Propylene resin composition

Abstract

To provide a propylene resin composition which is capable of producing a molded body having a large tensile fracture strain.SOLUTION: The present invention provides a propylene resin composition which contains a propylene polymer, a metal deactivator, and a hindered amine light stabilizer. The ratio of the weight of the hindered amine light stabilizer to the weight of the metal deactivator is 10 or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a propylene resin composition and a molded article thereof.

Background Art

[0002] Molded articles containing (manufactured from) propylene resin compositions are used in automotive materials, household electrical appliance materials, container packaging materials, and the like.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In recent years, molded articles used in automotive materials, household electrical appliance materials, container packaging materials, and the like are required to have high tensile fracture strain.

[0005] Therefore, an object of the present invention is to provide a propylene resin composition capable of manufacturing a molded article having a large tensile fracture strain. Another object of the present invention is to provide a molded article having a large tensile fracture strain.

Means for Solving the Problems

[0006] The present invention relates to, but is not limited to, the following. [Invention A1] A propylene resin composition containing a propylene - based polymer, a metal deactivator, and a hindered amine - type light stabilizer, wherein the ratio of the weight of the hindered amine - type light stabilizer to the weight of the metal deactivator is 10 or more. [Invention A2] The propylene resin composition according to Invention A1, wherein the ratio of the weight of the hindered amine light stabilizer to the weight of the metal deactivator is 50 or less. [Invention A3] The propylene resin composition according to Invention A1 or A2, wherein the propylene polymer contains a heterophasic propylene polymer material. [Invention A4] The propylene resin composition according to any one of Inventions A1 to A3, wherein the weight ratio of the metal deactivator is 10 to 1000 weight ppm based on 100 parts by weight of the total weight of the propylene resin composition. [Invention A5] The propylene resin composition according to any one of Inventions A1 to A4, wherein the weight ratio of the hindered amine light stabilizer is 200 to 10000 weight ppm based on 100 parts by weight of the total weight of the propylene resin composition. [Invention A6] The propylene resin composition according to any one of Inventions A1 to A5, wherein the weight ratio of the propylene polymer is 50 parts by weight or more based on 100 parts by weight of the total weight of the propylene resin composition. [Invention A7] The propylene resin composition according to any one of Inventions A1 to A6, wherein the melt flow rate (measured under the conditions of a temperature of 230°C and a load of 2.16 kgf) of the propylene resin composition is 0.1 g / 10 minutes or more. [Invention A8] The propylene resin composition according to any one of Inventions A1 to A7, wherein the melt flow rate (measured under the conditions of a temperature of 230°C and a load of 2.16 kgf) of the propylene polymer is 0.1 g / 10 minutes or more. [Invention A9] The propylene resin composition according to any one of Inventions A1 to A8, further comprising an ethylene-α-olefin copolymer. [Invention A10] The propylene resin composition according to Invention A9, wherein the weight ratio of the ethylene-α-olefin copolymer is 1 to 40 parts by weight based on 100 parts by weight of the total weight of the propylene resin composition. [Invention A11] The propylene resin composition according to any one of Inventions A1 to A10, further comprising an inorganic filler. [Invention A12] The propylene resin composition according to Invention A11, wherein the weight ratio of the inorganic filler is 1 part by weight to 40 parts by weight with respect to 100 parts by weight of the total weight of the propylene resin composition. [Invention A13] The propylene resin composition according to any one of Inventions A1 to A12, further comprising an ethylene-α-olefin copolymer and an inorganic filler. [Invention A14] A molded article comprising the propylene resin composition according to any one of Inventions A1 to A13.

[0007] Other aspects of the present invention are shown below. [Invention B1] A propylene resin composition containing a propylene-based polymer, a metal deactivator having a triazole skeleton or a triazine skeleton, and a hindered amine light stabilizer having a 2,2,6,6-tetramethylpiperidine skeleton, wherein the propylene-based polymer is a heterophasic propylene polymer material, wherein the weight ratio of the metal deactivator is 10 weight ppm to 1000 weight ppm and the weight ratio of the hindered amine light stabilizer is 200 weight ppm to 10000 weight ppm with respect to 100 parts by mass of the propylene polymer, wherein the ratio of the weight of the hindered amine light stabilizer to the weight of the metal deactivator is 10 or more, Propylene resin composition. [Invention B2] The propylene resin composition according to Invention B1, wherein the ratio of the weight of the hindered amine light stabilizer to the weight of the metal deactivator is 50 or less. [Invention B3] The propylene resin composition according to Invention B1 or B2, wherein the weight ratio of the propylene-based polymer is 50 parts by weight or more with respect to 100 parts by weight of the total weight of the propylene resin composition. [Invention B4] The propylene resin composition according to any one of Inventions B1 to B3, wherein the melt flow rate (measured under the conditions of a temperature of 230 ° C and a load of 2.16 kgf) is 0.1 g / 10 min or more. [Invention B5] The propylene resin composition according to any one of Inventions B1 to B4, wherein the melt flow rate (measured under the conditions of a temperature of 230 ° C and a load of 2.16 kgf) of the propylene polymer is 0.1 g / 10 min or more. [Invention B6] The propylene resin composition according to any one of Inventions B1 to B5, further comprising an ethylene-α-olefin copolymer. [Invention B7] The propylene resin composition according to Invention B6, wherein the weight ratio of the ethylene-α-olefin copolymer is 1 part by weight to 40 parts by weight with respect to 100 parts by weight of the total weight of the propylene resin composition. [Invention B8] The propylene resin composition according to any one of Inventions B1 to B7, further comprising an inorganic filler. [Invention B9] The propylene resin composition according to Invention B8, wherein the weight ratio of the inorganic filler is 1 part by weight to 40 parts by weight with respect to 100 parts by weight of the total weight of the propylene resin composition. [Invention B10] The propylene resin composition according to any one of Inventions B1 to B9, further comprising an ethylene-α-olefin copolymer and an inorganic filler. [Invention B11] A molded article comprising the propylene resin composition according to any one of Inventions B1 to B10. [Effects of the Invention]

[0008] According to the present invention, a molded article having a large tensile fracture strain and a propylene resin composition as a raw material thereof can be provided. [Modes for Carrying Out the Invention]

[0009] Hereinafter, embodiments of the present invention will be specifically described. The present invention is not limited to the specific embodiments shown below.

[0010] Term Explanation In explaining the embodiments of the present invention, first, terms commonly used will be explained.

[0011] In this specification, the "monomer unit" means a structural unit (residue) derived from a monomer contained in a polymer obtained by polymerizing a monomer (monomer).

[0012] In this specification, the "α-olefin" means an olefin containing a carbon atom chain composed of 3 or more carbon atoms having a carbon-carbon double bond at the terminal side (α-position).

[0013] In this specification, the "intrinsic viscosity (unit: dL / g)" (also referred to as [η]) is a value measured at a temperature of 135 °C using tetralin as a solvent by the following method.

[0014] Specifically, the intrinsic viscosity can be determined by the "extrapolation method" in which a reduced viscosity is measured for a plurality of concentrations using an Ubbelohde viscometer, the reduced viscosity is plotted against the concentration, and the concentration is extrapolated to zero. For example, the measurement is performed according to the method described in the examples.

[0015] In this specification, unless otherwise specified, "%" means weight %, and "parts" means "parts by weight".

[0016]

[0017] ​The description of "lower limit ~ upper limit" representing a numerical range means "not less than the lower limit and not more than the upper limit", and the description of "upper limit ~ lower limit" means "not more than the upper limit and not less than the lower limit". That is, these descriptions represent a numerical range including the lower limit and the upper limit. However, in one aspect, one or both of the upper limit and the lower limit may be excluded. That is, "lower limit ~ upper limit" may represent "more than the lower limit and not more than the upper limit", "not less than the lower limit and less than the upper limit", or "more than the lower limit and less than the upper limit". Similarly, "xxx or more" may represent "more than xxx", and "xxx or less" may represent "less than xxx".

