Thermoplastic resin composition and molded article
The thermoplastic resin composition with ethylene-α-olefin-non-conjugated diene copolymer, mineral oil, and phthalate ester addresses die swell issues, improving dimensional accuracy and efficiency in extrusion molding.
Patent Information
- Application Number
- JP2024105343
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-06-28
- Publication Date
- 2026-01-16
- Estimated Expiration
- 2044-06-28
AI Technical Summary
Conventional thermoplastic resin compositions experience significant die swell during extrusion molding, leading to dimensional inaccuracies and increased material and energy consumption.
A thermoplastic resin composition comprising an ethylene-α-olefin-non-conjugated diene copolymer, mineral oil, and phthalate ester, with specific content ratios to minimize die swelling.
The composition achieves a reduced die swelling ratio, enhancing dimensional accuracy and yield while reducing material loss and energy consumption.
Smart Images

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Abstract
Description
[Technical Field]
[0001] The present invention relates to a thermoplastic resin composition and a molded article. [Background technology]
[0002] Conventionally, thermoplastic resin compositions have been widely used as materials for automobile parts, etc., because they are highly recyclable, suitable for injection molding, and have excellent product performance such as strength and flexibility. As an example of such a thermoplastic resin composition, Patent Document 1 discloses a resin composition for automobile door grommets that contains an olefin copolymer rubber, an olefin resin, and a hydrocarbon rubber softener. [Prior art documents] [Patent documents]
[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-265715 Summary of the Invention [Problem to be solved by the invention]
[0004] However, conventional thermoplastic resin compositions have a problem in that, for example, immediately after being extruded from a die, their cross-sectional dimensions expand beyond the die exit dimensions. Therefore, there is a demand for a smaller expansion rate (die swell ratio) during extrusion molding and improved dimensional accuracy of the resulting molded products. It is expected that improving the dimensional accuracy of not only extrusion molded products but also blow molded products, injection molded products, and other products will lead to improved yields, reduced material loss, and reduced energy consumption.
[0005] The present invention has been made in view of the above problems, and an object of the present invention is to provide a thermoplastic resin composition and a molded article which have a relatively small die swelling ratio during extrusion molding. [Means for solving the problem]
[0006] The thermoplastic resin composition according to the present invention comprises (A) an ethylene-α-olefin-non-conjugated diene copolymer, (B) a mineral oil, and (C) a phthalate ester; (C) The content of phthalate esters is 5 ppm or more and 10,000 ppm or less per 100 parts by mass of (A) ethylene-α-olefin-non-conjugated diene copolymer.
[0007] The molded article according to the present invention contains a thermoplastic resin composition. [Effects of the Invention]
[0008] According to the present invention, it is possible to provide a thermoplastic resin composition and a molded article that have a relatively small die swelling ratio during extrusion molding. DETAILED DESCRIPTION OF THE INVENTION
[0009] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.
[0010] [Thermoplastic resin composition] The thermoplastic resin composition according to this embodiment contains (A) an ethylene-α-olefin-non-conjugated diene copolymer (hereinafter, sometimes simply referred to as (A)), (B) a mineral oil (hereinafter, sometimes simply referred to as (B)), and (C) a phthalate ester (hereinafter, sometimes simply referred to as (C)).
[0011] <(A) Ethylene-α-olefin-non-conjugated diene copolymer> (A) Ethylene-α-olefin-non-conjugated diene copolymer is a copolymer containing monomer units derived from ethylene, monomer units derived from α-olefin, and monomer units derived from non-conjugated diene. (A) may be used alone or in combination of two or more.
[0012] The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms. Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Among these, the α-olefin having 3 to 20 carbon atoms is preferably propylene or 1-butene, and more preferably propylene. The α-olefins may be used alone or in combination of two or more.
[0013] Examples of non-conjugated dienes include linear non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, and 5-methylene-2-norbornene. Examples of suitable non-conjugated dienes include cyclic non-conjugated dienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, and 4-ethylidene-8-methyl-1,7-nanodiene. Among these, the non-conjugated diene is preferably 5-ethylidene-2-norbornene or dicyclopentadiene. The non-conjugated dienes may be used alone or in combination of two or more.
