-1-butene) copolymer, a combination of (propylene-ethylene) copolymer and (propylene-ethylene) copolymer, a combination of (propylene-ethylene) copolymer and (propylene-ethylene-1-butene) copolymer, and a combination of (propylene-1-butene) copolymer and (propylene-1-butene) copolymer, with the combination of propylene homopolymer and (propylene-ethylene) copolymer being more preferred.

[0061] Heterophasic propylene polymer materials can be produced by multi-stage polymerization, which includes a polymerization step to produce polymer (I) and a polymerization step to produce polymer (II) in the presence of polymer (I) produced in the preceding step. Polymerization can be carried out using the catalyst system exemplified as a catalyst usable for the production of the propylene-based polymer.

[0062] The intrinsic viscosity number of polymer (I) (P portion) (hereinafter referred to as [η]I) is preferably 0.1 to 5 dL / g, more preferably 0.5 to 5 dL / g, and even more preferably 0.7 to 4 dL / g.

[0063] The intrinsic viscosity number of polymer (II) (EP portion) (hereinafter referred to as [η]II) is preferably 1 to 10 dL / g, more preferably 2 to 10 dL / g, and even more preferably 2.5 to 8 dL / g.

[0064] Furthermore, the ratio of [η]II to [η]I ([η]II / [η]I) is preferably 0.5 to 20, more preferably 0.8 to 10, and even more preferably 0.9 to 9.

[0065] If the propylene polymer is a polymer material consisting of polymer (I) and polymer (II) formed by multi-stage polymerization, the polymer formed in the first stage of polymerization can be partially extracted from the polymerization tank and its intrinsic viscosity number determined. The intrinsic viscosity number of the polymer material finally obtained by multi-stage polymerization (hereinafter referred to as ([η]Total)) can then be determined. Using these intrinsic viscosity numbers and the content of each polymer, the intrinsic viscosity number of the polymer formed in the second stage of polymerization can be calculated.

[0066] Furthermore, if the polymer material consisting of polymer (I) and polymer (II) is manufactured by a method in which polymer (I) is obtained in the preceding polymerization step and polymer (II) is obtained in the subsequent polymerization step, the procedure for measuring and calculating the respective contents of polymer (I) and polymer (II), and the intrinsic viscosity numbers ([η]Total, [η]I, [η]II) is as follows.

[0067] The intrinsic viscosity number [η]II of polymer (II) is calculated using the following formula based on the intrinsic viscosity number ([η]I) of polymer (I) obtained in the preceding polymerization step, the intrinsic viscosity number ([η]Total) of the final polymer after the subsequent polymerization step (i.e., the polymer consisting of polymer (I) and polymer (II)) measured by the method described above, and the content of polymer (II) contained in the final polymer.

[0068] [η]II=([η]Total-[η]I×XI) / XII [η] Total: Intrinsic viscosity number of the final polymer (unit: dL / g) [η]I: Intrinsic viscosity number of polymer (I) (unit: dL / g) XI: Mass ratio of polymer (I) to the final polymer XII: Mass ratio of polymer (II) to final polymer Furthermore, XI and XII are determined from the mass balance during polymerization.

[0069] The mass ratio XII of polymer (II) to the final polymer may be calculated using the following formula, based on the respective heats of fusion of polymer (I) and the final polymer. XII = 1 - (ΔHf)T / (ΔHf)P (ΔHf)T: Heat of fusion of the final polymer (polymer (I) and polymer (II)) (unit: cal / g) (ΔHf)P: Heat of fusion of polymer (I) (unit: cal / g)

[0070] Furthermore, the molecular weight distribution (Mw / Mn) of polymer (I) measured by GPC is preferably 1 or more and less than 10, more preferably 2 or more and less than 7, and even more preferably 3 or more and less than 5.

[0071] The content of the propylene polymer in the propylene resin composition of this embodiment is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, preferably 70% by mass or less, and preferably 30 to 70% by mass or less, when the total amount of the propylene resin composition is considered as 100% by mass.

[0072] (2) Component (B) Inorganic filler The propylene resin composition of this embodiment may contain component (B) an inorganic filler. The propylene resin composition may contain only one type of inorganic filler or two or more types.

[0073] Examples of inorganic fillers include glass, silicate minerals (e.g., talc), silicon dioxide (e.g., silica), titanium dioxide, iron oxide, aluminum oxide (e.g., alumina), 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, and cadmium sulfide.

[0074] The shape of the inorganic filler is not particularly limited. The inorganic filler may be in the form of a plate, needle, fiber, or any other shape.

[0075] From the viewpoint of rigidity, impact resistance, and dimensional stability of the molded article formed from the propylene resin composition, it is preferable that the propylene resin composition contains talc, which is a plate-shaped silicate mineral, as an inorganic filler. As talc, for example, commercially available MWUPN-TT-H (manufactured by Hayashi Chemical Co., Ltd.) can be used.

[0076] The inorganic filler content in the propylene resin composition is preferably 0.01 to 50% by mass, and more preferably 0.03 to 30% by mass, when the total amount of the propylene resin composition is considered to be 100% by mass.

[0077] When a propylene-based resin composition contains talc as an inorganic filler, the talc content in the propylene-based resin composition is preferably 0.01 to 50% by mass, more preferably 0.03 to 45% by mass, even more preferably 1% to 40% by mass, and particularly preferably 3% to 30% by mass, relative to the propylene-based resin composition.

[0078] (3) Component (C) Hindered amine light stabilizer The propylene resin composition of this embodiment may contain component (C) a hindered amine light stabilizer. The hindered amine light stabilizer that can be used has the function of capturing radicals generated by light (ultraviolet light) in the propylene resin composition (molded article) and preventing degradation by the decomposition of hydroperoxide. Component (C) the hindered amine light stabilizer may be either a low molecular weight hindered amine light stabilizer or a high molecular weight hindered amine light stabilizer.

