Propylene resin composition and molded body

Abstract

To provide: a molded body excellent in low-temperature impact strength; and a propylene resin composition that is a raw material of the molded body.SOLUTION: A propylene resin composition includes a recycled resin whose swell ratio is 1.3 or more, and a virgin propylene polymer.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Molded articles made of propylene resin compositions are used as automobile materials, home appliance materials, container and packaging materials, and the like. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2007-277366 A Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, molded articles used for automobile materials and the like are required to have high low-temperature impact strength.

[0005] Therefore, an object of the present invention is to provide a propylene resin composition capable of producing a molded article having excellent low-temperature impact strength. Another object of the present invention is to provide a molded article having excellent low-temperature impact strength. [Means for solving the problem]

[0006] The present invention relates to, but is not limited to, the following: [Invention 1] A propylene resin composition comprising a recycled resin having a swell ratio of 1.3 or more when measured under the following conditions, and a virgin propylene polymer: Measurement temperature = 220℃, orifice L / D = 40mm / 1mm, shear rate = 2432sec -1 . [Invention 2] The propylene resin composition according to Invention 1, wherein the recycled resin comprises at least one selected from the group consisting of a propylene polymer and an ethylene-α-olefin copolymer. [Invention 3] The propylene resin composition according to Invention 2, wherein the propylene polymer comprises at least one selected from the group consisting of a propylene homopolymer and a heterophasic propylene polymer material. [Invention 4] 4. The propylene resin composition according to any one of Inventions 1 to 3, wherein the recycled resin comprises a plurality of recycled resins. [Invention 5] 5. The propylene resin composition according to any one of Inventions 1 to 4, wherein the virgin propylene polymer comprises a propylene polymer. [Invention 6] The propylene resin composition according to Invention 5, wherein the propylene polymer comprises at least one selected from the group consisting of a propylene homopolymer and a heterophasic propylene polymer material. [Invention 7] 7. The propylene resin composition according to any one of Inventions 1 to 6, further comprising an inorganic filler. [Invention 8] The propylene resin composition according to claim 7, wherein the inorganic filler comprises a recycled inorganic filler. [Invention 9] 9. The propylene resin composition according to any one of Inventions 1 to 8, further comprising an ethylene-α-olefin copolymer as a component other than the recycled resin. [Invention 10] A molded article comprising the propylene resin composition according to any one of Inventions 1 to 9. [Invention 11] 10. A method for producing the propylene resin composition according to any one of Inventions 1 to 9. Effect of the Invention

[0007] According to the present invention, it is possible to provide a molded article having excellent low-temperature impact strength and a propylene resin composition which is a raw material thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] definition In this specification, the term "propylene polymer" means a polymer having 50% by weight or more of monomer units derived from propylene, as will be explained in detail later. In this specification, the term "propylene resin composition" means a composition containing a propylene polymer, which will be described in detail later. As used herein, the term "α-olefin" refers to an aliphatic unsaturated hydrocarbon having an α-position carbon-carbon unsaturated double bond. In this specification, the term "C4-10 hydrocarbon group" means a hydrocarbon group having 4 to 10 carbon atoms. The same applies to other similar expressions. In this specification, the term "ethylene-α-olefin copolymer" refers to a copolymer containing monomer units derived from ethylene and monomer units derived from an α-olefin having C4 or more (meaning 4 or more carbon atoms; the same applies to other similar expressions), and substantially does not contain monomer units derived from propylene. This will be described in detail later. In this specification, the term "heterophagic propylene polymerization material" means a mixture containing a polymer I containing 80% by weight or more of monomer units derived from propylene (wherein the total weight of the polymer I is 100% by weight) and a polymer II containing monomer units derived from at least one α-olefin selected from the group consisting of ethylene and C4-12 α-olefins and monomer units derived from propylene. In this specification, the term "xylene insoluble component (also referred to as "CXIS component")" means a component insoluble in p-xylene contained in a polymer, and a solid obtained by the following method: A method in which about 2 g of a polymer is dissolved in boiling p-xylene for 2 hours to obtain a solution, and then the solution is cooled to 20° C. to precipitate a solid. In this specification, the term "xylene soluble components (also referred to as "CXS components")" means components other than the "CXIS components" in the polymer.

[0009] All numbers disclosed herein are approximations, whether or not the word "about" or "approximately" is used in connection therewith. They may vary by 1 percent, 2 percent, 5 percent, or sometimes 10-20 percent. Whenever a numerical range with a lower limit RL and an upper limit RU is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R=RL+k*(RU-RL), where k is a variable ranging from 1 percent to 100 percent in increments of 1 percent, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, ..., 50 percent, 51 percent, 52 percent, ..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent. Additionally, any numerical range defined by two R numbers as set forth above is also specifically disclosed.

[0010] The description "lower limit to upper limit" expressing a numerical range means "lower limit or more, upper limit or less", and the description "upper limit to lower limit" expresses "upper limit or less, lower limit or more". That is, these descriptions express a numerical range including the lower limit and the upper limit, but in one embodiment, one or both of the upper limit and the lower limit may be excluded, that is, "lower limit to upper limit" may express "more than the lower limit and lower limit", "lower limit or more, less than the upper limit", or "more than the lower limit and less than the upper limit". Similarly, "xx or more" may express "more than xx", and "xx or less" may express "less than xx".

[0011] Hereinafter, several embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0012] Propylene resin composition The "propylene resin composition" of the present invention contains a recycled resin having a swell ratio of 1.3 or more and a virgin propylene polymer. The swell ratio is measured under the following conditions. Measurement temperature = 220℃, orifice L / D = 40mm / 1mm, shear rate = 2432sec -1 .

[0013] Recycled Resin In this specification, the term "recycled resin" means a resin that has been processed, such as molded, or used for some final purpose, and then goes through a recovery process before being reused. The same applies to other "recycled xxx" types.