[0018] Propylene resin composition The propylene resin composition according to the present invention is a propylene resin composition containing a propylene-based polymer, a metal deactivator, and a hindered amine-based light stabilizer, wherein the ratio of the weight of the hindered amine-based light stabilizer to the weight of the metal deactivator is 10 or more. In one embodiment, based on 100 parts by weight of the total weight of the propylene resin composition, the weight ratio of the metal deactivator is 10 parts by weight to 1000 weight ppm.

[0019] Hereinafter, the components that can be included in the propylene resin composition of the present embodiment will be described.

[0020] Propylene-based polymer (P) In the present specification, the propylene-based polymer (also referred to as component P) is a polymer containing propylene units in an amount of more than 50% by weight based on all the constituent units (100% by weight). The propylene units in the propylene-based polymer are usually 100% by weight or less.

[0021] Examples of the propylene-based polymer include a propylene homopolymer; and a propylene-based copolymer (a copolymer obtained by polymerizing propylene and one or more other monomers copolymerizable with the propylene in an arbitrary ratio combination).

[0022] Propylene homopolymer The intrinsic viscosity [η] of the propylene homopolymer is preferably 0.1 dL / g to 5 dL / g, more preferably 0.5 dL / g to 4 dL / g, and even more preferably 0.6 dL / g to 3 dL / g, from the viewpoint of improving the fluidity during melting of the propylene resin composition and the toughness of the molded article formed from the propylene resin composition.

[0023] Propylene-based copolymer The propylene-based copolymer may be a random copolymer or a block copolymer. Examples of other monomers copolymerizable with propylene include olefins other than propylene (e.g., ethylene, olefins having 4 or more carbon atoms). The number of carbon atoms of the olefin may be 12 or less.

[0024] The olefin having 4 or more carbon atoms may be a linear olefin or a branched olefin. The olefin having 4 or more carbon atoms may have a cyclic structure, and for example, may be an α-olefin having a cyclic structure such as vinylcyclopropane or vinylcyclobutane.

[0025] Examples of olefins other than propylene copolymerizable with propylene include α-olefins other than propylene (e.g., ethylene, 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, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene, and more preferably ethylene, 1-butene, 1-hexene, and 1-octene.

[0026] Propylene-based random copolymer Examples of the propylene-based random copolymer include a random copolymer containing propylene units and ethylene units (hereinafter also referred to as the random polymer (1)); a random copolymer containing propylene units and α-olefin units having 4 or more carbon atoms (hereinafter also referred to as the random polymer (2)); and a random copolymer containing propylene units, ethylene units, and α-olefin units having 4 or more carbon atoms (hereinafter also referred to as the random polymer (3)).

[0027] The α-olefin having 4 or more carbon atoms that can constitute the propylene-based random copolymer is preferably an α-olefin having 4 to 10 carbon atoms. Examples of the α-olefin having 4 to 10 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene, and preferably 1-butene, 1-hexene, and 1-octene.

[0028] Examples of the random polymer (2) include a propylene-1-butene random copolymer, a propylene-1-hexene random copolymer, a propylene-1-octene random copolymer, and a propylene-1-decene random copolymer.

[0029] Examples of the random polymer (3) include a propylene-ethylene-1-butene copolymer, a propylene-ethylene-1-hexene copolymer, a propylene-ethylene-1-octene copolymer, and a propylene-ethylene-1-decene copolymer.

[0030] The content ratio of the ethylene units in the random polymer (1) is preferably 0.1% by weight to 40% by weight.

[0031] The content ratio of the α-olefin units having 4 or more carbon atoms in the random polymer (2) is preferably 0.1% by weight to 40% by weight, more preferably 0.1% by weight to 30% by weight, and still more preferably 2% by weight to 15% by weight.

[0032] In the random copolymer (3), the total content ratio of ethylene units and α-olefin units having 4 or more carbon atoms is preferably 0.1% by weight to 40% by weight, more preferably 0.1% by weight to 30% by weight, and still more preferably 2% by weight to 15% by weight.

[0033] The content ratio of propylene units in these random copolymers (1) to (3) is preferably 60% by weight to 99.9% by weight, respectively.

[0034] The propylene-based polymer (P) can be produced, for example, by the following polymerization method using a polymerization catalyst.

[0035] Examples of the polymerization catalyst include Ziegler-type catalyst systems; Ziegler-Natta-type catalyst systems, catalyst systems containing a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane, catalyst systems containing a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that reacts with it to form an ionic complex, and an organoaluminum compound, and catalyst systems in which catalyst components (for example, a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that forms an ionic complex, an organoaluminum compound, etc.) are supported on inorganic particles (for example, silica, clay minerals, etc.) and modified. Further, a prepolymerization catalyst prepared by prepolymerizing monomers such as ethylene and α-olefin in the presence of such a catalyst system may also be used. Examples of the Ziegler-Natta-type catalyst system include catalyst systems that combine a titanium-containing solid transition metal component and an organometallic component.

[0036] Examples of such catalyst systems include those described in JP-A-61-218606, JP-A-5-194685, JP-A-7-216017, JP-A-9-316147, JP-A-10-212319, and examples of catalyst systems used for producing the heterophasic propylene polymer material described later include the catalyst system described in JP-A-2004-182981.

[0037] Examples of the polymerization method include bulk polymerization, solution polymerization, and gas-phase polymerization. Here, bulk polymerization refers to a method of performing polymerization using a liquid olefin as a medium at the polymerization temperature. Solution polymerization refers to a method of performing polymerization in an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, or octane. Gas-phase polymerization refers to a method of polymerizing a monomer in a gaseous state using the gaseous monomer as a medium.

[0038] In carrying out the polymerization method, examples of the polymerization system include a batch system, a continuous system, and combinations thereof. The polymerization system may also be a multi-stage system carried out using a plurality of polymerization reaction vessels connected in series.

[0039] Various conditions (polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, polymerization time, etc.) in the polymerization method can be appropriately determined according to the target propylene-based polymer.

[0040] In the production of a propylene-based polymer, the obtained propylene-based polymer is held at a temperature at which impurities such as residual solvent and the oligomer can volatilize and which is lower than the melting temperature of the propylene-based polymer, whereby a treatment for removing the residual solvent contained in the obtained propylene-based polymer and ultra-low molecular weight oligomers by-produced during production may be performed. Examples of methods for removing impurities such as residual solvent and oligomers include the methods described in JP-A-55-75410 and Japanese Patent No. 2565753.

[0041] The propylene resin composition of this embodiment may contain two or more types of propylene-based polymers as the propylene-based polymer (P).

[0042] Examples of the combination in the case of containing two or more types of propylene-based polymers include combinations of two or more types of propylene homopolymers having different weight average molecular weights, etc., and heterophasic propylene polymer materials.

[0043] Here, the "heterophagic propylene polymer material" means a material containing two or more propylene-based polymers, and the two or more propylene-based polymers are not compatible with each other and form different phases.

[0044] Examples of the heterophagic propylene polymer material include materials containing the following combination of polymer (I) and polymer (II).

[0045] Here, polymer (I) is a polymer having more than 80% by weight and 100% by weight or less of propylene units based on the total amount of all constituent units. Polymer (I) may be a propylene homopolymer or a copolymer of propylene and other monomers. The total content ratio of monomer units other than propylene units in polymer (I) is usually 0% by weight or more and less than 20% by weight, may be 0% by weight, or may be 0.01% by weight or more when the weight of polymer (I) is 100% by weight. When polymer (I) is a copolymer, polymer (I) may be a random copolymer.

[0046] 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.

[0047] 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 still more preferably 1-butene.

[0048] Examples of polymer (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.

[0049] Among these, as the polymer (I), a propylene homopolymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, and a propylene-ethylene-1-butene copolymer are preferable, and a propylene homopolymer is more preferable from the viewpoint of improving the rigidity of a molded article obtained by molding the propylene resin composition.

[0050] Further, the polymer (II) is a copolymer of a propylene unit and at least one monomer unit selected from the group consisting of an ethylene unit and an α-olefin unit having 4 or more carbon atoms. The polymer (II) is preferably a polymer having more than 0% by weight and 90% by weight or less of propylene units based on the total amount of all constituent units, and more preferably a polymer having more than 0% by weight and 80% by weight or less. The polymer (II) may be a random copolymer or a block copolymer.