[0079] Examples of hindered amine-based light stabilizers include, (1) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, (2) A mixture containing bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, (3) Bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, (4) Reaction product of bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) decandioate, 1,1-dimethylethyl hydroperoxide, and octane, (5) 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, (6) Ester mixture of 2,2,6,6-tetramethyl-4-piperidinol and higher fatty acids, (7) Tetrakis(2,2,6,6-tetra-methyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, (8) Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, (9) Polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, (10) Poly[{(6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}}], (11) Dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine) polycondensate of N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, (12) N,N',N'',N'''-Tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidine-4-yl)amino)-triazine-2-yl)-4,7-diazadecane-1,10-diamine, (13) Mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β,β,β',β'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]dimethyl}-1,2,3,4-butanetetracarboxylate, (14) N-(2,2,6,6-tetramethyl-4-piperidyl)maleimide, (15) Bis(1-undecaneoxy-2,2,6,6-tetramethylpiperidine-4-yl)carbonate, (16) 2,2,6,6-tetramethylpiperidine-4-yl hexadecanoate, (17) 2,2,6,6-Tetramethylpiperidine-4-yl octadecanoate Examples include copolymers consisting of α-olefins with 20 to 24 carbon atoms. These may be used individually or in combination of two or more types.

[0080] Hindered amine-based light stabilizers are used in resin compositions (molded articles) that have excellent light stability. (1) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, (4) Reaction product of bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) decandioate, 1,1-dimethylethyl hydroperoxide, and octane, (7) Tetrakis(2,2,6,6-tetra-methyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, (8) Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, (9) Polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, (10) Poly[{(6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}}], (14) It is preferable to use a copolymer consisting of N-(2,2,6,6-tetramethyl-4-piperidyl)maleimide and an α-olefin having 20 to 24 carbon atoms.

[0081] As component (C) a hindered amine-based light stabilizer, it is more preferable to use component (C-1) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate represented by the following formula (e.g., ADEKASTAB LA-77 (manufactured by ADEKA)), component (C-2) a sterically hindered amine oligomer "N-(2,2,6,6-tetramethyl-4-piperidyl) maleimide and a copolymer consisting of α-olefins having 20 to 24 carbon atoms (e.g., UVINUL® 5050H (manufactured by BASF Japan))", and component (C-3) Butanedioc acid, dimethyl ester, polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol CAS. 65447-77-0 (e.g., TINUVIN 622 SF (manufactured by BASF)).

[0082] [ka]

[0083] [ka]

[0084] In the propylene-based resin composition of this embodiment, the content of component (C) hindered amine-based light stabilizer is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, usually more than 0 parts by mass, preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.03 parts by mass or more, when the total amount of component (A) propylene polymer and component (B) inorganic filler contained in the propylene-based resin composition is 100 parts by mass.

[0085] By keeping the content of hindered amine-based light stabilizers below the upper limit, the odor of molded articles made from propylene resin compositions can be effectively reduced, and their thermal stability can be effectively improved.

[0086] (4) Component (D) Olefin polymer The propylene resin composition of this embodiment may contain component (D) an olefin polymer. Olefin polymers are, for example, olefin copolymers containing ethylene units and α-olefin units having 4 or more carbon atoms. Hereinafter, olefin copolymers containing ethylene units and α-olefin units having 4 or more carbon atoms will also be referred to as ethylene-α-olefin copolymers.

[0087] The propylene resin composition preferably contains an ethylene-α-olefin copolymer as component (D) olefin polymer. The propylene resin composition may contain only one type of ethylene-α-olefin copolymer, or it may contain two or more types.

[0088] The content of ethylene-α-olefin copolymer in the propylene resin composition is preferably 0 to 40% by mass, and more preferably 0 to 30% by mass, when the total amount of the propylene resin composition is 100% by mass.

[0089] In the ethylene-α-olefin copolymer, the content of ethylene units and α-olefin units having 4 or more carbon atoms is preferably 95% by mass or more, more preferably 98% by mass or more, even more preferably 99% by mass or more, and usually 100% by mass or less, or may be 100% by mass, based on the total mass of the ethylene-α-olefin copolymer.

[0090] Examples of α-olefins having 4 or more carbon atoms that can constitute an ethylene-α-olefin copolymer include α-olefins having 4 to 12 carbon atoms (e.g., 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene). Preferably, the α-olefins having 4 or more carbon atoms that can constitute an ethylene-α-olefin copolymer are 1-butene, 1-hexene, and 1-octene. The α-olefins having 4 or more carbon atoms may have a cyclic structure and may also be α-olefins having 4 or more carbon atoms (e.g., vinylcyclopropane, vinylcyclobutane).

[0091] The ethylene-α-olefin copolymer is preferably at least one polymer selected from the group consisting of 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 α-olefins having a cyclic structure. It is more preferable to use component (D-1) ethylene-1-butene copolymer as the ethylene-α-olefin copolymer.

[0092] The content of α-olefin units having 4 or more carbon atoms in the ethylene-α-olefin copolymer is preferably 1 to 49% by mass, more preferably 5 to 49% by mass, and even more preferably 24 to 49% by mass, relative to the total amount of the ethylene-α-olefin copolymer.

[0093] The ethylene-α-olefin copolymer has a melt flow rate (MFR) of preferably 0.1 g / 10 min to 80 g / 10 min, measured in accordance with JIS K7210-1:2014 and K7210-2:2014 under conditions of 190°C and a load of 2.16 kgf.

[0094] The density of the ethylene-α-olefin copolymer is 0.850 to 0.890 g / cm³ from the viewpoint of improving the impact resistance of molded articles formed from propylene-based resin compositions. 3Preferably, it is 0.850~0.880 g / cm³. 3 It is more preferable that the concentration be 0.855~0.870 g / cm³. 3 It is even more preferable that this be the case.

[0095] Ethylene-α-olefin copolymers can be produced, for example, by polymerizing ethylene and α-olefins having four or more carbon atoms using a polymerization catalyst. Examples of polymerization catalysts include those previously described as polymerization catalysts for producing propylene-based polymers.