[0014] Examples of raw materials subjected to the recovery process include used interior parts of automobiles (instrument panels, door trims, etc.), exterior parts of automobiles (bumpers, etc.), other automobile parts (battery cases, etc.), packaging containers (food retort pouches, refill pouches, detergent bottles, etc.), housings of household electrical appliances, office supplies (trays, etc.), and household daily necessities (contact lens cases, etc.). These recovered raw materials may contain elastomer components such as ethylene-α-olefin copolymers that increase impact resistance, and / or additives such as inorganic fillers, neutralizers, antioxidants, ultraviolet absorbers, nucleating agents, lubricants, antistatic agents, antiblocking agents, colorants (inorganic pigments, organic pigments, pigment dispersants, etc.), and flame retardants, depending on the application. The recovery process is not particularly limited, and examples thereof include known methods.

[0015] In one embodiment, the process for preparing the recycled resin may include any steps other than the recovery step, such as a crushing step, a refining step, a melting step, a kneading step with other substances, and a molding step into a pellet form. Examples of the refining step include washing with water, aqueous and / or oil-based chemicals, microbial treatment, magnetic separation, and gravity separation. The molded body may be, for example, an injection molded body, but is not limited thereto.

[0016] In this specification, the term "virgin propylene polymer" means a propylene polymer that is not molded into a product such as an automobile or a part thereof and is not used for any final use after the propylene polymer is produced by a process including a polymerization step, unlike the above-mentioned "recycled propylene polymer". The same applies to other "virgin xxx".

[0017] Swell Ratio The swell ratio is the degree of expansion of the strand diameter of the thermoplastic elastomer composition relative to the orifice diameter when the molten thermoplastic elastomer composition is extruded from an orifice using a capillary rheometer. The swell ratio was measured at a temperature of 220°C and a shear rate of 2432 sec. -1 The thermoplastic elastomer composition is extruded through an orifice having a diameter of 1 mm and a length of 40 mm under the above conditions, and the diameter of the resulting strand is divided by the diameter of the orifice. For example, it can be measured according to the method described in the Examples.

[0018] A resin composition having a desired swell ratio can be produced by appropriately selecting the types and content ratio of monomers constituting the polymer, polymerization conditions such as the type of catalyst, the type and content of filler, etc. After the virgin resin composition produced in this way is used for some purpose, the recycled resin obtained through recycling can be used to produce the propylene resin composition of the present invention.

[0019] Since the propylene resin composition of the present invention contains a recycled resin having a swell ratio of 1.3 or more, a molded article containing (produced from) the propylene resin composition of the present invention has excellent low-temperature impact strength.

[0020] In one embodiment, the preferred form of the recycled resin is a crushed molded product or pellets granulated from the crushed molded product. More preferably, the recycled resin has a swell ratio of 1.3 or more measured in the state of crushed molded products, so that the molded product containing (produced from) the propylene resin composition of the present invention has excellent low-temperature impact strength.

[0021] The "recycled resin having a swell ratio of 1.3 or more" (also referred to as component A) preferably contains at least one selected from the group consisting of a propylene polymer P and an ethylene-α-olefin copolymer E, and preferably contains a propylene polymer P. Component A may contain a plurality of recycled resins.

[0022] Each component represented by "propylene polymer P" etc. will also be simply referred to as "component P" etc.

[0023] Each component will be described below.

[0024] Propylene polymer P (component P) The propylene resin composition of the present invention may contain a propylene polymer P (component P) as component A. Component P is a polymer having 50% by weight or more of monomer units derived from propylene, with the total weight of component P being 100% by weight. Examples of component P include a propylene homopolymer, a random copolymer of propylene and a monomer other than propylene, and a heterophasic propylene polymerization material. The propylene resin composition of the present invention may contain only one type of component P as component A, or may contain two or more types. From the viewpoint of rigidity and impact resistance of a molded product, it is preferable that component P contains at least one type selected from the group consisting of a propylene homopolymer and a heterophasic propylene polymerization material.

[0025] Propylene homopolymer When a propylene homopolymer is contained as component P, the intrinsic viscosity number ([η]) of the propylene homopolymer is preferably 0.10 to 4.00 dL / g, more preferably 0.50 to 3.00 dL / g, and further preferably 0.70 to 2.00 dL / g, from the viewpoints of the fluidity of the resin composition when melted and the toughness of the molded body.

[0026] In this specification, the intrinsic viscosity (unit: dL / g) means a value measured at a temperature of 135° C. using tetralin as a solvent by the following method.

[0027] Using an Ubbelohde viscometer, the reduced viscosity is measured at three concentrations: 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL. The reduced viscosity is plotted against the concentration, and the intrinsic viscosity is calculated by the extrapolation method in which the concentration is extrapolated to zero. The method for calculating the intrinsic viscosity by the extrapolation method is described, for example, in "Polymer Solutions, Polymer Experiments 11" (published by Kyoritsu Publishing Co., Ltd. in 1982), page 491.

[0028] The molecular weight distribution (Mw / Mn) of the propylene homopolymer is preferably 3.0 or more, and more preferably 4.0 or more. The molecular weight distribution may be 15.0 or less, or may be 10.0 or less. The molecular weight distribution is preferably 3.0 to 15.0, and more preferably 4.0 to 10.0.

[0029] In this specification, the molecular weight distribution means the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), calculated using the weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) under the following conditions. Equipment: Tosoh Corporation HLC-8121 GPC / HT Separation column: 3 GMHHR-H(S)HT, manufactured by Tosoh Corporation Measurement temperature: 140℃ Carrier: Orthodichlorobenzene Flow rate: 1.0mL / min Sample concentration: Approximately 1 mg / mL Sample injection volume: 400 μL Detector: Differential Refraction Calibration curve creation method: Use standard polystyrene

[0030] The propylene homopolymer may be, for example, a recycled product produced by polymerizing propylene using a polymerization catalyst.