[0051] The total content ratio of the ethylene unit and the α-olefin unit having 4 or more carbon atoms in the polymer (II) is preferably 20% by weight to 80% by weight, more preferably 20% by weight to 60% by weight, when the weight of the polymer (II) is 100% by weight.

[0052] The α-olefin having 4 or more carbon atoms that can constitute the polymer (II) is preferably an α-olefin having 4 to 10 carbon atoms, and examples similar to those of the α-olefins that can constitute the polymer (I) described above can be given.

[0053] Examples of the 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. The polymer (II) is preferably a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-ethylene-1-butene copolymer, and more preferably a propylene-ethylene copolymer.

[0054] When the total weight of the polymer (I) and the polymer (II) is 100% by weight, the content ratio of the polymer (II) in the heterophasic propylene polymer material is preferably 1% to 50% by weight, more preferably 1% to 45% by weight, still more preferably 5% to 40% by weight, and particularly preferably 7% to 35% by weight.

[0055] Each of the polymer (I) and the polymer (II) may consist of only one kind of polymer or may contain two or more kinds of polymers.

[0056] Examples of the heterophasic propylene polymer material include combinations of a propylene homopolymer (where the polymer (I) is a propylene homopolymer) with a (propylene-ethylene) copolymer, a (propylene-ethylene-1-butene) copolymer, a (propylene-ethylene-1-hexene) copolymer, a (propylene-ethylene-1-octene) copolymer, a (propylene-1-butene) copolymer, a (propylene-1-hexene) copolymer, a (propylene-1-octene) copolymer, and a (propylene-1-decene) copolymer.

[0057] Further, as the heterophasic propylene polymer material, a combination in which the polymer (I) is a polymer containing a propylene unit and a monomer unit other than the propylene unit may be used. When the type of the polymer (I) is described first and the type of the polymer (II) is described later, specific examples of such a heterophasic propylene polymer material include a combination of a (propylene-ethylene) copolymer and a (propylene-ethylene) copolymer, a combination of a (propylene-ethylene) copolymer and a (propylene-ethylene-1-butene) copolymer, a combination of a (propylene-ethylene) copolymer and a (propylene-ethylene-1-hexene) copolymer, a combination of a (propylene-ethylene) copolymer and a (propylene-ethylene-1-octene) copolymer, a combination of a (propylene-ethylene) copolymer and a (propylene-ethylene-1-decene) copolymer, a combination of a (propylene-ethylene) copolymer and a (propylene-1-butene) copolymer, a combination of a (propylene-ethylene) copolymer and a (propylene-1-hexene) copolymer, a combination of a (propylene-ethylene) copolymer and a (propylene-1-octene) copolymer, a combination of a (propylene-ethylene) copolymer and a (propylene-1-decene) copolymer, a combination of a (propylene-1-butene) copolymer and a (propylene-ethylene) copolymer, a combination of a (propylene-1-butene) copolymer and a (propylene-ethylene-1-butene) copolymer, a combination of a (propylene-1-butene) copolymer and a (propylene-ethylene-1-hexene) copolymer, a combination of a (propylene-1-butene) copolymer and a (propylene-ethylene-1-octene) copolymer, a combination of a (propylene-1-butene) copolymer and a (propylene-ethylene-1-decene) copolymer, a combination of a (propylene-1-butene) copolymer and a (propylene-1-butene) copolymer, a combination of a (propylene-1-butene) copolymer and a (propylene-1-hexene) copolymer, a combination of a (propylene-1-butene) copolymer and a (propylene-1-octene) copolymer, a combination of a (propylene-1-butene) copolymer and a (propylene-1-decene) copolymer, a combination of a (propylene-1-hexene) copolymer and a (propylene-1-hexene) copolymer,Combinations of a (propylene-1-hexene) copolymer and a (propylene-1-octene) copolymer, combinations of a (propylene-1-hexene) copolymer and a (propylene-1-decene) copolymer, combinations of a (propylene-1-octene) copolymer and a (propylene-1-octene) copolymer, and combinations of a (propylene-1-octene) copolymer and a (propylene-1-decene) copolymer are exemplified.

[0058] Examples of the heterophasic propylene polymer material that can be included in the propylene resin composition of this embodiment include combinations of a propylene homopolymer and a (propylene-ethylene) copolymer, combinations of a propylene homopolymer and a (propylene-ethylene-1-butene) copolymer, combinations of a (propylene-ethylene) copolymer and a (propylene-ethylene) copolymer, combinations of a (propylene-ethylene) copolymer and a (propylene-ethylene-1-butene) copolymer, and combinations of a (propylene-1-butene) copolymer and a (propylene-1-butene) copolymer. Combinations of a propylene homopolymer and a (propylene-ethylene) copolymer are more preferred.

[0059] The heterophasic propylene polymer material can be produced by multistage polymerization having a polymerization step in the previous stage for producing polymer (I) and a polymerization step in the subsequent stage for further producing polymer (II) in the presence of polymer (I) produced in the previous stage. The polymerization can be carried out using the catalyst systems exemplified as the catalyst systems that can be used for the production of the propylene-based polymers.

[0060] The propylene-based polymer (P) preferably contains one or more selected from the group consisting of a propylene homopolymer and a heterophasic propylene polymer material, and more preferably is a heterophasic propylene polymer material.

[0061] The propylene-based polymer (P) is 13The isotactic pentad fraction (also referred to as the [mmmm] fraction), measured by 13C-NMR, is preferably 0.97 or more, more preferably 0.98 or more. The closer the isotactic pentad fraction of the propylene-based polymer is to 1, the higher the stereoregularity of the molecular structure of the propylene-based polymer and the higher the crystallinity of the propylene-based polymer. When the propylene-based polymer is a copolymer, the isotactic pentad fraction can be measured for the chain of propylene units in the copolymer.

[0062] The melt flow rate (MFR) of the propylene-based polymer (P) measured under the conditions of a temperature of 230 °C and a load of 2.16 kgf is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, preferably 500 g / 10 min or less, more preferably 400 g / 10 min or less, and preferably 0.1 g / 10 min to 500 g / 10 min, from the viewpoint of improving the processability in the molding of the propylene resin composition.

[0063] Incidentally, the intrinsic viscosity of the propylene-based polymer (P) of the present embodiment is usually less than 5 dL / g, 0.1 dL / g or more, preferably 0.5 dL / g or more, more preferably 0.7 dL / g or more and less than 4 dL / g, and still more preferably 0.8 dL / g or more and less than 3 dL / g, from the viewpoints of improving the fluidity and processability of the propylene resin composition.

[0064] In the present embodiment, the weight average molecular weight in terms of polystyrene of the propylene-based polymer (P) is usually 100,000 to 1,000,000, preferably 500,000 to 1,000,000, from the viewpoints of improving the appearance and elongation properties of the molded article.

[0065] The molecular weight distribution (Mw / Mn) of the propylene-based polymer (P) may usually be 10 or less, preferably 3 to 8, from the viewpoints of improving the moldability and mechanical properties.

[0066] In this specification, Mw represents the weight-average molecular weight, Mn represents the number-average molecular weight, and the molecular weight distribution can be measured by gel permeation chromatography (GPC) under the following conditions. Apparatus: HLC-8121 GPC / HT manufactured by Tosoh Corporation Separation column: Three GMHHR-H(S)HT columns manufactured by Tosoh Corporation Measurement temperature: 140 °C Carrier: Orthodichlorobenzene Flow rate: 1.0 mL / min Sample concentration: Approximately 1 mg / mL Sample injection volume: 400 μL Detector: Differential refractive index Calibration curve preparation method: Using standard polystyrene for conversion

[0067] When the propylene-based polymer is a heterophasic propylene polymer material substantially composed of polymer (I) and polymer (II) formed by multi-stage polymerization, a part of polymer (I) prepared in the previous stage of polymerization is withdrawn from the polymerization reactor to obtain its intrinsic viscosity (also referred to as [η]I). The intrinsic viscosity ([η]Total) of the polymer finally obtained by multi-stage polymerization is determined. Using these values of the intrinsic viscosity and the content ratio of each polymer, the intrinsic viscosity ([η]II) of polymer (II) formed in the subsequent stage of polymerization can be calculated. The calculation procedure is as follows. Note that XI and XII can be obtained from the material balance during polymerization. [η]II = ([η]Total - [η]I × XI) / XII [η]Total: Intrinsic viscosity of the final polymer (unit: dL / g) [η]I: Intrinsic viscosity of polymer (I) (unit: dL / g) XI: Weight ratio of polymer (I) to the final polymer XII: Weight ratio of polymer (II) to the final polymer

[0068] The intrinsic viscosity [η]I of polymer (I) is preferably 0.1 dL / g to 5 dL / g, more preferably 0.5 dL / g to 4 dL / g, and even more preferably 0.6 dL / g to 3 dL / g.