[0096] As component (D) ethylene-α-olefin copolymer, commercially available products may be used. Examples of such commercially available products include ethylene-butene-1 copolymers such as "Engage® 7447" manufactured by Dow Chemical Japan, "Tafmer®" manufactured by Mitsui Chemicals, "Neozex®" and "Urtzex®" manufactured by Prime Polymer, and "Excellen FX®", "Sumikasen®", and "Esplen SPO®" manufactured by Sumitomo Chemical.

[0097] (5) Components (E) Metal-based additives The propylene resin composition of this embodiment may contain a metal-based additive (E). Preferably, the metal-based additive (E) is at least one compound selected from the group consisting of fatty acid zinc salts and fatty acid aluminum salts. By containing the metal-based additive (E) in the propylene resin composition, the odor of the molded article formed from the propylene resin composition can be effectively reduced, and the thermal stability can be effectively improved.

[0098] The propylene resin composition of this embodiment may contain only one type of fatty acid zinc salt as component (E) metal additive, or it may contain two or more types.

[0099] The propylene resin composition of this embodiment may contain only one type of fatty acid aluminum salt as component (E) metal additive, or it may contain two or more types.

[0100] Here, a fatty acid refers to a compound represented as R-COOH, where R represents a monovalent aliphatic hydrocarbon group.

[0101] The monovalent aliphatic hydrocarbon group represented by R may be linear or branched, and is preferably linear.

[0102] The monovalent aliphatic hydrocarbon group represented by R may or may not have a carbon-carbon unsaturated bond, and it is preferable that it does not have a carbon-carbon unsaturated bond.

[0103] Examples of carbon-carbon unsaturated bonds that a monovalent aliphatic hydrocarbon group represented by R may have include carbon-carbon double bonds and carbon-carbon triple bonds, with carbon-carbon double bonds being preferred.

[0104] In component (E), a fatty acid salt which is a metal-based additive, the number of carbon atoms in the fatty acid is preferably 10 or more, more preferably 11 or more, preferably 20 or less, and more preferably 18 or less.

[0105] Component (E), the metal-based additive, is a zinc fatty acid salt, which may be a mono(fatty acid) zinc salt or a di(fatty acid) zinc salt. Preferably, the zinc fatty acid salt is a di(fatty acid) zinc salt.

[0106] Component (E), the metal-based additive, is an aluminum fatty acid salt. It may be a mono(fatty acid)aluminum salt, a di(fatty acid)aluminum salt, or a tri(fatty acid)aluminum salt. Preferably, the aluminum fatty acid salt is a di(fatty acid)aluminum salt.

[0107] The propylene resin composition of this embodiment may also contain a calcium fatty acid salt as component (E) a metal-based additive.

[0108] Component (E), the metal-based additive, is a calcium fatty acid salt, which may be a mono(fatty acid) calcium salt or a di(fatty acid) calcium salt. Preferably, the calcium fatty acid salt is a di(fatty acid) calcium salt.

[0109] Component (E) Examples of zinc fatty acid salts, which are metal-based additives, include zinc fatty acids formed by the bonding of monounsaturated fatty acids such as lauric acid, stearic acid, palmitic acid, and linoleic acid, and polyunsaturated fatty acids such as oleic acid and linoleic acid with zinc. These fatty acids may contain saturated or unsaturated functional groups and / or cyclic structures, as well as hydroxyl groups.

[0110] Component (E) Metal-based additives include aluminum fatty acid salts, such as monounsaturated fatty acids like lauric acid, stearic acid, palmitic acid, and linoleic acid, and polyunsaturated fatty acids like oleic acid and linoleic acid, which are bonded to aluminum. These fatty acids may contain saturated or unsaturated functional groups and / or cyclic structures, as well as hydroxyl groups.

[0111] Component (E) Examples of calcium fatty acid salts, which are metal-based additives, include calcium fatty acids formed by the bonding of monounsaturated fatty acids such as lauric acid, stearic acid, palmitic acid, and linoleic acid, and polyunsaturated fatty acids such as oleic acid and linoleic acid with calcium. These fatty acids may contain saturated or unsaturated functional groups and / or cyclic structures, as well as hydroxyl groups.

[0112] The propylene resin composition of this embodiment may also contain calcium hydroxide as component (E) a metal additive.

[0113] If the propylene-based resin composition of this embodiment contains two or more compounds as component (E) metal-based additives, it is preferable that it contains zinc distearate and aluminum distearate, and more preferably that it further contains calcium hydroxide in addition to zinc distearate and aluminum distearate.

[0114] When a propylene-based resin composition contains a metal-based additive (E), the content of the metal-based additive (E) in the propylene-based resin composition is usually 0 parts by mass or more, preferably 0.01 parts by mass or more, preferably 0.04 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, and particularly preferably 0.6 parts by mass or less, based on the total amount of the propylene polymer and inorganic filler contained in the propylene-based resin composition being 100 parts by mass. By setting the content of the metal-based additive to be above the lower limit, the odor of the molded article formed from the propylene-based resin composition can be effectively reduced, and the thermal stability can be effectively improved.

[0115] (6) Component (F) Lubricant The propylene resin composition of this embodiment may contain component (F) a lubricant. Any conventionally known and suitable lubricant can be used as component (F) a lubricant.

[0116] Specific examples of component (F) lubricants include ethylenebis-stearamide (e.g., Alflow H-50S (manufactured by NOF Corporation)), erucic acid amide, behenic acid amide, and oleic acid amide.

[0117] When the propylene-based resin composition of this embodiment contains component (F) lubricant, the content of component (F) lubricant in the propylene-based resin composition is usually 0 parts by mass or more, preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, preferably 5 parts by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.1 parts by mass, based on 100 parts by mass of the total amount of propylene polymer and inorganic filler contained in the propylene-based resin composition. By setting the content of component (F) lubricant in this way, the odor of the molded article formed from the propylene-based resin composition can be effectively reduced and the thermal stability can be effectively improved.

[0118] (7) Ingredient (G) Antioxidant The propylene resin composition of this embodiment may contain component (G) antioxidant. Any conventionally known and suitable antioxidant can be used as component (G) antioxidant.