[0014] When the total amount of the (A) ethylene-α-olefin-non-conjugated diene copolymer is taken as 100% by mass, the content of monomer units derived from ethylene is usually 30% by mass or more and 80% by mass or less, and preferably 40% by mass or more and 80% by mass or less, the content of monomer units derived from α-olefin is usually 5% by mass or more and 50% by mass or less, and preferably 15% by mass or more and 45% by mass or less, and the content of monomer units derived from non-conjugated diene is preferably 4% by mass or more and 15% by mass or less, and more preferably 6% by mass or more and 15% by mass or less.
[0015] The (A) ethylene-α-olefin-non-conjugated diene copolymer is preferably an ethylene-propylene-5-ethylidene-2-norbornene copolymer, an ethylene-propylene-dicyclopentadiene copolymer, an ethylene-propylene-1,4-hexadiene copolymer, or an ethylene-propylene-5-vinyl-2-norbornene copolymer.
[0016] In one embodiment, the (A) ethylene-α-olefin-non-conjugated diene copolymer is an ethylene-propylene-5-ethylidene-2-norbornene copolymer having a content of monomer units derived from ethylene of 40% by mass or more and 80% by mass or less, a content of monomer units derived from propylene of 15% by mass or more and 45% by mass or less, and a content of monomer units derived from 5-ethylidene-2-norbornene of 3% by mass or more and 15% by mass or less.
[0017] The contents of the monomer units derived from ethylene, the monomer units derived from α-olefins, and the monomer units derived from non-conjugated dienes can be determined by infrared spectroscopy (IR). Specifically, (A) the ethylene-α-olefin-non-conjugated diene copolymer is formed into a film having a thickness of about 0.5 mm, and then, using an infrared spectrophotometer, the peaks derived from non-conjugated dienes (for the peak derived from 5-ethylidene-2-norbornene, 1688 cm) of the film are measured. -1The content of the monomer units derived from the non-conjugated diene in the copolymer is calculated by measuring the absorption peak of the non-conjugated diene in the copolymer. Next, the copolymer is formed into a film having a thickness of about 0.1 mm, and the infrared absorption spectrum of the film is measured using an infrared spectrophotometer. The ratio of the monomer units derived from ethylene to the monomer units derived from the α-olefin is determined according to a method described in the literature (Characterization of Polyethylene by Infrared Absorption Spectroscopy, Takayama, Usami et al., or Die Makromolekulare Chemie, 177, 461 (1976) by McRae, MA, Madam S, WF et al.), and the content of the monomer units derived from ethylene and the content of the monomer units derived from the α-olefin can be calculated from the ratio and the content of the monomer units derived from the non-conjugated diene.
[0018] (A) Ethylene-α-olefin-non-conjugated diene copolymer can be obtained by polymerization using a known method, such as a Ziegler-Natta catalyst or a metallocene catalyst, in an inert solvent such as hexane, heptane, toluene, or xylene.
[0019] (A) Mooney viscosity (ML) of ethylene-α-olefin-non-conjugated diene copolymer 1+4 100°C) is preferably 40 or more, more preferably 50 or more. 1+4 The Mooney viscosity (ML 1+4 100°C) is in the above range, a molded product having excellent mechanical strength and excellent appearance can be obtained. 1+4 100℃) is measured according to JIS K6300 and 1+4 "100°C" has the following meaning. M: Mooney viscosity L: Uses a large rotor 100℃: Measurement temperature 1+4: Measurement value when the sample is heated for 1 minute and then the rotor is rotated at 2 rpm for 4 minutes
[0020] The JIS K 6253 A hardness of the (A) ethylene-α-olefin-non-conjugated diene copolymer is preferably 85 or less.
[0021] The (A) ethylene-α-olefin-non-conjugated diene copolymer may be uncrosslinked or may be partially crosslinked as long as it exhibits thermoplasticity. The (A) ethylene-α-olefin-non-conjugated diene copolymer can be crosslinked using various crosslinking agents such as sulfur, peroxides, sulfur-containing organic compounds, alkylphenols, and formaldehyde resins.