[0031] Examples of polymerization catalysts include Ziegler-type catalysts; Ziegler-Natta-type catalysts; catalysts containing a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; catalysts containing a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound; and catalysts modified by supporting a catalyst component (a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that forms an ionic complex, an organoaluminum compound, etc.) on inorganic particles (silica, clay minerals, etc.).

[0032] Examples of the polymerization catalyst include the catalysts described in JP-A-61-218606, JP-A-5-194685, JP-A-7-216017, JP-A-9-316147, JP-A-10-212319, JP-A-2004-182981, JP-A-2010-168545, and JP-A-2011-246699.

[0033] Furthermore, a polymer obtained by prepolymerizing propylene in the presence of the above-mentioned polymerization catalyst may be used as the polymerization catalyst.

[0034] Examples of polymerization methods include bulk polymerization, solution polymerization, and gas phase polymerization. Here, bulk polymerization refers to a method in which polymerization is carried out using an olefin that is liquid at the polymerization temperature as a medium, and 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 gaseous monomer is used as a medium and a gaseous monomer is polymerized in the medium.

[0035] Examples of the polymerization method include a batch method, a continuous method, and a combination thereof. The polymerization method may be a multi-stage method in which a plurality of polymerization reaction vessels are connected in series.

[0036] From the viewpoint of industrial and economical superiority, a continuous gas phase polymerization method or a bulk-gas phase polymerization method in which a bulk polymerization method and a gas phase polymerization method are carried out continuously is preferred.

[0037] Various conditions in the polymerization step (polymerization conditions such as polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, and polymerization time) can be appropriately determined depending on the molecular structure of the desired polymer.

[0038] Other steps may be carried out before or after the polymerization step. For example, after the polymerization step, the polymer may be dried at a temperature equal to or lower than the melting temperature of the polymer, if necessary, in order to remove residual solvent contained in the polymer, ultralow molecular weight oligomers produced as by-products during production, etc. Examples of drying methods include those described in JP-A-55-75410 and JP-A-2565753.

[0039] Random copolymer of propylene and monomers other than propylene The random copolymer of propylene and a monomer other than propylene contains monomer units derived from propylene and monomer units derived from a monomer other than propylene. When the random copolymer is contained as component P, the random copolymer preferably contains 0.01 to 20% by weight of monomer units derived from a monomer other than propylene based on the weight of the random copolymer.

[0040] Examples of the monomer other than propylene include ethylene and C4 to 12 α-olefins. Among them, at least one selected from the group consisting of ethylene and C4 to 10 α-olefins is preferred, at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, and 1-octene is more preferred, and at least one selected from the group consisting of ethylene and 1-butene is even more preferred.

[0041] Examples of the random copolymer include propylene-ethylene random copolymer, propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer, propylene-ethylene-1-butene random copolymer, propylene-ethylene-1-hexene random copolymer, and propylene-ethylene-1-octene random copolymer.

[0042] When component P contains a random copolymer of propylene and a monomer other than propylene, the intrinsic viscosity number ([η]) of the random copolymer is preferably 0.10 to 4.00 dL / g, more preferably 0.50 to 3.00 dL / g, and even more preferably 0.70 to 2.00 dL / g, from the viewpoint of fluidity of the resin composition when melted.

[0043] The molecular weight distribution (Mw / Mn) of the random polymer is preferably 3.0 or more, and more preferably 4.0 or more. The molecular weight distribution of the random polymer may be 10.0 or less, or may be 7.0 or less. The molecular weight distribution of the random polymer is preferably 3.0 to 10.0, and more preferably 4.0 to 7.0.

[0044] The random copolymer may be prepared, for example, by polymerizing propylene and a monomer other than propylene according to a polymerization catalyst, polymerization method, polymerization scheme, and polymerization conditions that can be used in the preparation of the propylene homopolymer.

[0045] Heterophagic propylene polymer materials When a heterophasic propylene polymerization material is included as component P, the heterophasic propylene polymerization material can be produced, for example, by carrying out a first polymerization step for forming a polymer I and a second polymerization step for forming a polymer II. These polymerization steps can be carried out according to a polymerization catalyst, a polymerization method, a polymerization scheme, and polymerization conditions that can be used in the production of the propylene homopolymer. In the heterophasic propylene polymerization material, the total weight of the heterophasic propylene polymerization material may be 98 to 100% by weight, with the total weight of the heterophasic propylene polymerization material being 100% by weight.

[0046] As described above, polymer I contains 80% by weight or more of monomer units derived from propylene (where the total weight of polymer I is taken as 100% by weight). Polymer I may be, for example, a propylene homopolymer, or may contain monomer units derived from a monomer other than propylene. When polymer I contains monomer units derived from a monomer other than propylene, the content of such monomer units may be, for example, 0.01% by weight or more and less than 20% by weight based on the total weight of polymer I.

[0047] Examples of the monomer other than propylene include ethylene and C4 or higher α-olefins. Among them, at least one selected from the group consisting of ethylene and C4 to C10 α-olefins is preferred, at least one selected from the group consisting of ethylene, 1-butene, 1-hexene and 1-octene is more preferred, and at least one selected from the group consisting of ethylene and 1-butene is even more preferred.

[0048] Examples of copolymers containing monomer units derived from a monomer other than propylene include propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-1-octene copolymers, propylene-ethylene-1-butene copolymers, propylene-ethylene-1-hexene copolymers, and propylene-ethylene-1-octene copolymers.

[0049] From the viewpoint of dimensional stability of the molded article, polymer I is preferably a propylene homopolymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-ethylene-1-butene copolymer, and more preferably a propylene homopolymer.