[0119] Specific examples of component (G) antioxidants include phenolic antioxidants (e.g., Sumirizer GA80 (manufactured by Sumitomo Chemical Co., Ltd.)), sulfur-based antioxidants (e.g., Sumirizer TPM (manufactured by Sumitomo Chemical Co., Ltd.)), and phosphorus-based antioxidants (e.g., SONGNOX6260 (manufactured by Songwon Co., Ltd.)).

[0120] When the propylene-based resin composition of this embodiment contains component (G) antioxidant, the content of component (G) antioxidant in the propylene-based resin composition is usually 0 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, based on the total amount of propylene polymer and inorganic filler contained in the propylene-based resin composition being 100 parts by mass. By setting the content of component (G) antioxidant in this way, the odor of the molded article formed from the propylene-based resin composition can be effectively reduced and the thermal stability can be effectively improved.

[0121] The propylene resin composition of this embodiment may contain component (H) an ultraviolet absorber. Any conventionally known and suitable ultraviolet absorber can be used as component (H) the ultraviolet absorber.

[0122] Specific examples of component (H) UV absorbers include benzoate-based UV absorbers (e.g., Sumisorb 400) and phenol-based UV absorbers (e.g., Chemisorb 114 (manufactured by Chemipro Chemical Co., Ltd.)).

[0123] When the propylene-based resin composition of this embodiment contains component (H) ultraviolet absorber, the content of component (H) ultraviolet absorber in the propylene-based resin composition is usually 0 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, preferably 0.3 parts by mass or less, more preferably 0.2 parts by mass or less, and even more preferably 0.1 parts by mass or less, based on the total amount of propylene polymer and inorganic filler contained in the propylene-based resin composition being 100 parts by mass. By setting the content of component (H) ultraviolet absorber in this way, the odor of the molded article formed from the propylene-based resin composition can be effectively reduced and the thermal stability can be effectively improved.

[0124] (8)Optional ingredients The propylene resin composition of this embodiment may contain, in addition to the components (A) to (H) already described, any further optional components that are conventionally known and suitable.

[0125] Examples of optional components that may be included in the propylene resin composition of this embodiment include modifiers, pigments such as inorganic pigments and organic pigments (e.g., carbon black), pigment dispersants, neutralizing agents, weathering agents, nucleating agents, antistatic agents, antiblocking agents, processing aids, organic peroxides, foaming agents, foaming nucleating agents, plasticizers, flame retardants, crosslinking agents, crosslinking aids, brightness enhancers, antibacterial agents, adsorbents, deodorants, crosslinking-mediated fluidity and impact resistance enhancers, and light diffusing agents.

[0126] The propylene resin composition may contain only one of the above-mentioned optional components, or it may contain two or more of them.

[0127] 2. Physical properties of propylene-based resin compositions (1) Amine compounds and their quantitative determination (unit: mass ppm) The propylene-based resin composition of this embodiment contains an amine compound in the volatile gas generated when a molded article, obtained by injection molding the propylene-based resin composition under the following molding conditions X, is heated at 100°C for 15 minutes, with a concentration of 3 to 40 ppm by mass. Molding conditions X: Molten resin temperature 200°C, mold temperature 40°C, filling pressure 15 MPa, holding pressure 4.3 MPa, holding time 40 s, molded body removal temperature ≤ 60°C, total cycle time 60 s

[0128] In this embodiment, the amine compound contained in the volatile gas generated when a molded article obtained by injection molding a propylene-based resin composition under the above conditions is heated at 100°C for 15 minutes is determined by gas chromatography-mass spectrometry (GC-MS) to be a compound containing N (m / z=14) and NH (m / z=15) as constituent components.

[0129] Examples of the above amine compounds include propan-2-amine, tert-butylamine, 2-methylpropan-2-amine, tert-butyl(methyl)-14-azan, 2-methylbutan-2-amine, N,2-dimethylpropan-2-amine, 2-methylpentan-2-amine, N,2,6-trimethylheptan-2-amine, N-isopropyl-2-methylpentan-2-amine, N,2,6-trimethylheptan-2-amine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, 2,2,6,6-tetramethylpiperidine-4-ol, 1,2,2,6,6-pentamethylpiperidine-4-amine, 1 Examples include 2,2,6,6-pentamethylpiperidine-4-ol, 2,2,6,6-tetramethylpiperidine-4-amine, N-(1,2,2,6,6-pentamethylpiperidine-4-yl)formamide, (E)-4-hydroxy-N-(2,2,6,6-tetramethylpiperidine-4-yl)buto-2-enamide, N-(1,2,2,6,6-pentamethylpiperidine-4-yl)acrylamide, (E)-4-oxo-4-((1,2,2,6,6-pentamethylpiperidine-4-yl)amino)buto-2-enoic acid, and (E)-4-oxo-4-((2,2,6,6-tetramethylpiperidine-4-yl)amino)buto-2-enoic acid.

[0130] The quantitative determination of amine compounds can be performed using any suitable conventionally known apparatus, namely a gas chromatograph-mass spectrometer (GC-MS) equipped with a mass spectrometer (MS) as a detector (e.g., GC-2010 (manufactured by Shimadzu Corporation)).

[0131] Specifically, by using a sample obtained by cutting a molded body made from the propylene-based resin composition of this embodiment into a predetermined shape, it is possible to quantify amine compounds composed of N (m / z=14) and NH (m / z=15).

[0132] In the propylene-based resin composition and molded article thereof according to this embodiment, the content of the amine compound is preferably 3 to 40 ppm by mass, more preferably 3 to 30 ppm by mass, even more preferably 5 to 30 ppm by mass, even more preferably 5 to 20 ppm by mass, and most preferably 5 to 12 ppm by mass.

[0133] In the propylene-based resin composition of this embodiment, by setting the content of the amine compound as described above, the odor of the molded article formed from the propylene-based resin composition can be effectively reduced, and the thermal stability can be effectively improved.