[0022] <(B) Mineral oil> (B) Mineral oil is a high-boiling fraction of petroleum, and preferably has an average molecular weight of 300 or more and 1500 or less, and a pour point of 0°C or less. Examples of (B) mineral oil include paraffinic mineral oil, naphthenic mineral oil, and aromatic mineral oil. (B) Mineral oil is preferably paraffinic mineral oil or naphthenic mineral oil, and more preferably paraffinic mineral oil.
[0023] (B) Mineral oil may be mixed with (A) ethylene-α-olefin-non-conjugated diene copolymer, i.e., (A) ethylene-α-olefin-non-conjugated diene copolymer may be extended with (B) mineral oil.
[0024] When (B) mineral oil is added as an extender oil to (A) ethylene-α-olefin-non-conjugated diene copolymer, known methods can be used for the addition, such as a method of mechanically kneading the two using a kneading device such as a roll or a Banbury mixer, or a method of adding (B) to a solution of (A) produced in solution form, followed by removing the solvent by a method such as steam stripping.
[0025] When (B) mineral oil is added as an extender oil to (A) ethylene-α-olefin-non-conjugated diene copolymer, the Mooney viscosity (ML 1+4 100°C) is preferably 5 or more and 300 or less, more preferably 10 or more and 250 or less, and further preferably 40 or more and 200 or less. 1+4 100°C) can be measured in the same manner as in (A) above.
[0026] The content of (B) mineral oil is preferably 30 parts by mass or more and 200 parts by mass or less, more preferably 50 parts by mass or more and 150 parts by mass or less, per 100 parts by mass of (A) ethylene-α-olefin-non-conjugated diene copolymer.
[0027] <(C) Phthalate esters> Examples of (C) phthalate esters include diisononyl phthalate, di-2-ethylhexyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, di-n-octyl phthalate, and isomers thereof. The (C) phthalate ester is preferably at least one selected from the group consisting of diisononyl phthalate, di-2-ethylhexyl phthalate, and isomers thereof, and more preferably diisononyl phthalate and its isomers. Diisononyl phthalate isomers contain multiple isomers, such as dimethylheptanol and methyloctanol, in the alcohol moiety. (C) may be used alone or in combination of two or more.
[0028] The content of (C) phthalate ester is 5 ppm or more and 10,000 ppm or less, and preferably 50 ppm or more and 5,000 ppm or less, relative to 100 parts by mass of (A) ethylene-α-olefin-non-conjugated diene copolymer, from the viewpoint of reducing the die swelling ratio during extrusion molding.
[0029] <(D) Olefin Polymer> The thermoplastic resin composition according to this embodiment may further contain (D) an olefin polymer (excluding (A) ethylene-α-olefin-non-conjugated diene copolymer) (hereinafter, sometimes simply referred to as (D)). The (D) olefin polymer is preferably at least one selected from the group consisting of ethylene polymers and propylene polymers.
[0030] An ethylene-based polymer is a polymer containing more than 50% by mass of monomer units derived from ethylene. Examples of the ethylene-based polymer include an ethylene homopolymer and an ethylene-α-olefin copolymer. The ethylene-based polymer is preferably an ethylene-α-olefin copolymer. The ethylene-based polymer may be used alone or in combination of two or more types.
[0031] The ethylene homopolymer is preferably an ethylene homopolymer obtained by polymerizing ethylene by a high-pressure method, and is produced, for example, by polymerizing ethylene in the presence of a radical generator using a tank reactor or a tubular reactor at a polymerization pressure of 140 MPa or more and 300 MPa or less and a polymerization temperature of 200°C or more and 300°C or less.
[0032] The density of the ethylene homopolymer is preferably 910 kg / m from the viewpoint of improving heat resistance. 3 More preferably, 915 kg / m 3 More preferably, it is 920 kg / m or more. 3 The density is measured according to Method A specified in JIS K7112-1980 after annealing as specified in JIS K6760-1995.