[0069] The intrinsic viscosity [η]II of the polymer (II) is preferably from 1 dL / g to 10 dL / g, more preferably from 1.5 dL / g to 9 dL / g, still more preferably from 2 dL / g to 8 dL / g.

[0070] Also, the ratio of [η]II to [η]I ([η]II / [η]I) is preferably from 1 to 20, more preferably from 1 to 10.

[0071] The weight ratio XII of the polymer (II) to the final polymer may be calculated from the following formula using the heat of fusion of crystallization of each of the polymer (I) and the final polymer. XII = 1 - (ΔHf)Total / (ΔHf)I (ΔHf)Total: Heat of fusion of the final polymer (polymer (I) and polymer (II)) (unit: cal / g) (ΔHf)I: Heat of fusion of the polymer (I) (unit: cal / g)

[0072] Also, the molecular weight distribution (Mw / Mn) of the polymer (I) is preferably 1 or more and less than 10, more preferably 2 or more and less than 7, still more preferably 3 or more and less than 5.

[0073] Metal deactivator The propylene resin composition of the present invention contains a metal deactivator (also referred to as component D). A metal deactivator is a compound that has the function of chelating metal ions and prevents the thermal oxidative degradation of a polymer material by metal from progressing in an environment where the polymer material comes into contact with the metal. As component D, a known metal deactivator can be used. For example, benzotriazole derivatives, compounds having one or more groups represented by -CO-NH- (for example, oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives, hydroxybenzoic acid anilide derivatives), sulfur-containing phosphites, etc., which are disclosed in "New Developments in Polymer Additives" (Nikkkan Kogyo Shimbunsha, pages 76 to 85) or Japanese Patent Application Laid-Open No. 8-302331. These metal deactivators can be used alone, and two or more metal deactivators can also be used in combination. Although overlapping with the above, as other examples, compounds containing a nitrogen-containing monocyclic heterocycle in the molecule, compounds containing a nitrogen-containing condensed heterocycle in the molecule, compounds containing a phenolic hydroxyl group in the molecule, compounds containing a salicyl group in the molecule, hydrazones and bis-hydrazones of aliphatic and aromatic aldehydes, hydrazides of aliphatic and aromatic mono- and dicarboxylic acids, and bis-acylated hydrazine derivatives can be mentioned.

[0074] A metal deactivator having a triazole skeleton or a triazine skeleton is preferred.

[0075] Specific preferred examples of the metal deactivator include unsubstituted or alkyl-substituted benzotriazole, 2,4,6-triamino-1,3,5-triazine, 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, ethylenediamine-tetraacetic acid, alkali metal salts (Li, Na, K) of ethylenediamine-tetraacetic acid, N,N'-disalicylidene-ethylenediamine, N,N'-disalicylidene-1,2-propylenediamine, N,N''-disalicylidene-N'-methyl-dipropylenetriamine, 3-(N-salicyloyl)amino-1,2,4-triazole (Adekastab CDA-1M), decamethylenedicarboxylic acid-bis(N'-salicyloylhydrazide), nickel-bis(1-phenyl-3-methyl-4-decanoyl-5-pyrazolate), 2-ethoxy-2'-ethyloxanilide, 5-t-butyl-2-ethoxy-2'-ethyloxanilide, N,N-diethyl-N',N'-diphenyloxamide, N,N'-diethyl-N,N'-diphenyloxamide, oxalic acid-bis(benzylidenehydrazide), thiodipropionic acid-bis(benzylidenehydrazide), isophthalic acid-bis(2-phenoxypropionylhydrazide), bis(salicyloylhydrazine), N-salicylidene-N'-salicyloylhydrazone, 2',3-bis[[3-[3,5-di-t-butyl-4-hydroxyphenyl]propionyl]]propionohydrazide, trimethyl phosphate, tris[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butyl)phenyl-5-methyl]-phenyl phosphite, bis[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenyl]-pentaerythritol-diphosphite, tetrakis[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenyl]-1,6-Hexamethylene-bis(N-hydroxyethyl-N-methylsemicarbazide)-diphosphite, tetrakis[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenyl]-1,10-decamethylene-di-carboxylic acid-di-hydroxyethylcarbonylhydrazide-diphosphite, tetrakis[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenyl]-1,10-decamethylene-di-carboxylic acid-di-salicyloylhydrazide-diphosphite, tetrakis[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenyl]-di(hydroxyethylcarbonyl)hydrazide-diphosphite, tetrakis[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenyl]-N,N'-bis(hydroxyethyl)oxamide-diphosphite, 2,2'-oxamidobis[ethyl 3-(3,5-t-butyl-4-hydroxyphenyl)propionate], N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N'-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]propanohydrazide, melamine and the like can be mentioned.,

[0076] More preferred examples include 3-(N-salicyloyl)amino-1,2,4-triazole, trimethyl phosphate, N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide, melamine, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N'-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]propanohydrazide.,

[0077] Hindered amine light stabilizer (H) The propylene resin composition of the present invention contains a hindered amine stabilizer (also referred to as component H). A hindered amine stabilizer is a compound having a 2,2,6,6-tetramethylpiperidine skeleton in the molecule, and is a light stabilizer that captures radicals generated by light (ultraviolet rays) and prevents organic materials and polymer materials from deteriorating due to the decomposition of hydroperoxides in organic materials, polymer materials, etc. For example, low molecular weight or high molecular weight light stabilizers can be mentioned. In addition, the hindered amine light stabilizer (H) may be used alone or in combination of two or more kinds.

[0078] A low molecular weight light stabilizer is a light stabilizer having a molecular weight of less than 1000. For example, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: Tinuvin770, molecular weight: 480), bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: Tinuvin765, molecular weight: 508), tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate (trade name: Adeka Stab LA-57, molecular weight: 792), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate (trade name: Adeka Stab LA-52, molecular weight: 847), bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) decanedioate and the reaction product of 1,1-dimethylethyl hydroperoxide and octane (trade name: TINUVIN123, molecular weight: 737), etc. can be mentioned.

[0079] A high molecular weight light stabilizer refers to a light stabilizer with a molecular weight of 1000 or more. For example, a sterically hindered amine oligomer, "N-(2,2,6,6-tetramethyl-4-piperidyl) maleimide, and a copolymer composed of α-olefin (C20-24)" (trade name: UVINUL[registered trademark]5050H, molecular weight 3500), a formaldehyde polycondensate, a reaction product of {2,4,6-trichloro-1,3,5-triazine·[N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diyldiamine]·morpholine polymer} and formic acid (trade name: Cyasorb UV-3529, molecular weight: about 1700), a polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (trade name: Tinuvin 622LD, molecular weight: about 3100 - 4000), a mixture of N,N',N'',N'''-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine (molecular weight: 2286, 90%) and a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (molecular weight: about 3100 - 4000) (trade name: Chimassorb 119FL), a mixture of {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 (Adekastab LA-63, molecular weight: about 2000), a 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}} (trade name: Chimassorb 944LD, molecular weight 2000 - 3100), dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethylpiperidin-1,6-hexamethylenediamine and N-(2,2,6,Polycondensates of (6 - tetramethyl - 4 - piperidyl) butylamine (trade name: CHIMASORB 2020 FDL, molecular weight: about 2600 - 3400), etc. may be mentioned.

[0080] Ethylene - α - olefin copolymer (E) The propylene resin composition of this embodiment may contain an ethylene - α - olefin copolymer (also referred to as component E).