[0134] A propylene-based resin composition in which the concentration of amine compounds in the volatile gas generated when a molded article obtained by injection molding a propylene-based resin composition under the above conditions is heated at 100°C for 15 minutes is 3 to 40 ppm by mass can be obtained, for example, by adding (E) a metal-based additive in the amount described above to a propylene-based resin composition containing (A) a propylene polymer, (B) an inorganic filler, and (C) a hindered amine-based light stabilizer. Furthermore, the amine compound concentration can be adjusted to 3 to 40 ppm by mass by adjusting the content of (C) the hindered amine-based light stabilizer. The preferred content of (C) the hindered amine-based light stabilizer in the resin composition is as described above.

[0135] The propylene-based resin composition of this embodiment has a melt flow rate (MFR) of 1 g / 10 min or more, measured in accordance with JIS K7210-1:2014 and K7210-2:2014 under conditions of 230°C and a load of 2.16 kgf, from the viewpoint of improving the processability of the propylene-based resin composition in molding. More preferably, it is 5 g / 10 min or more, even more preferably 10 g / 10 min or more, and particularly preferably 15 g / 10 min or more.

[0136] 3. Method for producing a propylene resin composition The propylene resin composition of this embodiment can be manufactured (prepared) using the components already described by any suitable conventional manufacturing method.

[0137] The propylene-based resin composition of this embodiment can be produced, for example, by melt-mixing components that may be included in the propylene-based resin composition. The melt-mixing temperature can be, for example, 180°C or higher, and may be, for example, 180°C to 300°C, or 180°C to 250°C.

[0138] Examples of apparatus for producing the propylene-based resin composition of this embodiment by melt kneading include a Banbury mixer, a single-screw extruder, and a twin-screw extruder (e.g., a twin-screw co-rotating extruder).

[0139] The order in which the components that may be included in the propylene-based resin composition of this embodiment are added is not particularly limited.

[0140] The manufactured propylene-based resin composition can be in any conventionally known and suitable shape and size, such as strands, sheets, plates, or pellets.

[0141] From the viewpoint of improving processability and stability when manufacturing molded articles containing a propylene-based resin composition, it is preferable that the propylene-based resin composition be in the form of pellets with a length of 1 to 50 mm.

[0142] 4. Method for manufacturing molded articles The method for manufacturing a molded article containing the propylene-based resin composition of this embodiment is not particularly limited. A preferred example of a method for manufacturing a molded article containing the propylene-based resin composition of this embodiment is a conventionally known and suitable injection molding method. Specific examples of injection molding methods include 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. Furthermore, the molded article containing the propylene-based resin composition of this embodiment can also be suitably used for material recycling applications. After crushing or pulverizing the molded article containing the propylene-based resin composition of this embodiment, the pulverized product can be melt-kneaded to produce the propylene-based resin composition. When melt-kneading the pulverized product, the pulverized product may be mixed with other resin compositions if necessary. If the propylene-based resin composition produced in this manner satisfies the above-mentioned conditions, it can be considered the propylene-based resin composition of this embodiment. The following methods are examples of methods for producing propylene-based resin compositions when recycling materials. A method for producing a propylene resin composition, comprising steps (α) and (β). Step (α): A step of grinding a molded body containing the propylene resin composition of this embodiment to obtain a pulverized product. Process (β): A process of melting and kneading the pulverized material to obtain a propylene-based resin composition. In step (β), at least one selected from the group consisting of a propylene polymer, an inorganic filler, and a hindered amine light stabilizer may be melt-kneaded together with the pulverized product. The resulting propylene resin composition is adjusted as appropriate so that it satisfies the above conditions. The following methods are examples of methods for producing molded articles containing olefin resin compositions when material recycling is performed. A method for producing a molded article containing a propylene resin composition, comprising steps (α') and (β'). Step (α'): A step of grinding a molded body containing the propylene resin composition of this embodiment to obtain a pulverized product. Step (β'): A step of molding the pulverized product to obtain a molded body containing a propylene-based resin composition. In step (β'), at least one selected from the group consisting of a propylene polymer, an inorganic filler, and a hindered amine light stabilizer may be mixed with the pulverized product and then molded.

[0143] 5. Uses of propylene resin compositions and molded articles thereof The applications of the propylene-based resin composition and its molded articles in this embodiment are not particularly limited. The propylene-based resin composition can be suitably applied to various applications where high thermal stability and odor reduction are required.

[0144] Molded articles produced by molding the propylene resin composition of this embodiment can be suitably used, for example, as components of automobiles, components of household electrical appliances, and containers. In particular, they can be suitably used as materials for automotive interior components where high thermal stability and suppression (reduction) of odor generation are required. Specific examples of automotive interior components include door trims, pillars, and instrument panels.

[0145] 6. Characteristics of molded articles made from propylene-based resin compositions (1) Evaluation of thermal stability Thermal stability can be evaluated using any suitable differential thermogravimetric analyzer that is conventionally known (e.g., TG / DTA 6200 (manufactured by Seiko Instruments Corporation)).

[0146] Specifically, when using a test piece molded from the propylene resin composition of this embodiment into a predetermined shape as a sample, and measuring the oxidation induction time (in minutes) at a set temperature of 190°C and then 210°C, the time until the rise of the exothermic peak due to oxidation of the test piece is defined as the oxidation induction time, and the thermal stability can be evaluated based on this.

[0147] In this embodiment, the oxidation induction time (minutes) at a set temperature of 190°C and the oxidation induction time (minutes) at a set temperature of 210°C can both be evaluated as good if they are 10 minutes or more, and are more preferably 12 minutes or more. For the oxidation induction time (minutes) at a set temperature of 190°C, it is more preferably 120 minutes or more.

[0148] (2) Evaluation of odor The odor of molded articles made from propylene resin compositions can be evaluated by multiple panelists (testers) who score them based on predetermined scoring criteria.