[0033] The ethylene-α-olefin copolymer is a copolymer containing monomer units derived from ethylene and monomer units derived from an α-olefin. The α-olefin is preferably an α-olefin having 3 to 10 carbon atoms. Examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 2-methylpropene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Among these, the α-olefin having 3 to 10 carbon atoms is preferably propylene, 1-butene, or 1-octene. The α-olefins may be used alone or in combination of two or more.
[0034] When the total amount of the ethylene-α-olefin copolymer is taken as 100% by mass, the content of monomer units derived from ethylene is preferably more than 50% by mass and not more than 90% by mass, more preferably from 55% by mass to 85% by mass, and even more preferably from 60% by mass to 75% by mass, and the content of monomer units derived from α-olefin is preferably from 10% by mass to less than 50% by mass, more preferably from 15% by mass to 45% by mass, and even more preferably from 25% by mass to 40% by mass.
[0035] The contents of the ethylene-derived monomer units and the α-olefin-derived monomer units can be determined by infrared spectroscopy (IR method). Specifically, the infrared absorption spectrum of an ethylene-α-olefin copolymer is measured using an infrared spectrophotometer, and the contents of the ethylene-derived monomer units and the α-olefin-derived monomer units are calculated according to the method described in the literature (Characterization of Polyethylene by Infrared Absorption Spectroscopy, Takayama, Usami et al., or Die Makromolekulare Chemie, 177, 461 (1976) by McRae, MA, Madam S, WF et al.).
[0036] The ethylene-α-olefin copolymer may contain other monomer units in addition to ethylene and α-olefins having 3 to 10 carbon atoms. Examples of such other monomers include conjugated dienes having 4 to 8 carbon atoms, such as 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene; vinyl carboxylic acid esters, such as vinyl acetate; unsaturated carboxylic acid esters, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate; and unsaturated carboxylic acids, such as acrylic acid and methacrylic acid. The other monomers may be used alone or in combination of two or more.
[0037] Taking the total amount of the ethylene-α-olefin copolymer as 100% by mass, the content of monomer units derived from other monomers is preferably 30% by mass or less, more preferably 20% by mass or less. The content of monomer units derived from other monomers can be determined by infrared spectroscopy (IR method). Specifically, the peak intensity of the peak derived from the other monomer in the ethylene-α-olefin copolymer is measured using an infrared spectrophotometer, and the content of monomer units derived from other monomers is calculated from the peak intensity.
[0038] Examples of the ethylene-α-olefin copolymer include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, an ethylene-propylene-1-butene copolymer, an ethylene-propylene-1-hexene copolymer, an ethylene-propylene-1-octene copolymer, etc. The ethylene-α-olefin copolymer is preferably an ethylene-propylene copolymer.
[0039] Examples of methods for producing ethylene-α-olefin copolymers include copolymerizing ethylene and α-olefins in the presence of known complex catalysts such as Ziegler-Natta catalysts, metallocene complexes, non-metallocene complexes, etc. Polymerization methods include slurry polymerization, solution polymerization, bulk polymerization, and gas phase polymerization.
[0040] A propylene-based polymer is a polymer containing more than 50% by mass of monomer units derived from propylene. Propylene-based polymers are suitable for constituting the sea phase of the sea-island structure of a thermoplastic resin composition. Examples of propylene-based polymers include propylene homopolymers, heterophasic polymer materials, and propylene random copolymers. The propylene-based polymer is preferably at least one selected from the group consisting of propylene homopolymers, heterophasic polymer materials, and propylene random copolymers, and more preferably a propylene homopolymer, heterophasic polymer material, or propylene random copolymer. The propylene-based polymers may be used alone or in combination of two or more.