[0050] Provided that the swell ratio of the heterophasic propylene polymer material is 1.3 or more, the swell ratio of the polymer I is not limited, but is preferably 1.1 or more, for example, 1.2 or more, or may be 1.3. The upper limit is not particularly limited, but may be, for example, 2.0 or less.

[0051] The content of polymer I is preferably from 50 to 99% by weight, and more preferably from 60 to 95% by weight, based on the total weight of the heterophasic propylene polymerization material.

[0052] As described above, polymer II contains monomer units derived from at least one α-olefin selected from the group consisting of ethylene and C4-12 α-olefins and monomer units derived from propylene. Preferably, polymer II contains 30% by weight or more of monomer units derived from at least one α-olefin selected from the group consisting of ethylene and C4-12 α-olefins, and also contains monomer units derived from propylene (where the total weight of polymer II is taken as 100% by weight).

[0053] In polymer II, the content of monomer units derived from at least one α-olefin selected from the group consisting of ethylene and C4-12 α-olefins may be 30 to 70% by weight, or may be 35 to 60% by weight (where the total weight of polymer II is taken as 100% by weight).

[0054] In polymer II, the at least one α-olefin selected from the group consisting of ethylene and C4 to C12 α-olefins is preferably at least one selected from the group consisting of ethylene and C4 to C10 α-olefins, more preferably at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, 1-octene and 1-decene, and still more preferably at least one selected from the group consisting of ethylene and 1-butene.

[0055] Examples of polymer II include propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, propylene-ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer and propylene-1-decene copolymer. Among them, propylene-ethylene copolymer, propylene-1-butene copolymer and propylene-ethylene-1-butene copolymer are preferred, and propylene-ethylene copolymer is more preferred.

[0056] The content of polymer II is preferably from 1 to 50% by weight, and more preferably from 5 to 40% by weight, based on the total weight of the heterophasic propylene polymerization material.

[0057] In the heterophasic propylene polymerization material, the content of monomer units derived from at least one α-olefin selected from the group consisting of ethylene and C4-12 α-olefins may be 0.3-35% by weight, or 0.7-24% by weight (wherein the total weight of the heterophasic propylene polymerization material is 100% by weight).

[0058] The content of xylene insoluble components (CXIS components) in the heterophasic propylene polymerization material is preferably 50 to 99% by weight, and more preferably 60 to 95% by weight, based on the total weight of the heterophasic propylene polymerization material.

[0059] The content of the xylene soluble component (CXS component) in the heterophasic propylene polymerization material is preferably 1 to 50% by weight, and more preferably 5 to 40% by weight, based on the total weight of the heterophasic propylene polymerization material.

[0060] Provided that the swell ratio of the heterophasic propylene polymerization material is 1.3 or more, the swell ratio of CXIS of the heterophasic propylene polymerization material is not limited, but is preferably 1.1 or more, for example, 1.2 or more, or may be 1.3. The upper limit is not particularly limited, but may be, for example, 2.0 or less.

[0061] In the present invention, it is considered that the CXIS component in the heterophasic propylene polymerization material is mainly composed of polymer I, and the CXS component in the heterophasic propylene polymerization material is mainly composed of polymer II.

[0062] Examples of heterophasic propylene polymeric materials include (propylene)-(propylene-ethylene) polymeric materials, (propylene)-(propylene-ethylene-1-butene) polymeric materials, (propylene)-(propylene-ethylene-1-hexene) polymeric materials, (propylene)-(propylene-ethylene-1-octene) polymeric materials, (propylene)-(propylene-1-butene) polymeric materials, (propylene)-(propylene-1-hexene) polymeric materials, (propylene)-(propylene-1-octene) polymeric materials, (propylene)-(propylene-1-decene) polymeric materials, (Propylene-ethylene)-(propylene-ethylene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-hexene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-octene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-decene) polymerization material, (propylene-ethylene)-(propylene-1-butene) polymerization material, (propylene-ethylene)-(propylene-1-hexene) polymerization material, (propylene-ethylene (propylene-1-octene) polymerization materials, (propylene-ethylene)-(propylene-1-decene) polymerization materials, (propylene-1-butene)-(propylene-ethylene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-butene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-hexene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-octene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-decene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-decene) polymerization materials, (propylene-1-butene)-(propylene (propylene-1-butene) polymerization material, (propylene-1-butene)-(propylene-1-hexene) polymerization material, (propylene-1-butene)-(propylene-1-octene) polymerization material, (propylene-1-butene)-(propylene-1-decene) polymerization material, (propylene-1-hexene)-(propylene-1-hexene) polymerization material, (propylene-1-hexene)-(propylene-1-octene) polymerization material, (propylene-1-hexene)-(propylene-1-decene) polymerization material, (propylene-1-octene)-(propylene-1-octene) polymerization material,and (propylene-1-octene)-(propylene-1-decene) polymer materials.

[0063] Here, the expression "(propylene)-(propylene-ethylene) polymer material" means "a heterophasic propylene polymer material in which polymer I is a propylene homopolymer and polymer II is a propylene-ethylene copolymer." The same applies to other similar expressions.

[0064] As the heterophasic propylene polymerization material, a (propylene)-(propylene-ethylene) polymerization material, a (propylene)-(propylene-ethylene-1-butene) polymerization material, a (propylene-ethylene)-(propylene-ethylene) polymerization material, a (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization material, or a (propylene-1-butene)-(propylene-1-butene) polymerization material is preferred, and a (propylene)-(propylene-ethylene) polymerization material is more preferred.

[0065] The intrinsic viscosity number ([η]I) of polymer I is preferably from 0.10 to 4.00 dL / g, more preferably from 0.50 to 3.00 dL / g, and even more preferably from 0.70 to 2.00 dL / g.