[0149] Specifically, a test piece molded from the propylene resin composition of this embodiment into a predetermined shape is used as a sample. The sample is placed in an odorless container (e.g., a glass bottle) and sealed. After heat treatment under predetermined temperature conditions of 50°C or higher, considering the temperature inside a car during summer (e.g., heating at 80°C for 2 hours, followed by standing at 60°C), the odor of the sample in the container is scored based on the scoring criteria below, for example. The total score obtained by summing the scores is then divided by the number of panelists to calculate the average score, and the odor can be objectively evaluated based on this average score.

[0150] (Scoring Criteria) 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 smell. 5 points: It has a very unpleasant smell. 6 points: The smell is unbearable.

[0151] Regarding the evaluation of odor, the average score is preferably 3.2 points or less, more preferably 3.1 points or less, and most preferably 3.0 points or less.

[0152] In addition to the "Odor Evaluation" described above, the odor quality can also be evaluated. Regarding odor quality, it is preferable that there are no unpleasant odors such as burnt odor, amine odor, or acrylic odor, and it is particularly preferable that there is no burnt odor. [Examples]

[0153] The present invention will be described more specifically below with reference to examples and comparative examples. The present invention is not limited to the examples described below.

[0154] The components used in the examples and comparative examples are shown below.

[0155] 1. Component (A): Propylene polymer Component (A-1): Heterophagic propylene polymerization material Using a polymerization catalyst obtained by the method described in Example 1 of Japanese Patent Publication No. 2004-182981, a propylene polymer component (A-1) heterophagic propylene polymerization material was produced by liquid-phase-gas-phase polymerization, containing 87 parts by mass of polymer (I), which is a propylene homopolymer component (a), and 13 parts by mass of polymer (II), which is an ethylene-α-olefin copolymer component (b), which is an ethylene-propylene random copolymer component.

[0156] The physical properties of component (A-1), the heterophagic propylene polymerization material, are as follows. Melt flow rate (230℃, 2.16kg load): 55g / 10min (a) Propylene monopolymer component (P portion) Intrinsic viscosity number: 0.90dL / g (b) Ethylene-propylene random copolymer component (EP portion) Intrinsic viscosity number: 6.0dL / g Content of structural units derived from ethylene: 32% by mass

[0157] Component (A-2) Propylene homopolymer Using a polymerization catalyst obtained by the method described in Example 1 of Japanese Patent Publication No. 2004-182981, a component (A-2) propylene homopolymer was produced by liquid-phase-gas-phase polymerization.

[0158] The physical properties of component (A-2) propylene homopolymer are as follows. Melt flow rate (230℃, load 2.16kgf): 3.2g / 10min Intrinsic viscosity number: 2.0dL / g

[0159] Here, the intrinsic viscosity number (unit: dL / g) refers to the value measured at a temperature of 135°C using tetralin as the solvent by the method described below.

[0160] The intrinsic viscosity number (unit: dL / g) was determined by measuring the reduced viscosity for multiple concentrations using an Ubbelohde viscometer, plotting the reduced viscosity against the concentration, and extrapolating the concentration to zero using the "extrapolation method."

[0161] More specifically, the method described on page 491 of "Polymer Solutions, Polymer Experiments 11" (Kyoritsu Shuppan Co., Ltd., 1982) was adopted to measure the reduced viscosity at three points with concentrations of 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL. The reduced viscosity was then plotted against the concentration and the value was determined by extrapolating the concentration to zero.

[0162] 2. Component (B) Inorganic filler Component (B) uses talc as an inorganic filler. Its physical properties are as follows. MWUPN-TT-H (manufactured by Hayashi Chemical Co., Ltd.) CAS No. 14807-96-6 Average particle size (50% particle size): 4.7 μm (measured using a laser diffraction type SALD1100 (Shimadzu Corporation))

[0163] 3. Ingredients (C) Hindered amine light stabilizer Ingredient (C-1) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate CAS.52829-07-9 As component (C), a hindered amine-based light stabilizer, component (C-1) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, represented by the following formula, was used. Its physical properties are as follows.

[0164] [ka]

[0165] ADEKA ASTAB LA-77 (manufactured by ADEKA) Molecular weight: 481

[0166] Component (C-2) Sterically hindranced amine oligomer "Copolymer consisting of N-(2,2,6,6-tetramethyl-4-piperidyl)maleimide and α-olefins with 20 to 24 carbon atoms" CAS.152261-33-1 As component (C-2) above, a copolymer represented by the following formula was used. Its physical properties are as follows.

[0167] [ka]

[0168] UVINUL (registered trademark) 5050H (manufactured by BASF Japan) Molecular weight: 3500 pKa:7.0 Weight reduction rate due to TG-DTA: 2.2%

[0169] Component (C-3) Butanedioc acid, dimethylester, polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol CAS. 65447-77-0 The following product was used as component (C-3). Its physical properties are as follows. TINUVIN 622 SF (manufactured by BASF Japan) Molecular weight: 3100~4000

[0170] 4. Component (D) Olefin polymer As the ethylene-α-olefin copolymer, which is an olefin polymer of component (D), component (D-1) ethylene-butene-1 copolymer was used. The physical properties of component (D-1) ethylene-butene-1 copolymer are as follows. Engage® 7447 (manufactured by DOW Corporation) Content of structural units derived from ethylene: 70% by mass Content of structural units derived from butene-1: 30% by mass Melt flow rate (190℃, load 2.16kgf): 5g / 10min Density: 0.865g / cm 3

[0171] 5. Components (E) Metal-based additives (zinc fatty acid salts, aluminum fatty acid salts, calcium fatty acid salts, and calcium hydroxide) (1) Aluminum distearate Aluminum stearate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) CAS No. 300-92-5

[0172] (2) Zinc distearate Zinc stearate (manufactured by Nitto Chemical Industries, Ltd.) CAS No. 557-05-1

[0173] (3) Calcium distearate Calcium stearate (manufactured by Sakai Chemical Industry Co., Ltd.) CAS No. 1592-23-0

[0174] (4) Calcium hydroxide Calcium hydroxide CLS-B (manufactured by Shiraishi Calcium Co., Ltd.) CAS No. 1305-62-0