[0081] In the ethylene - α - olefin copolymer (E), when the total weight of the ethylene - α - olefin copolymer is 100% by weight, the total of the content ratio of monomer units derived from ethylene and the content ratio of monomer units derived from α - olefins having 4 or more carbon atoms may be 100% by weight.

[0082] Examples of α - olefins having 4 or more carbon atoms include α - olefins having 4 to 12 carbon atoms. Examples of α - olefins having 4 to 12 carbon atoms include 1 - butene, 1 - pentene, 1 - hexene, 4 - methyl - 1 - pentene, 1 - octene, and 1 - decene. Among α - olefins having 4 or more carbon atoms, 1 - butene, 1 - hexene, and 1 - octene are preferable. The above α - olefins may be α - olefins having a cyclic structure such as vinylcyclopropane and vinylcyclobutane.

[0083] Examples of the ethylene - α - olefin copolymer (E) include ethylene - 1 - butene copolymers, ethylene - 1 - hexene copolymers, ethylene - 1 - octene copolymers, ethylene - 1 - decene copolymers, ethylene - (3 - methyl - 1 - butene) copolymers, and copolymers of ethylene and α - olefins having a cyclic structure.

[0084] In the ethylene-α-olefin copolymer (E), the content ratio of monomer units derived from α-olefins having 4 or more carbon atoms is preferably 1% by weight to 49% by weight, more preferably 5% by weight to 49% by weight, and even more preferably 24% by weight to 49% by weight, based on the total weight of the ethylene-α-olefin copolymer (100% by weight).

[0085] The ethylene-α-olefin copolymer (E) preferably has an MFR (measured at a temperature of 190 °C and a load of 2.16 kgf) of 0.1 g / 10 min or more and 100 g / 10 min or less. More preferably, the MFR is 0.5 g / 10 min or more and 70 g / 10 min or less.

[0086] From the viewpoint of improving the impact resistance of the molded article, the density of the ethylene-α-olefin copolymer (E) is 3 ~0.890 g / cm 3 preferably, 3 ~0.880 g / cm 3 more preferably, 3 ~0.870 g / cm 3 and even more preferably.

[0087] The ethylene-α-olefin copolymer (E) can be produced by polymerizing ethylene and an α-olefin having 4 or more carbon atoms using a polymerization catalyst.

[0088] Examples of the polymerization catalyst for production include homogeneous catalysts typified by metallocene catalysts and Ziegler-Natta type catalysts.

[0089] Examples of homogeneous catalysts include: a catalyst consisting essentially of a compound of a Group 4 transition metal of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; a catalyst containing a compound of a Group 4 transition metal of the periodic table having a cyclopentadienyl ring, a compound that reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound; and a catalyst obtained by supporting and modifying an inorganic particle (such as silica, clay mineral, etc.) with a catalyst component (such as a compound of a Group 4 transition metal of the periodic table having a cyclopentadienyl ring, a compound that forms an ionic complex, an organoaluminum compound, etc.).

[0090] Examples of Ziegler-Natta type catalysts include a catalyst obtained by combining a titanium-containing solid transition metal component and an organometallic component.

[0091] As the ethylene-α-olefin copolymer (E), commercially available products may be used. Examples of commercially available ethylene-α-olefin copolymers (E) include Engage (registered trademark) manufactured by The Dow Chemical Company Japan, Toughmer (registered trademark) manufactured by Mitsui Chemicals, Inc., Neozex (registered trademark), Ultzex (registered trademark) manufactured by Prime Polymer Co., Ltd., Exxelen FX (registered trademark), Sumika Sen (registered trademark), and Esprene SPO (registered trademark) manufactured by Sumitomo Chemical Co., Ltd.

[0092] Inorganic filler (F) From the viewpoint of improving mechanical properties, dimensional stability, etc., the propylene resin composition according to this embodiment may further contain an inorganic filler (also referred to as component F).

[0093] Examples of the inorganic filler (F) include (i) fibrous inorganic fillers and (ii) non-fibrous inorganic fillers. In this embodiment, two or more kinds of inorganic fillers (F) may be used in combination. Specific examples will be described below.

[0094] (i) Fibrous inorganic filler In this embodiment, the fibrous inorganic filler preferably has an average fiber diameter of 0.2 μm to 20 μm, an average fiber length of 5 μm to 200 μm, and an aspect ratio of 10 to 30. From the viewpoints of improving the rigidity of the molded body and improving the appearance of the molded body, the average fiber diameter is more preferably 0.3 μm to 10 μm, the average fiber length is more preferably 7 μm to 150 μm, and the aspect ratio is more preferably 12 to 25.

[0095] The average fiber diameter and the average fiber length of the fibrous inorganic filler are, for example, the average values of the fiber diameters and the fiber lengths respectively measured by randomly selecting 50 or more from the images of the fibrous inorganic filler obtained by an electron microscope, and the aspect ratio can be calculated using these average values.

[0096] Examples of the fibrous inorganic filler include fibrous magnesium oxysulfate, potassium titanate fiber, magnesium hydroxide fiber, aluminum borate fiber, calcium silicate fiber, calcium carbonate fiber, carbon fiber, glass fiber, and metal fiber. Among these, it is preferable to use fibrous magnesium oxysulfate and calcium silicate fiber.

[0097] The fibrous inorganic filler can be used as it is. From the viewpoints of improving the interfacial adhesion and further improving the dispersibility, the fibrous inorganic filler may be further surface-treated with, for example, a silane coupling agent or a higher fatty acid metal salt before use.

[0098] Examples of the higher fatty acid metal salt that can be used for the surface treatment include calcium stearate, magnesium stearate, and zinc stearate.

[0099] In this embodiment, examples of the form of the fibrous inorganic filler include powder form, flake form, and granular form. In this embodiment, any of the above forms of the fibrous inorganic filler may be used. From the viewpoint of good handleability, it is preferable to use a granular fibrous inorganic filler as the fibrous inorganic filler.

[0100] (ii) Non-fibrous inorganic filler Examples of the non-fibrous inorganic filler include talc, mica, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, calcium sulfate, silica sand, carbon black, titanium oxide, magnesium hydroxide, molybdenum, diatomaceous earth, sericite, shirasu, calcium hydroxide, calcium sulfite, sodium sulfate, bentonite, graphite, etc. From the viewpoint of improving the impact strength of the molded body and achieving good appearance, it is preferable to use talc.

[0101] The average particle diameter of the non-fibrous inorganic filler is preferably 15 μm or less, and more preferably 10 μm or less. Here, the average particle diameter of the non-fibrous inorganic filler is determined based on the volume-based particle size distribution measurement data measured by the laser diffraction method according to the method specified in JIS R1629, and in the particle size distribution measurement data, it means the particle diameter (50% equivalent particle diameter) when the cumulative number of particles from the smaller particle diameter side reaches 50%. The particle diameter defined in this way is generally referred to as the "50% equivalent particle diameter" and is denoted as "D50".

[0102] The non-fibrous inorganic filler can be used as it is. From the viewpoint of improving the interfacial adhesion and dispersibility, the surface of the non-fibrous inorganic filler may be treated with a silane coupling agent, a titanium coupling agent, or a surfactant before use.

[0103] Examples of the surfactant that can be used for the surface treatment include higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acid salts.

[0104] The fibrous inorganic filler may be used as it is, or the surface may be treated with a silane coupling agent or a higher fatty acid metal salt from the viewpoint of improving the interfacial adhesion and dispersibility before use.

[0105] Other additive (A) In order to improve properties - for example, to improve rigidity, impact resistance, heat aging resistance, or water resistance, and / or to increase the tensile fracture strain - the propylene resin composition of this embodiment may contain, as additional optional components, various other additives (also referred to as component A) in addition to the components described above.

[0106] Examples of such optional component additives include antioxidants, neutralizing agents, ultraviolet absorbers, lubricants, antistatic agents, colorants (e.g., inorganic pigments, organic pigments), flame retardants, elastomers, antiblocking agents, processing aids, organic peroxides, pigment dispersants, foaming agents, foaming nucleating agents, plasticizers, crosslinking agents, crosslinking aids, brightening agents, antibacterial agents, light diffusing agents, and molecular weight regulators.

[0107] The propylene resin composition of this embodiment may contain these additives singly or in any combination of two or more optional components in any ratio.