[0041] Examples of propylene random copolymers include: (1) A propylene-ethylene random copolymer in which the content of monomer units derived from propylene is 90% by mass or more and 99.5% by mass or less, and the content of monomer units derived from ethylene is 0.5% by mass or more and 10% by mass or less, relative to 100% by mass of the total amount of monomer units derived from propylene and monomer units derived from ethylene; (2) A propylene-ethylene-α-olefin random copolymer in which the content of the monomer units derived from propylene is 81% by mass or more and 99% by mass or less, the content of the monomer units derived from ethylene is 0.5% by mass or more and 9.5% by mass or less, and the content of the monomer units derived from the α-olefin having 4 to 10 carbon atoms is 0.5% by mass or more and 9.5% by mass or less, relative to 100% by mass of the total amount of the monomer units derived from propylene, the monomer units derived from ethylene, and the monomer units derived from the α-olefin having 4 to 10 carbon atoms; or (3) Examples include a propylene-α-olefin random copolymer in which the content of monomer units derived from propylene is 90% by mass or more and 99.5% by mass or less, and the content of monomer units derived from α-olefins having 4 to 10 carbon atoms is 0.5% by mass or more and 10% by mass or less, relative to 100% by mass of the total amount of monomer units derived from propylene and monomer units derived from α-olefins having 4 to 10 carbon atoms.
[0042] Examples of the α-olefins having 4 to 10 carbon atoms in the above (2) and (3) include linear α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene; and branched α-olefins such as 3-methyl-1-butene and 3-methyl-1-pentene. The α-olefins having 4 to 10 carbon atoms may be used alone or in combination of two or more.
[0043] Methods for producing propylene homopolymers and propylene random copolymers include, for example, slurry polymerization, solution polymerization, bulk polymerization, and gas phase polymerization using known complex catalysts such as Ziegler-Natta catalysts, metallocene complexes, and non-metallocene complexes.
[0044] The heterophasic polymeric material is a polymeric material comprising a propylene homopolymer component (I) and an ethylene copolymer component (II) having monomer units derived from at least one selected from the group consisting of propylene and α-olefins having 4 or more carbon atoms and monomer units derived from ethylene. The heterophasic polymeric material preferably contains 70% to 90% by mass of the propylene homopolymer component (I) and 10% to 30% by mass of the ethylene copolymer component (II), relative to 100% by mass of the total amount of the heterophasic polymeric material. More preferably, the content of the propylene homopolymer component (I) is 75% to 90% by mass and the content of the ethylene copolymer component (II) is 10% to 25% by mass.
[0045] The α-olefin having 4 or more carbon atoms in the ethylene copolymer component (II) is preferably an α-olefin having 4 to 20 carbon atoms. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, and 2,2,4-trimethyl-1-pentene. The α-olefin having 4 or more carbon atoms is more preferably an α-olefin having 4 to 10 carbon atoms, and even more preferably 1-butene, 1-hexene, or 1-octene. The α-olefin having 4 or more carbon atoms may be used alone or in combination of two or more kinds.
[0046] The content of monomer units derived from ethylene in the ethylene copolymer component (II) is preferably from 22 to 90% by mass, more preferably from 25 to 80% by mass, and even more preferably from 27 to 70% by mass, based on 100% by mass of the total amount of monomer units derived from ethylene and at least one selected from the group consisting of propylene and an α-olefin having 4 or more carbon atoms. The content of monomer units derived from at least one selected from the group consisting of propylene and an α-olefin having 4 or more carbon atoms in the ethylene copolymer component (II) is preferably from 20 to 78% by mass, more preferably from 30 to 75% by mass, and even more preferably from 40 to 73% by mass, based on 100% by mass of the total amount of monomer units derived from ethylene and at least one selected from the group consisting of propylene and an α-olefin having 4 or more carbon atoms. The content of monomer units derived from ethylene and the content of monomer units derived from at least one selected from the group consisting of propylene and α-olefins having 4 or more carbon atoms in the ethylene copolymer component (II) can be determined, for example, by infrared spectroscopy (IR method). Specifically, the infrared absorption spectrum of the ethylene copolymer component (II) is measured using an infrared spectrophotometer, and the content of units derived from ethylene and the content of monomer units derived from at least one selected from the group consisting of propylene and α-olefins having 4 or more carbon atoms are calculated according to the method described in the literature (Characterization of Polyethylene by Infrared Absorption Spectroscopy, Takayama, Usami et al., or Die Makromolekulare Chemie, 177, 461 (1976) by McRae, MA, Madam S, WF et al.).