[0175] Ingredient (F): Lubricant (1) Ethylene bis-stearamide Alflow H-50S (manufactured by NOF Corporation) CAS No. 324-27431

[0176] Ingredient (G): Antioxidant (1) Sumirizer GA80 (manufactured by Sumitomo Chemical Co., Ltd.) CAS.90498-90-1 (2) SONGNOX6260 (manufactured by Songwon Co., Ltd.) CAS.26741-53-7 (3) Sumirizer TPM (manufactured by Sumitomo Chemical Co., Ltd.) CAS.16545-54-3 (4) IRGAFOS168 (manufactured by BASF) CAS. 31570-04-4

[0177] Ingredients (H) UV absorber Sumisorb 400 (manufactured by Sumika Chemtex Co., Ltd.) CAS.4221-80-1

[0178] The molded articles formed from the propylene-based resin composition described below were evaluated.

[0179] 1. Amine compounds Using a Meiki Seisakusho M70 injection molding machine, a propylene-based resin composition was injection 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 s (seconds), molded body removal temperature ≤ 60°C, and total cycle time 60 s (seconds). This produced a flat molded body with a length of 60 mm, a width of 60 mm, and a thickness of 2.0 mm. Subsequently, the obtained molded body was cut to produce pieces with a length of 6 mm, a width of 6 mm, and a thickness of 2.0 mm.

[0180] Using the cuttings prepared as described above, the classification of "amine compounds" containing N (m / z=14) and NH (m / z=15) as constituent components, which may cause odor, was determined by gas chromatography-mass spectrometry (GC-MS) using the following method.

[0181] For GC-MS measurements, a GC-2010 gas chromatograph (manufactured by Shimadzu Corporation) was used as the measuring instrument, a Rix-5 column (packing material: 5% diphenylpolysiloxane / 95% dimethylpolysiloxane, length 30 m, inner diameter 0.32 mm, thickness 1.0 μm) was used, and helium gas was used as the carrier gas.

[0182] For the measurement, 2.0 g of the prepared cuttings were sealed in a sample vial (volume 20 mL). The sample vial was heated at 100°C for 15 minutes, and the volatile components were injected into the GC inlet. The temperature of the inlet was set to 250°C, the column oven temperature was set to 40°C and held for 10 minutes, then the temperature was increased at 10°C / min, and then held at 290°C for another 10 minutes. At this time, the flow rate was 1 mL / min and the split ratio was 50:1.

[0183] A mass spectrometer (MS) was used as the detector, and the electron impulse ionization (EI) mode was selected as the ionization mode. Measurements were performed in the range of mass / charge number (m / z) from 30 to 500.

[0184] For the measurements, we used the selective ion monitoring (SIM) method, which allows us to observe only specific mass numbers (m / z).

[0185] Settings such as ion acceleration voltage were determined by auto-tuning using a standard sample of perfluorotributylamine.

[0186] In this embodiment, "amine compound" is defined as a component containing N and NH as constituent elements.

[0187] 2. Determination of amine compounds (unit: mass ppm) The quantification of amine compounds was performed by gas chromatography (GC) measurement according to the following procedure.

[0188] Specifically, a gas chromatograph flash GC nose Heracles (AlphaMoss) was used as the apparatus, a Tenax TA (solid adsorbent trap) was used as the trap, and an MXT-5 column (packing material: diphenyl dimethyl polysiloxane, length 10 m, inner diameter 0.18 mm, thickness 0.14 μm) was used.

[0189] A flame ionization detector (FID) was used as the detector, and hydrogen gas was used as the carrier gas.

[0190] First, to quantify the amine compounds, 2.0 g of the cut piece formed as described above was sealed in a sample vial (volume 20 mL). The sample vial was heated at 100°C for 15 minutes, and the volatile components were injected into the GC inlet and collected by cooling in a trap. The trap was then heated to introduce the components into the GC column, and the generated amine compounds were quantified.

[0191] For the GC measurement conditions, the injection volume was set to 5000 μL, the inlet temperature to 220°C, the trap temperature to 70°C, the trap desorption temperature to 240°C, and the column oven temperature was set to 40°C for 10 seconds, then increased at a rate of 1.5°C / second to 250°C for 90 seconds. The split ratio was set to 10:1. The FID detector temperature was set to 260°C.

[0192] Using a standard substance (toluene), 1 μL, 5 μL, and 10 μL samples were weighed into sample bottles, and calibration curves were created by measuring them in the same manner as described above. The amine compounds were quantified using the obtained calibration curves.

[0193] 3. Evaluation of thermal stability (unit: minutes) Using a Sumitomo Heavy Industries SE130 injection molding machine, a propylene-based resin composition was molded into a flat plate shape measuring 90 mm in length, 60 mm in width, and 3.0 mm in thickness at a molding temperature of 220°C, a mold cooling temperature of 50°C, and a pressure of 50 MPa.

[0194] The formed flat molded body was further shaped by vacuum pressing to a size suitable for measurement to create a test specimen.

[0195] Vacuum pressing was performed by setting the molding press temperature to 190°C, applying pressure at 0 MPa for 5 minutes, then at 1 MPa for 5 minutes, followed by cooling at 25°C and 0 MPa for 5 minutes. As a result, a test specimen with a thickness of 300 μm was obtained.

[0196] Next, the oxidation induction time was measured using the obtained test specimens and a differential thermogravimetric analyzer (TG / DTA 6200, manufactured by Seiko Instruments Corporation) with the set temperature set to 190°C and then to 210°C.

[0197] Specifically, the atmospheric gas was nitrogen gas (N2), and the temperature was rapidly raised to the set temperature. Then, the atmospheric gas was switched from nitrogen gas to air. The time from the time of the switch until the rise of the exothermic peak due to oxidation of the test specimen was defined as the oxidation induction time (in minutes), and the thermal stability was evaluated based on this.

[0198] The measurement time was set to a maximum of 2 hours, and if no heat generation or weight loss was observed within the measurement time, the oxidation induction time was set to "120 minutes or more."