[0108] Among them, antioxidants, neutralizing agents, ultraviolet absorbers, and colorants are preferably used as additive (A). Specific explanations are given below. The propylene resin composition of this embodiment preferably further contains at least one selected from the group consisting of organic peroxides, neutralizing agents, antioxidants, ultraviolet absorbers, and colorants in addition to the above components.

[0109] Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydroxylamine-based antioxidants, etc., and preferably phenolic antioxidants, phosphorus-based antioxidants, or sulfur-based antioxidants.

[0110] Examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, tetrakis[methylene-3(3’,5’-di-tert-butyl-4-hydroxyphenyl)propionate]methane (Irganox 1010), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1076), 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5·5]undecane, 1,3,5-tris 2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol-N-bis-3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thiobis-diethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2’-methylene-bis-(4-methyl-6-tert-butylphenol), 2,2’-methylene-bis-(4-ethyl-6-tert-butylphenol), 2,2’-methylene-bis-(4,6-di-tert-butylphenol), 2,2’-ethylidene-bis-(4,6-di-tert-butylphenol), 2,2’-butylidene-bis-(4-methyl-6-tert-butylphenol), 4,4’-butylidenebis(3-methyl-6-tert-butylphenol), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-di-tert-amyl-6-(1-(3,Examples include 5-di-tert-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate and tocopherols. Examples of tocopherols include vitamin E, which is α-tocopherol. Preferably, 2,6-di-tert-butyl-4-methylphenol, tetrakis[methylene-3(3’,5’-di-tert-butyl-4-hydroxyphenyl)propionate]methane (Irganox 1010), 2,6-di-tert-butyl-4-methylphenol, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1076), 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5·5]undecane, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, or vitamin E, more preferably tetrakis[methylene-3(3’,5’-di-tert-butyl-4-hydroxyphenyl)propionate]methane (Irganox 1010), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1076), or vitamin E.,

[0111] Examples of phosphorus-based antioxidants include tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168), distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-diphenylenediphosphonite, 2,2'-methylenebis(4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl) fluorophosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2-(2,4,6-tri-tert-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxaphospholane, 2,2',2''-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy] dibenzo[d,f][1,3,2] dioxaphosphepine. Preferably, tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168) or 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy] dibenzo[d,f][1,3,2] dioxaphosphepine.

[0112] Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, neopentanetetrayl tetrakis(3-laurylthiopropionate), and bis[2-methyl-4-(3-n-alkyl(C12-C14)thiopropionyloxy)-5-tert-butylphenyl]sulfide. Preferably, they are dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, or distearyl 3,3'-thiodipropionate.

[0113] The hydroxylamine-based compound is a compound represented by the following general formula, and in the process of the degradation reaction of the polymer material by heat and oxygen, it forms a nitroxyl radical to suppress the thermal oxidation degradation of the polymer material.

Chemical formula

[0114] R in the hydroxylamine-based compound represented by the above general formula 4 and R 5 are C12-30 alkyl groups, and R 4 and R 5 may be the same or different. As the alkyl group, preferably a linear alkyl group or an alkyl group substituted with a cyclic alkyl group, preferably an alkyl group having 12 to 22 carbon atoms, more preferably a linear saturated alkyl group having 12 to 22 carbon atoms.

[0115] Examples of the linear saturated alkyl group include linear saturated alkyl groups such as tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group, etc. Preferably, they are tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group.

[0116] Preferably, at least one selected from phenolic antioxidants and phosphorus-based antioxidants is used. Each of the above various antioxidants may be used alone or in combination of two or more.

[0117] Examples of the neutralizing agent include calcium stearate, hydrotalcite, alkaline earth metal oxides, alkaline earth metal hydroxides, etc. These neutralizing agents may be used alone or in combination of two or more.

[0118] Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, trisdiamine-based ultraviolet absorbers, anilide-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, etc. These neutralizing agents may be used alone or in combination of two or more.

[0119] Examples of the colorant include inorganic pigments and organic pigments. Examples of the inorganic pigment include carbon black, iron oxide, titanium oxide, zinc oxide, red lead, cadmium red, cadmium yellow, ultramarine blue, cobalt blue, titanium yellow, lead white, red lead, lead yellow, indigo, etc. Examples of the organic pigment include quinacridone, polyazo yellow, anthraquinone yellow, polyazo red, azo lake yellow, perylene, phthalocyanine green, phthalocyanine blue, isoindolinone yellow, etc.

[0120] The propylene resin composition may contain other additives such as resins and rubbers as additives other than the additives already described.

[0121] Examples of the other additive (A) include 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 resin, fluororesins, polyacetal, grafted polyphenylene ether resin and polyphenylene sulfide resin, polyurethane, polyamide, polyester resins (e.g., polyethylene terephthalate, polybutylene terephthalate), polycarbonate, polysulfone, polyetheretherketone, polyethersulfone, thermoplastic resins such as aromatic polyester resins, epoxy resins, diallyl phthalate prepolymer, silicone resins, silicone rubbers, polybutadiene, 1,2-polybutadiene, polyisoprene, styrene / butadiene copolymer, butadiene / acrylonitrile copolymer, epichlorohydrin rubber, acrylic rubber, natural rubber, and further PLA resin (polylactic acid) produced by polymerizing plant-derived monomers extracted from bio-based raw materials.

[0122] At least one of various components such as propylene polymers, ethylene-α-olefin copolymers, and inorganic fillers used as raw materials for producing the propylene resin composition may be recycled.

[0123] Content of each component In the propylene resin composition of the present invention, the content of each component is not particularly limited on the condition that the ratio of the weight of the hindered amine-based light stabilizer to the weight of the metal deactivator is 10 or more. The ratio is preferably 13 or more, 15 or more, 18 or more, or 20 or more. The upper limit of the ratio is not particularly limited, but may be, for example, 200 or less, 150 or less, 100 or less, or 70 or less. All combinations of "any of the above lower limits to any of the above upper limits" are considered to be specified herein.

[0124] When the weight ratio of the hindered amine light stabilizer to the weight of the metal deactivator is 10 or more, the propylene resin composition of the present invention and a molded article containing (manufactured from) the same have a large tensile fracture strain and / or low mold fouling property. Due to the large tensile fracture strain, the molded article is less likely to be sharply cracked, improving safety. The tensile fracture strain is measured, for example, according to the method described in the examples. Due to the low mold fouling property, the number of mold washings can be reduced and / or the reduction of the mold and the life (number of durable times) of the mold can be extended, reducing the environmental load. The mold fouling property is measured, for example, according to the method described in the examples.

[0125] The content ratio of the propylene-based polymer (P) to 100 parts by weight of the propylene resin composition of the present invention is preferably 50 parts by weight or more, may be 60 parts by weight or more, may be 70 parts by weight or more, may be 80 parts by weight or more, may be 90 parts by weight or more, may be about 100 parts by weight or less, may be 99 parts by weight or less, may be 50 parts by weight to 95 parts by weight, or may be 60 parts by weight to 95 parts by weight. When the propylene resin composition of the present invention contains other polymers in addition to component P, the content ratio of the total weight of component P and the other polymers to 100 parts by weight of the propylene resin composition may be as described above. The "other polymer" is preferably an ethylene-α-olefin copolymer (E).

[0126] When the propylene resin composition of the present invention contains an ethylene-α-olefin copolymer (E), the content ratio of the ethylene-α-olefin copolymer (E) in the propylene resin composition is usually more than 0 part by weight and 40 parts by weight or less, preferably 1 part by weight or more and 40 parts by weight or less, preferably 5 parts by weight or more and 35 parts by weight or less, and more preferably 5 parts by weight or more and 30 parts by weight or less, when the total amount of the propylene resin composition is 100 parts by weight. In one aspect, the weight ratio of component E to the weight of component P is more than 0 part by weight and 40 parts by weight or less, preferably 1 part by weight or more and 40 parts by weight or less, preferably 5 parts by weight or more and 35 parts by weight or less, and more preferably 5 parts by weight or more and 30 parts by weight or less. The above “more than 0 part by weight” may be replaced with “0 part by weight or more”. In this specification, “0 part by weight or more” used for the content ratio of any component means both the aspect in which the component is included and the aspect in which the component is not included.