[0066] The intrinsic viscosity number ([η]II) of the polymer II is preferably from 1.00 to 10.00 dL / g, more preferably from 2.00 to 10.00 dL / g, and further preferably from 2.00 to 9.00 dL / g.

[0067] The ratio ([η]II / [η]I) of the intrinsic viscosity number ([η]II) of polymer II to the intrinsic viscosity number ([η]I) of polymer I is preferably 1-20, and more preferably 1-10.

[0068] An example of a method for measuring the intrinsic viscosity number ([η]I) of polymer I is a method in which polymer I formed is extracted from a reactor in which polymer I is formed, and the intrinsic viscosity number of the polymer is measured.

[0069] The intrinsic viscosity number ([η]II) of polymer II can be calculated, for example, from the intrinsic viscosity number ([η]Total) of the heterophasic propylene polymerization material, the intrinsic viscosity number ([η]I) of polymer I, and the contents of polymer II and polymer I, according to the following formula.

[0070] [η]II=([η]Total-[η]I×XI) / XII [η]Total: Intrinsic viscosity number of heterophasic propylene polymer material (dL / g) [η]I: Intrinsic viscosity number of polymer I (dL / g) XI: Ratio of the weight of polymer I to the total weight of the heterophasic propylene polymer material (weight of polymer I / weight of heterophasic propylene polymer material) XII: Ratio of the weight of polymer II to the total weight of the heterophasic propylene polymer material (weight of polymer II / weight of heterophasic propylene polymer material)

[0071] Here, XI and XII can be determined from the material balance during polymerization.

[0072] Incidentally, XII may be calculated by measuring the heat of fusion of the polymer I and the heat of fusion of the heterophasic propylene polymer material and using the following formula. XII = 1-(ΔHf)T / (ΔHf)P (ΔHf)T: Heat of fusion of the heterophasic propylene polymer material (J / g) (ΔHf)P: Heat of fusion of polymer I (J / g)

[0073] The intrinsic viscosity number ([η]CXIS) of the CXIS component is preferably 0.10 to 4.00 dL / g, more preferably 0.50 to 3.00 dL / g, and even more preferably 0.70 to 2.00 dL / g.

[0074] The intrinsic viscosity number ([η]CXS) of the CXS component is preferably from 1.00 to 10.00 dL / g, more preferably from 2.00 to 10.00 dL / g, and further preferably from 2.00 to 9.00 dL / g.

[0075] The ratio ([η]CXS / [η]CXIS) of the intrinsic viscosity number of the CXS component ([η]CXS) to the intrinsic viscosity number of the CXIS component ([η]CXIS) is preferably 1-20, and more preferably 1-10.

[0076] The molecular weight distribution (Mw(I) / Mn(I)) of polymer I is preferably 3.0 or more, and more preferably 4.0 or more.

[0077] The molecular weight distribution of the CXIS component (Mw(CXIS) / Mn(CXIS)) is preferably 3.0 or more, and more preferably 4.0 or more.

[0078] In this specification, the melt flow rate refers to a value measured in accordance with JIS K7210.

[0079] Ethylene-α-olefin copolymer E (component E) The propylene resin composition of the present invention may contain an ethylene-α-olefin copolymer E (component E) as component A. Component E is a polymer having a total content of monomer units derived from ethylene and monomer units derived from C4 or higher α-olefins of 50% by weight or more, and preferably, the total content is 98 to 100% by weight, with the total weight of component E being 100% by weight. Component E may be an ethylene-α-olefin random polymer Er.

[0080] Examples of the C4 or higher α-olefin include C4-12 α-olefins. Examples of the C4-12 α-olefin include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene. Among them, 1-butene, 1-hexene, and 1-octene are preferred. The α-olefin may be an α-olefin having a cyclic structure, such as vinylcyclopropane or vinylcyclobutane.

[0081] Examples of component 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 an α-olefin having a cyclic structure.

[0082] In Component E, the content of monomer units derived from C4 or higher α-olefins is preferably 1 to 49 wt%, more preferably 5 to 49 wt%, and even more preferably 24 to 49 wt%, based on the total weight of Component E.

[0083] The density of component E is 0.85 to 0.89 g / cm from the viewpoint of impact resistance of the molded product. 3 and preferably 0.85 to 0.88 g / cm 3 More preferably, the density is 0.85 to 0.87 g / cm 3 It is more preferable that:

[0084] In one embodiment, the melt flow rate (MFR) of component A (temperature 230°C, load 2.16 kgf) is preferably 0.1 to 300 g / 10 min or more from the viewpoint of molding processability of the resin composition and / or low-temperature impact strength of the molded product. The lower limit of MFR is more preferably 1 g / 10 min, and may be 5 g / 10 min, 10 g / 10 min, 15 g / 10 min, 20 g / 10 min, 25 g / 10 min, or 30 g / 10 min. The upper limit of MFR is more preferably 200 g / 10 min, and may be 100 g / 10 min, 80 g / 10 min, 70 g / 10 min, 60 g / 10 min, 50 g / 10 min, or 40 g / 10 min. From the viewpoint of molding processability of the resin composition, the MFR of recycled resin A is preferably 20 g / 10 min or more.

[0085] Manufacturing method of component E Component E may be produced by polymerizing ethylene and a C4 or higher α-olefin using a polymerization catalyst.

[0086] Examples of polymerization catalysts include homogeneous catalysts such as metallocene catalysts and Ziegler-Natta type catalysts.

[0087] Examples of homogeneous catalysts include catalysts containing a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; catalysts containing a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound; and catalysts modified by supporting a catalyst component (a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that forms an ionic complex, an organoaluminum compound, etc.) on inorganic particles (silica, clay minerals, etc.).

[0088] An example of a Ziegler-Natta type catalyst is a catalyst that combines a titanium-containing solid transition metal component with an organometallic component.