[0199] 4. Odor evaluation A propylene-based resin composition was supplied to an injection molding machine (Meiki Seisakusho's "M70 type injection molding machine"), and a flat molded body with a length of 60 mm, a width of 60 mm, and a thickness of 2.0 mm was formed using the following settings: molten resin temperature of 200°C, mold temperature of 40°C, filling pressure of 15 MPa, holding pressure of 4.3 MPa, holding time of 40 s (seconds), molded body removal temperature of ≤60°C, and total cycle time of 60 s (seconds). Subsequently, the obtained flat molded body was cut into pieces measuring 60 mm in length, 30 mm in width, and 2.0 mm in thickness to form samples.

[0200] The three obtained samples were placed in a 0.5L odorless glass bottle, sealed with a lid, and heated in an oven at 80°C for 2 hours.

[0201] The glass bottles were then left to stand at 60°C for 15 minutes. Subsequently, three or more panelists evaluated the odor of the samples in the glass bottles.

[0202] Specifically, each panelist scored the odor based on the following scoring criteria.

[0203] (Scoring Criteria) 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 smell. 5 points: It has a very unpleasant smell. 6 points: The smell is unbearable.

[0204] Based on the scoring criteria described above, the panelists' scores were totaled, and the average score was calculated by dividing the total score by the number of panelists. This average score was then used for evaluation. Odor quality was also evaluated.

[0205] [Example 1] When the total of component (A) propylene polymer and component (B) inorganic filler is 100 parts by mass, the composition is as follows: component (A-1) propylene-ethylene block copolymer 65 parts by mass, component (A-2) propylene homopolymer 9 parts by mass, component (B) talc 25.9 parts by mass, component (C) hindered amine light stabilizer ADEKASTAB LA-77 0.12 parts by mass, component (D) olefin polymer (component (D-1) ethylene-butene-1 copolymer) 20.5 parts by mass, component (E) metal additive zinc stearate 1.2 parts by mass, calcium hydroxide 0.48 parts by mass, calcium stearate 0.024 parts by mass, component (F) lubricant ethylenebisstearate amide 0.084 parts by mass, component (G) antioxidant Smirizer GA80 0.024 parts by mass, SONG 0.06 parts by mass of NOX6260, 0.024 parts by mass of SumiLizer TPM, and 0.06 parts by mass of Sumisorb 400 were weighed out and mixed until uniform. The mixture was then introduced into the upstream raw material inlet of a Japan Steel Works twin-screw kneader TEX44αII, and the mixture was melt-kneaded at 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 section to prepare a pelletized propylene-based resin composition.

[0206] The oxygen concentration in the feed hopper section was measured by inserting a portable oxygen concentration meter's sensor into the purge resin inlet attached to the feed hopper. Furthermore, an oxygen concentration of 2% was achieved by circulating nitrogen gas into the feed hopper section.

[0207] Next, after drying the pelletized propylene resin composition at 100°C for 1 hour, a molded body was formed using an injection molding machine as described above. Then, the molded body was cut and further shaped to produce test pieces, which were used to evaluate the amount of amine decomposition, odor, thermal stability, and odor quality using the method already described. The results are shown in Table 3.

[0208] [Examples 2-6] Except for the amounts of each component used in Tables 1 and 2 below, the propylene resin compositions according to Examples 2 to 6 were prepared in the same manner as in Example 1, which has already been described, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0209] [Comparative Examples 1-3] The propylene resin compositions according to Comparative Examples 1 to 3 were prepared in the same manner as in Example 1, except that the amounts of each component were as shown in Tables 1 and 2 below, and were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0210] [Table 1]

[0211] [Table 2]

[0212] [Table 3]

Claims

1. (A) Propylene polymer and (B) Inorganic filler and (C) Hindered amine-based light stabilizers, (E) A propylene resin composition comprising a metal-based additive, (E) The metal-based additive comprises zinc stearate or aluminum stearate, calcium hydroxide, and calcium stearate. A propylene-based resin composition wherein the concentration of amine compounds in the volatile gas generated when a molded article, obtained by molding the propylene-based resin composition under the following molding conditions X, is heated at 100°C for 15 minutes, is 3 to 40 ppm by mass. Molding conditions X: Molten resin temperature 200°C, mold temperature 40°C, filling pressure 15 MPa, holding pressure 4.3 MPa, holding time 40 s, molded body removal temperature ≤ 60°C, total cycle time 60 s

2. (B) The propylene resin composition according to claim 1, wherein the inorganic filler is talc.

3. (B) The propylene resin composition according to claim 1 or 2, wherein the inorganic filler comprises at least one selected from the group consisting of glass, calcium carbonate, and basic magnesium sulfate.

4. (D) Further comprising an olefin polymer, (D) The propylene resin composition according to any one of claims 1 to 3, wherein the olefin polymer is at least one polymer selected from the group consisting of ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, ethylene-(3-methyl-1-butene) copolymer, and copolymer of ethylene and an α-olefin having a cyclic structure.

5. The propylene resin composition according to any one of claims 1 to 4, wherein the content of (C) a hindered amine-based light stabilizer is 0.3 parts by mass or less when the total amount of (A) a propylene polymer and (B) an inorganic filler is 100 parts by mass.

6. (C) The propylene resin composition according to any one of claims 1 to 5, wherein the hindered amine light stabilizer is other than bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.

7. A propylene-based resin composition according to any one of claims 1 to 6, wherein the concentration of the amine compound in the volatile gas is 3 to 30 ppm by mass.

8. A molded article comprising the propylene resin composition according to any one of claims 1 to 7.

9. A method for producing a molded article comprising the propylene resin composition according to claim 8, comprising steps (α') and (β'). Step (α'): A step of grinding a molded article containing the propylene resin composition described in any one of claims 1 to 8 to obtain a pulverized product. Step (β'): A step of molding the pulverized product to obtain a molded article containing the propylene resin composition described in any one of claims 1 to 8.

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