[0127] The content ratio of the metal deactivator (D) to 100 parts by weight of the propylene-based polymer (P), 100 parts by weight of the total weight of the polymer components, or 100 parts by weight of the propylene resin composition is preferably 10 weight ppm to 1000 weight ppm, more preferably 50 weight ppm to 800 weight ppm, and still more preferably 80 weight ppm to 500 weight ppm. In order to exhibit the metal deactivating effect, the content of component D is preferably not less than the above lower limit value. Further, in order not to adversely affect the hue of the propylene resin composition, the content of component D is preferably not more than the above upper limit value.

[0128] The content ratio of the hindered amine light stabilizer (H) to 100 parts by weight of the propylene-based polymer (P), 100 parts by weight of the total weight of the polymer components, or 100 parts by weight of the propylene resin composition is preferably 200 ppm by weight to 10,000 ppm by weight, more preferably 500 ppm by weight to 8,000 ppm by weight, and still more preferably 1,000 ppm by weight to 5,000 ppm by weight. In order for the resin composition of the present invention to have sufficient light stability, the content of component H is preferably not less than the above lower limit value. Further, in order to avoid component H bleeding out on the surface of the molded article, whitening of the surface, smoking during the molding process, or mold contamination, the content of component H is preferably not more than the above upper limit value.

[0129] When the polypropylene resin composition of the present invention contains an inorganic filler, the content ratio of the inorganic filler (F) to 100 parts by weight of the propylene-based polymer (P), 100 parts by weight of the total weight of the polymer components, or 100 parts by weight of the propylene resin composition is usually more than 0 part by weight and 40 parts by weight or less, preferably 1 part by weight or more and 40 parts by weight or less, preferably 5 parts by weight or more and 35 parts by weight or less, and more preferably 5 parts by weight or more and 30 parts by weight or less. The above "more than 0 part by weight" may be replaced by "not less than 0 part by weight".

[0130] When the polypropylene resin composition of the present invention contains an antioxidant, the content ratio of the antioxidant to 100 parts by weight of the propylene-based polymer (P) or 100 parts by weight of the total weight of the polymer components is preferably more than 0 part by weight and 5 parts by weight, preferably 0.001 part by weight to 5 parts by weight, more preferably 0.01 part by weight to 3 parts by weight, still more preferably 0.05 part by weight to 2 parts by weight, and even more preferably 0.1 part by weight to 1 part by weight. The above "more than 0 part by weight" may be replaced with "0 part by weight or more". In order to make the rigidity, impact resistance, heat aging resistance, or water resistance good, and / or in order to make the tensile fracture strain larger, the content of the antioxidant is preferably not less than the above lower limit value. Also, in order to make the appearance of the molded body such as hue and gloss good, the content of the antioxidant is preferably not more than the above upper limit value. On the other hand, in order to reduce the mold contamination property, the content ratio of the antioxidant may be 0 part by weight to 0.05 part by weight, 0 part by weight to 0.01 part by weight, 0 part by weight to 0.005 part by weight, or 0 part by weight (i.e., not contained). The mold contamination property is measured, for example, according to the method described in the examples. The water resistance is measured, for example, according to the method described in the examples.

[0131] Method for producing a propylene resin composition The propylene resin composition of the present embodiment can be produced by melt-kneading each of the components already described. The temperature during melt-kneading may be 180°C or higher, may be 180°C to 300°C, or may be 180°C to 250°C.

[0132] Examples of the melt-kneading apparatus in the melt-kneading for the production of the propylene resin composition of the present embodiment include any conventionally known and suitable Banbury mixer, single-screw extruder, co-rotating twin-screw extruder, and counter-rotating twin-screw extruder.

[0133] Specific examples of the melt kneading device include ZSK (registered trademark) manufactured by Coperion, TEM (registered trademark) manufactured by Shibaura Machine Co., Ltd., TEX (registered trademark) manufactured by Nippon Steel & Sumitomo Metal Corporation, KZW (registered trademark) manufactured by Technovel Corporation, CMP (registered trademark), TEX (registered trademark) manufactured by Nippon Steel & Sumitomo Metal Corporation, FCM (registered trademark), NCM (registered trademark), and LCM (registered trademark) manufactured by Kobe Steel, Ltd.

[0134] The order of kneading the raw materials is not particularly limited. For example, all the raw materials may be kneaded by charging them into the manufacturing apparatus all at once, or after kneading some of the selected components, the obtained kneaded product and other components may be kneaded.

[0135] The properties of the propylene resin composition of the present embodiment are not particularly limited. The propylene resin composition of the present embodiment can be, for example, in the form of strands (filaments), sheets, flat plates, or pellets. The pellet shape can be produced, for example, by preparing a strand-like propylene resin composition and then cutting it to an appropriate length.

[0136] Molded article The present invention also relates to a molded article formed from the propylene resin composition. That is, the propylene resin composition of the present embodiment can be suitably used as a material for forming a molded article. The molded article can be obtained by molding the propylene resin composition by various molding methods. The shape, size, etc. of the molded article may be determined as appropriate.

[0137] The propylene resin composition of the present embodiment can be used, for example, as a material for molded articles such as automotive materials, home appliance materials, monitor materials, OA equipment materials, medical materials, drain pans, toiletries materials, food packaging containers, bottles, containers, sheets, and films. The propylene resin composition of the present embodiment is less likely to be charged and can suppress the adhesion of, for example, dust, so it is preferably applied to materials for vehicle-related members, home appliance materials, and food packaging containers such as retort pouches and pouches that can be heated in a microwave oven.

[0138] The propylene resin composition of this embodiment is preferably used as a material for injection molding in particular.

[0139] Hereinafter, an example of an injection molded article manufactured by using the propylene resin composition of this embodiment as a material for injection molding will be described.

[0140] The injection molded article is a molded article obtained by molding the propylene resin composition of this embodiment. The injection molded article generally has excellent dimensional stability.

[0141] The injection molded article can be manufactured by any conventionally known suitable injection molding method. Examples of the injection molding method include an injection foam molding method, a supercritical injection foam molding method, a super high-speed injection molding method, an injection compression molding method, a gas assist injection molding method, a sandwich molding method, a sandwich foam molding method, and an insert / outset molding method.

[0142] The molded article (such as an injection molded article) of this embodiment can be manufactured by the above method with any suitable shape and dimensions corresponding to the application.

[0143] Here, as the material applications of vehicle-related members that are injection molded articles, for example, interior parts such as door trims, pillars, instrument panels, consoles, rocker panels, armrests, door panels, spare tire covers, and exterior parts such as bumpers, spoilers, fenders, side steps, and other parts such as air intake ducts, coolant reserve tanks, fender liners, fans, under deflectors, and integral molded parts such as front end panels can be mentioned.

[0144] As household electrical appliance materials, for example, materials for washing machines (outer tubs, inner tubs, lids, pulsators, balancers, etc.), materials for dryers, materials for vacuum cleaners, materials for rice cookers, materials for pots, materials for warmers, materials for dishwashers, materials for air purifiers can be mentioned.

Examples

[0145] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[0146] In the examples and comparative examples, the following raw materials were used.

[0147] Component P: Propylene-based polymer The following propylene-based polymer P1 was prepared as Component P.

[0148] (P1) Heterophasic propylene polymer material The heterophasic propylene polymer material was produced by a gas-phase polymerization method in the presence of a polymerization catalyst obtained by the method described in Example 1 of JP-A-2004-182981. The physical properties of the obtained Component P1 are as follows.

[0149] Melt flow rate (MFR) (230 °C, 2.16 kg load): 27.5 g / 10 min (a) Propylene homopolymer component (Polymer I) Intrinsic viscosity: 1.06 dL / g (b) Propylene-ethylene random copolymer component (Polymer II) Intrinsic viscosity: 2.8 dL / g Proportion of propylene-ethylene random copolymer component: 21.0% by weight Ethylene content in Polymer II: 39.0% by weight

[0150] In Component P1, the "ethylene content in Polymer II" indicates the content ratio of monomer units derived from ethylene based on the total weight of Polymer II.