[0089] Component E may be a recycled commercial product. Examples of commercially available components E include Engage (registered trademark) manufactured by Dow Chemical Japan Co., Ltd., Tafmer (registered trademark) manufactured by Mitsui Chemicals, Inc., Neozex (registered trademark) and Ultzex ​​(registered trademark) manufactured by Prime Polymer Co., Ltd., Excellen FX (registered trademark), Sumikasen (registered trademark), and Esprene SPO (registered trademark) manufactured by Sumitomo Chemical Co., Ltd.

[0090] The propylene resin composition of the present invention may contain, as component A, a component other than components P and E. Examples of such components include thermoplastic resins (polystyrenes (e.g., polystyrene, poly(p-methylstyrene), poly(α-methylstyrene), AS (acrylonitrile / styrene copolymer) resin), ABS (acrylonitrile / butadiene / styrene copolymer) resin, AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin, ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin, polychloroprene, chlorinated rubber, polyvinyl chloride, polyvinylidene chloride, acrylic resin, ethylene / vinyl alcohol copolymer resin, fluororesin, polyacetal, grafted polyphenylene ether resin, and polyphenylene sulfide resin). Examples of such resins include polylactic acid (PLA) resins, polyurethanes, polyamides, polyester resins (e.g., polyethylene terephthalate, polybutylene terephthalate), polycarbonates, polysulfones, polyether ether ketones, polyether sulfones, aromatic polyester resins, polybutadiene, 1,2-polybutadiene, polyisoprene, styrene / butadiene copolymers, butadiene / acrylonitrile copolymers, natural rubber, etc., epoxy resins, diallyl phthalate prepolymers, silicone resins, silicone rubbers, epichlorohydrin rubbers, acrylic rubbers, and even PLA resins (polylactic acid) produced by polymerizing monomers derived from plants extracted from biomaterials.

[0091] In one embodiment, the recycled resin A (component A) contained in the propylene resin composition of the present invention may contain a filler F.

[0092] Filler F (component F) Examples of component F include an inorganic filler FI and an organic filler FO. Component A may contain only one type of component F, or may contain two or more types of component F.

[0093] Inorganic fillers FI include glass, silicate minerals, alumina, silica, silicon dioxide, titanium oxide, iron oxide, aluminum oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, carbonate minerals, calcium sulfate, magnesium sulfate, basic magnesium sulfate, calcium sulfite, carbon black, and cadmium sulfide.

[0094] The organic filler FO includes polyester, aromatic polyamide, cellulose and vinylon.

[0095] The shape of the filler may be plate-like, needle-like, or fibrous.

[0096] From the viewpoints of rigidity, impact resistance and dimensional stability of the molded article, component F is preferably an inorganic filler, and more preferably talc which is a plate-like silicate mineral.

[0097] From the viewpoints of rigidity, impact resistance, and dimensional stability of the molded article, the average particle diameter D50[L] of component F is preferably 20.0 μm or less, and more preferably 15.0 μm or less. The average particle diameter D50[L] of component F may be 2.0 μm or more, or may be 4.0 μm or more. The average particle diameter D50[L] of component F is preferably 2.0 to 20.0 μm, and more preferably 4.0 to 15.0 μm. The average particle size D50[S] of component F is preferably 5.0 μm or less, and more preferably 3.0 μm or less, from the viewpoints of rigidity, impact resistance and dimensional stability of the molded article. The average particle size D50[S] of component F may be 0.5 μm or more, or may be 1.0 μm or more. The average particle size D50[S] of component F is preferably 0.5 to 5.0 μm, more preferably 1.0 to 3.0 μm. The ratio of the average particle diameter D50[L] to the average particle diameter D50[S] of component F (D50[L] / D50[S]) may be 1.5 or more, or 2.5 or more, from the viewpoint of the rigidity and dimensional stability of the molded article. D50[L] / D50[S] may be 10 or less, or 8 or less. D50[L] / D50[S] may be 1.5 to 10, 1.5 to 8, 2.5 to 10, or 2.5 to 8.

[0098] In this specification, the term "average particle size D50[L]" refers to a particle size distribution measured based on volumetric particle size distribution data measured by a laser diffraction method according to the method specified in JIS R1629, and refers to the particle size (50% equivalent particle size) when the cumulative number of particles from the smaller particle size side reaches 50% in the particle size distribution measurement data. The particle size defined in this way is generally called the "50% equivalent particle size" and is represented by "D50". In this specification, the term "average particle size D50 [S]" refers to a particle size distribution measurement data based on volume measured by a centrifugal sedimentation method in accordance with the method specified in JIS R1619, and means the particle size when the cumulative number of particles from the smaller particle size side reaches 50% in the particle size distribution measurement data (50% equivalent particle size). The larger the ratio of the average particle diameter D50[L] to the average particle diameter D50[S] of component F (D50[L] / D50[S]), the more excellent the rigidity and dimensional stability of the molded body.

[0099] In one embodiment, component (A) and / or component (B) contain ash. The ash content refers to the components remaining as ash after heating the crushed material at 600° C. for 60 minutes. The amount of ash is determined by the following method.

[0100] (Method of measuring ash content) The crucible is heated at 600°C for 60 minutes using an electric furnace, and the crucible is removed and cooled in a desiccator for 1 hour, after which it is weighed on a precision balance. 10 g of the crushed material is weighed into the crucible, and heated at 600°C for 60 minutes using an electric furnace to completely incinerate it. Next, the crucible is cooled in a desiccator for 1 hour, and the mass of the ash is measured to the nearest 0.1 mg using a precision balance, and the ash content (mass%) for component (A) or component (B) is calculated.

[0101] When component (A) or component (B) contains a filler, the majority of the filler is contained in the ash content of component (A) or component (B). When component (A) or component (B) contains a filler, the content of the filler is considered to roughly correspond to the ash content of component (A) or component (B).

[0102] Virgin propylene polymer The propylene resin composition of the present invention contains a virgin propylene polymer. The definition and preferred embodiments of the propylene polymer are the same as those of the component P described above.

[0103] The propylene resin composition of the present invention may contain components other than "recycled resin having a swell ratio of 1.3 or more" and "virgin propylene polymer". An example of such a component is a recycled resin having a swell ratio of less than 1.3. The definition and preferred embodiments of the component are the same as those of component A (component P, component E, etc.) except for the description of the swell ratio. Another example is a virgin resin other than a virgin propylene polymer. The definition and preferred embodiments of the component are the same as those of component A (component E, etc.) except for the description of the swell ratio, the description of the recycling, and the description of the component P. Another example is a filler. The definition and preferred embodiments of the component are the same as those of component F. Other examples include a neutralizing agent, an antioxidant, an ultraviolet absorber, a nucleating agent, a lubricant, an antistatic agent, an antiblocking agent, a processing aid, an organic peroxide, a colorant (inorganic pigment, organic pigment, pigment dispersant, etc.), a foaming agent, a foam nucleating agent, a plasticizer, a flame retardant, a crosslinking agent, a crosslinking aid, a brightness enhancer, an antibacterial agent, and a light diffusing agent.

[0104] Content of each ingredient In the propylene resin composition of the present invention, the content of each component is not particularly limited. From the viewpoint of low-temperature impact strength of a molded product, the content of component A is preferably 40 to 99 parts by weight, 50 to 95 parts by weight, or 60 to 90 parts by weight, based on 100 parts by weight of the total content of components A and E. The content of component A is preferably 40 to 99 parts by weight, 50 to 95 parts by weight, or 60 to 90 parts by weight, based on 100 parts by weight of the propylene resin composition.

[0105] In the propylene resin composition of the present invention, from the viewpoint of low-temperature impact strength of a molded product, the content of component E is preferably 1 to 60 parts by weight, 5 to 50 parts by weight, or 10 to 40 parts by weight per 100 parts by weight of the total content of components A and E. The content of component E is preferably 1 to 60 parts by weight, 5 to 50 parts by weight, or 10 to 40 parts by weight per 100 parts by weight of the propylene resin composition.

[0106] When the propylene resin composition of the present invention contains component F as a component other than components A and E, the content of component F may be, for example, 0.1 to 50 parts by weight, 1 to 40 parts by weight, or 5 to 30 parts by weight relative to 100 parts by weight of the total content of components A, E, and F. In another embodiment, the content of component F may be 0.1 to 50 parts by weight, 1 to 40 parts by weight, or 5 to 30 parts by weight relative to 100 parts by weight of the propylene resin composition.

[0107] From the viewpoint of low-temperature impact strength of the molded product, the total amount of the polymers contained is preferably 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the total weight of the propylene resin composition of the present invention.

[0108] From the viewpoint of low-temperature impact strength of the molded product, it is preferable that the total content of components A and E is 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the total weight of the propylene resin composition of the present invention.

[0109] Method for producing propylene resin composition The propylene resin composition of the present invention can be obtained by melt-kneading the raw material components. The temperature during melt-kneading may be 180°C or higher, may be 180 to 300°C, or may be 180 to 250°C.

[0110] For the melt kneading, a Banbury mixer, a single screw extruder, a twin screw co-rotating extruder, or the like can be used.

[0111] The order of mixing the raw material components is not particularly limited. For example, the raw material components may be mixed all at once, or some of the raw material components may be mixed and then the resulting mixture may be mixed with the other components.

[0112] The shape of the propylene resin composition is not particularly limited, and the propylene resin composition may be, for example, in the form of a strand, a sheet, a plate, or a pellet. The pellet-shaped resin composition can be produced, for example, by forming a strand-shaped resin composition and then cutting it to an appropriate length.

[0113] From the viewpoint of the moldability of the resin composition and production stability when producing a molded article, the resin composition before being molded into a molded article is preferably in the form of pellets having a length of about 1 to 50 mm.

[0114] Properties of propylene resin compositions In one embodiment, the melt flow rate (MFR) (temperature 230°C, load 2.16 kgf) of the propylene resin composition of the present invention is preferably 1 to 300 g / 10 min from the viewpoint of molding processability of the resin composition and / or low-temperature impact strength of the molded product. The lower limit of the MFR may be 110 g / 10 min, 12 g / 10 min, or 15 g / 10 min. The upper limit of the MFR may be 100 g / 10 min, 70 g / 10 min, or 40 g / 10 min.

[0115] The propylene resin composition of the present invention can be used as a material for forming a molded article by molding. The propylene resin composition of the present invention is preferably used as an injection molding material. Hereinafter, an example of an injection molded article produced by using the propylene resin composition of the present invention as an injection molding material will be described.

[0116] Molded body The molded article of the present invention contains (is made from) the propylene resin composition of the present invention. The molded article of the present invention has excellent low-temperature impact strength.

[0117] The injection molded article can be manufactured by injection molding. Examples of injection molding include general injection molding, injection foam molding, supercritical injection foam molding, ultra-high speed injection molding, injection compression molding, gas-assisted injection molding, sandwich molding, sandwich foam molding, and insert-outsert molding. There is no particular restriction on the shape of the injection molded article.

[0118] The injection molded article of the present invention can be preferably used for, for example, automotive material applications, home appliance material applications, and container applications, and is particularly suitable for automotive interior and exterior applications. Examples of automotive interior and exterior parts include door trims, pillars, instrument panels, and bumpers. EXAMPLES

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

[0120] Recycled resin A1~A4 Recycled resins A1 to A4, each having a swell ratio of 1.3 or more, were prepared. All of these were recycled propylene compositions.