[0151] Ethylene content in Polymer II The content ratio of ethylene in the polymer II was determined based on the 13C-NMR spectrum measured under the following conditions according to the report by Kakugo et al. (Macromolecules, 15, 1150-1152 (1982)). The 13C-NMR spectrum was measured under the following conditions using a sample prepared by uniformly dissolving approximately 200 mg of a heterophagic propylene polymerization material in 3 mL of orthodichlorobenzene in a test tube with a diameter of 10 mm. Measurement temperature: 135 °C Pulse repetition time: 10 seconds Pulse width: 45° Number of integrations: 2500 times

[0152] Intrinsic viscosity (unit: dL / g) The intrinsic viscosity is a value measured at a temperature of 135 °C using tetralin as a solvent by the following method.

[0153] Using an Ubbelohde viscometer, the reduced viscosity is measured at three points with concentrations of 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL. The intrinsic viscosity is determined by the extrapolation method of plotting the reduced viscosity against the concentration and extrapolating the concentration to zero. The calculation method of the intrinsic viscosity by the extrapolation method is described, for example, on page 491 of "Polymer Solutions, Polymer Experimentation 11" (published by Kyoritsu Shuppan Co., Ltd. in 1982).

[0154] Component D: Metal deactivator The following metal deactivators were prepared as Component D.

[0155] (D1) ADEKA STAB CDA-1M manufactured by ADEKA CORPORATION: 3-(N-salicyloyl)amino-1,2,4-triazole (D2) ADEKA STAB CDA-1 manufactured by ADEKA CORPORATION: 2-Hydroxy-N-1H-1,2,4-triazol-3-ylbenzamide (D3) ADEKA STAB ZS-19 manufactured by ADEKA CORPORATION: Melamine resin ((1,3,5-triazine-2,4,6-triamine)H 2 C=O (formaldehyde)), phenol compound, composite of organic compounds

[0156] Component H: Hindered amine light stabilizer The following hindered amine light stabilizers were prepared as Component H.

[0157] (H1) Uvinul 5050H manufactured by BASF Japan Ltd. (H2) Adeka Stab LA-52 manufactured by ADEKA Corporation: Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate (H3) SABO STAB UV 119 manufactured by SABO S.p.A.: The following mixture N,N',N'',N'''-tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1,10-diamine Dimethyl succinate·1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate

[0158] Component A: Other additives As Component A, which is other optional suitable components, the following components were prepared.

[0159] (A1) Irganox 1010 manufactured by BASF Japan Ltd. (A2) Irgfos 168 manufactured by BASF Japan Ltd.

[0160] Examples 1 to 7 and Comparative Examples 1 to 4

[0161] Production of propylene resin composition The raw materials having the composition shown in Table 1 were preliminarily mixed uniformly with a Henschel mixer or a tumbler, and then melt-kneaded using a twin-screw kneading extruder (TEX44αII-49BW-3V type manufactured by Japan Steel Works, Ltd.) to obtain a pelletized propylene resin composition.

Table 1

[0162] The conditions for melt-kneading were as follows: cylinder temperature 210 °C; screw rotation speed 200 rpm; the screen mesh was three layers of 40 mesh, 80 mesh, and 40 mesh, and the extrusion rate was 50 kg / hr. The evaluation results are shown in Table 1.

[0163] Manufacture of injection molded article for evaluating tensile fracture strain The pelletized propylene resin composition was injection molded under the following conditions within the range described in JIS K7152 to produce an injection molded article for evaluating tensile fracture strain. The propylene resin composition melted by the injection molding machine was supplied into the mold cavity from the gate by the injection molding machine. The measurement results are shown in Table 1. Injection molding machine: Toyo Machine Metal Si30III Injection molding machine: Toyo Machine Metal Si30III (Clamping force 30 tons, cylinder diameter 18 mm) Cylinder temperature: 200 °C Mold temperature: 50 °C Injection speed: 20 mm / second Cooling time: 30 seconds

[0164] Evaluation of mold contamination (mold contaminated area) After drying the pelletized propylene resin composition at 100 °C for 1 hour, it was continuously injection molded 60 shots under the following conditions, and after taking out the molded article, a transparent heat-resistant polyester film was attached to the mold, clamped, held for 5 seconds, and then taken out. The area of the mold contamination part transferred to the film (unit: mm 2 ) was measured with an image analyzer. It was assumed that the smaller the area of the mold contamination part, the smaller the mold contamination. Injection molding machine: Toyo Machine Metal Si30III (Clamping force 30 tons, cylinder diameter 18 mm) Cylinder temperature: 260 °C Mold temperature: 50 °C Injection speed: 40 mm / second Cooling time: 10 seconds

[0165] Color difference evaluation before and after the water resistance test The pellet-shaped propylene resin composition was dried at 100°C for 1 hour and then injection-molded under the following conditions to produce a flat molded body with a length of 80 mm, a width of 35 mm, and a thickness of 2.0 mm. Injection molding machine: Toyo Machine Metal Si30III (Clamping force 30 tons, cylinder diameter 18 mm) Cylinder temperature: 220°C Mold temperature: 50°C Injection speed: 20 mm / second Cooling time: 30 seconds

[0166] One of the obtained flat molded bodies was placed in a 0.5 L glass bottle, then water was added, the lid was closed and sealed, and the molded body was submerged and fixed in a constant temperature water bath adjusted to 60°C and left standing for 1000 hours.

[0167] After the glass bottle was taken out of the constant temperature water bath, the flat molded body was taken out and the water on the surface was wiped off.

[0168] The central part of the surface of the flat molded body was measured using a color difference meter (manufactured by BYK: BYK-mac) with a measurement area of Φ23 mm, an illumination of 45 degrees, and a measurement angle of 45 degrees. Using the value before the water resistance test as a reference, the value after the water resistance test was measured, and the color difference ΔE*ab was obtained.

[0169] From Table 1, it can be seen that the molded body according to the example has a large tensile fracture strain. That is, it was confirmed that according to the propylene resin composition of the present invention, a molded body with a large tensile fracture strain can be produced and the molded body of the present invention has a large tensile fracture strain.

Claims

1. A propylene resin composition comprising a propylene polymer, a metal deactivator having a triazole skeleton or a triazine skeleton, and a hindered amine light stabilizer having a 2,2,6,6-tetramethylpiperidine skeleton, the propylene-based polymer is a heterophasic propylene polymer material; a weight ratio of the metal deactivator is 10 ppm by weight to 1,000 ppm by weight, and a weight ratio of the hindered amine light stabilizer is 200 ppm by weight to 10,000 ppm by weight, relative to 100 parts by mass of the propylene polymer; the ratio of the weight of the hindered amine light stabilizer to the weight of the metal deactivator is 10 or more; Propylene resin composition.

2. The propylene resin composition according to claim 1 , wherein the ratio of the weight of the hindered amine light stabilizer to the weight of the metal deactivator is 50 or less.

3. The propylene resin composition according to claim 1, wherein a weight ratio of the propylene-based polymer is 50 parts by weight or more based on 100 parts by weight of the total weight of the propylene resin composition.

4. The propylene resin composition according to claim 1, wherein the propylene resin composition has a melt flow rate (measured under conditions of a temperature of 230° C. and a load of 2.16 kgf) of 0.1 g / 10 min or more.

5. The propylene resin composition according to claim 1, wherein the propylene polymer has a melt flow rate (measured under conditions of a temperature of 230° C. and a load of 2.16 kgf) of 0.1 g / 10 min or more.

6. The propylene resin composition according to claim 1, further comprising an ethylene-α-olefin copolymer.

7. The propylene resin composition according to claim 6, wherein the weight ratio of the ethylene-α-olefin copolymer is 1 part by weight to 40 parts by weight based on 100 parts by weight of the total weight of the propylene resin composition.

8. The propylene resin composition of claim 1 further comprising an inorganic filler.

9. The propylene resin composition according to claim 8, wherein the weight ratio of the inorganic filler is 1 part by weight to 40 parts by weight based on 100 parts by weight of the total weight of the propylene resin composition.

10. The propylene resin composition according to claim 1, further comprising an ethylene-α-olefin copolymer and an inorganic filler.

11. A molded article comprising the propylene resin composition according to any one of claims 1 to 10.

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