[0121] Recycled Resin A1 Swell ratio: 1.30 MFR (230℃, 2.16kg load): 53.9g / 10min Ash content: 22.4% by weight

[0122] Recycled Resin A2 Swell ratio: 1.34 MFR (230℃, 2.16kg load): 45.1g / 10min Ash content: 7.0% by weight

[0123] Recycled Resin A3 Swell ratio: 1.35 MFR (230℃, 2.16kg load): 40.7g / 10min Ash content: 16.4% by weight

[0124] Recycled Resin A4 Swell ratio: 1.37 MFR (230℃, 2.16kg load): 32.4g / 10min Ash content: 8.6% by weight

[0125] Recycled resin B1~B3 Recycled resins B1 to B3, each having a swell ratio of less than 1.3, were prepared. All of these were recycled propylene compositions.

[0126] Recycled Resin B1 Swell ratio: 1.10 MFR (230℃, 2.16kg load): 43.2g / 10min Ash content: 19.9% ​​by weight

[0127] Recycled Resin B2 Swell ratio: 1.24 MFR (230℃, 2.16kg load): 34.1g / 10min Ash content: 13.3% by weight

[0128] Recycled Resin B3 Swell ratio: 1.27 MFR (230℃, 2.16kg load): 24.8g / 10min Ash content: 29.3% by weight

[0129] How to measure swell ratio (unit: -) A capillary rheometer (Capilograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.) equipped with a capillary with a capillary diameter (D) of 1 mm and a capillary length (L) of 40 mm, i.e., L / D = 40, was used. The test temperature was 220°C and the shear rate was 2432 sec -1 The molten composition was extruded from the outlet of the capillary at a piston pressing speed of 200 mm / min to produce a strand. The diameter of the strand was measured by a laser at a point 12 mm vertically downward from the outlet of the capillary. The swell ratio at each shear rate is expressed by the following formula. Swell ratio = strand diameter (mm) / capillary diameter (mm)

[0130] Virgin propylene polymer As the virgin propylene polymer, the following virgin heterophasic propylene polymer material was prepared.

[0131] Virgin propylene polymer C1 A propylene polymer (heterophagic propylene polymerization material) C1 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 C1 are as follows. MFR (230℃, 2.16kg load): 27.5g / 10min CXIS component amount: 84.1% by weight CXS component amount: 15.9% by weight

[0132] Production of propylene resin composition The raw materials of the composition in Table 1 and 0.03 parts by mass of "calcium stearate", 0.03 parts by mass of "Sumilizer GA80", and 0.03 parts by mass of "SONGNOX6260" were weighed as additives, and then all the components were mixed and melt-kneaded under the following conditions to obtain a pellet-shaped propylene resin composition. Mixer: Technovel Co., Ltd. Twin-screw mixer KZW-15 / 45MG (cylinder inner diameter 15.5 mm, screw outer diameter 15.0 mm, L / D=45) Cylinder temperature: 200℃; Screw speed: 500 rpm; Screen mesh: 2 layers of 100 mesh and 50 mesh; Output: 6kg / hr

[0133] Manufacture of injection molded products for evaluation of low-temperature impact strength and Rockwell hardness Each crushed molded product was injection molded under the following conditions within the range specified in JIS K7152 to produce an injection molded product for evaluating low-temperature impact strength and Rockwell hardness. The resin composition melted in the injection molding machine was supplied from the gate into the mold cavity by the injection molding machine. Injection molding machine: Toyo Machinery & Metals Si30III (clamping force 30 tons, cylinder diameter 18 mm) Cylinder temperature: 220℃ Mold temperature: 50℃ Injection speed: 20mm / sec Cooling time: 30 seconds

[0134] Low temperature impact strength measurement A test piece having a thickness of 4 mm was cut out from the above-mentioned injection molded article and measured at −30° C. using an IZOD impact tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with ASTM D256. The results are shown in Table 1.

[0135] Rockwell hardness measurement A test piece having a thickness of 4 mm was cut out from the above-mentioned injection molded article, and was measured on the R scale using a Rockwell hardness tester (ARK-F1000, manufactured by Akashi Seisakusho Co., Ltd.) in accordance with ASTM D785. The results are shown in Table 1.

[0136] [Table 1] Examples 1 to 7 are working examples of the present invention, and Examples 8 to 10 are comparative examples.

[0137] It is clear from Table 1 that the molded articles according to the examples have excellent low-temperature impact strength. That is, it was confirmed that the propylene resin composition of the present invention can produce a molded article having excellent low-temperature impact strength, and that the molded article of the present invention has excellent low-temperature impact strength.

Claims

1. A propylene resin composition comprising a recycled resin having a swell ratio of 1.3 or more when measured under the following conditions, and a virgin propylene polymer: Measurement temperature = 220℃, orifice L / D = 40mm / 1mm, shear rate = 2432sec -1 .

2. The propylene resin composition according to claim 1, wherein the recycled resin comprises at least one selected from the group consisting of propylene polymers and ethylene-α-olefin copolymers.

3. The propylene resin composition according to claim 2 , wherein the propylene polymer comprises at least one selected from the group consisting of a propylene homopolymer and a heterophasic propylene polymer material.

4. The propylene resin composition according to claim 1 , wherein the recycled resin comprises a plurality of recycled resins.

5. The propylene resin composition according to claim 1 , comprising a propylene polymer as the virgin propylene polymer.

6. The propylene resin composition according to claim 5 , wherein the propylene polymer comprises at least one selected from the group consisting of a propylene homopolymer and a heterophasic propylene polymer material.

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

8. The propylene resin composition according to claim 7, comprising a recycled inorganic filler as the inorganic filler.

9. The propylene resin composition according to claim 1, further comprising an ethylene-α-olefin copolymer as a component other than the recycled resin.

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

11. A method for producing the propylene resin composition according to any one of claims 1 to 9.

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