[0047] Examples of the ethylene copolymer component (II) include a propylene-ethylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, a propylene-ethylene-1-butene copolymer, a propylene-ethylene-1-hexene copolymer, a propylene-ethylene-1-octene copolymer, etc. The ethylene copolymer component (II) is preferably a propylene-ethylene copolymer or a propylene-ethylene-1-butene copolymer.
[0048] Examples of methods for producing heterophasic polymerized materials include multi-stage polymerization using a polymerization catalyst.
[0049] Examples of polymerization catalysts used in the production of heterophasic polymerization materials include Ziegler catalysts, Ziegler-Natta catalysts, catalysts consisting of a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane, transition metal compounds of Group 4 of the periodic table having a cyclopentadienyl ring, compounds that react with the transition metal compounds to form ionic complexes, and catalysts consisting of organoaluminum compounds.
[0050] In addition, a prepolymerization catalyst may be used in the presence of the polymerization catalyst. Examples of the prepolymerization catalyst include those described in JP-A Nos. 61-218606, 61-287904, 5-194685, 7-216017, 9-316147, 10-212319, and 2004-182981.
[0051] Polymerization methods for producing heterophasic polymeric materials include, for example, bulk polymerization, solution polymerization, slurry polymerization, and gas-phase polymerization. Examples of inert hydrocarbon solvents used in solution polymerization and slurry polymerization include propane, butane, isobutane, pentane, hexane, heptane, and octane. Two or more of these polymerization methods may be combined, and may be either batch or continuous. The polymerization method for producing heterophasic polymeric materials is preferably continuous gas-phase polymerization, or bulk-gas-phase polymerization, in which bulk polymerization and gas-phase polymerization are carried out continuously.
[0052] The melt flow rate (MFR) of the propylene polymer measured in accordance with JIS K7210 at a temperature of 230°C and a load of 2.16 kg is preferably 60 g / 10 min or less, more preferably 30 g / 10 min or less, and even more preferably 10 g / 10 min or less, from the viewpoint of reducing the compression set of the thermoplastic resin composition. The MFR of the propylene polymer is preferably 0.05 g / 10 min or more, more preferably 0.1 g / 10 min or more. The MFR of the propylene polymer is preferably 0.05 g / 10 min or more and 60 g / 10 min or less, more preferably 0.1 g / 10 min or more and 30 g / 10 min or less, and even more preferably 0.1 g / 10 min or more and 10 g / 10 min or less. When two or more propylene polymers are used in combination, the MFR of the propylene polymer with the largest content is taken as the MFR of the propylene polymer.
[0053] The content of (D) olefin polymer is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 20 parts by mass or more and 80 parts by mass or less, per 100 parts by mass of (A) ethylene-α-olefin-non-conjugated diene copolymer.
[0054] The thermoplastic resin composition of the present embodiment may further contain other additives.
[0055] Examples of other additives include crosslinking agents, crosslinking aids, inorganic fillers, organic fillers, ultraviolet absorbers, heat stabilizers, light stabilizers, antistatic agents, nucleating agents, pigments, adsorbents, metal chlorides, silicone compounds, antibacterial agents, antiviral agents, antimoss agents, and anti-algae agents.
[0056] Examples of inorganic fillers include talc, calcium carbonate, and calcined kaolin.
[0057] Examples of organic fillers include fibers, wood flour, and cellulose powder.
[0058] Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, tridiamine-based ultraviolet absorbers, anilide-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers.
[0059] Examples of the light stabilizer include hindered amine light stabilizers and benzoate light stabilizers.
[0060] Examples of pigments include inorganic pigments and organic pigments. Examples of inorganic pigments include carbon black, titanium oxide, calcium carbonate, zinc oxide, lead carbonate, barium sulfate, cerium oxide, kaolin clay, zinc white, red iron oxide, molybdenum orange, cobalt blue, ultramarine blue, and manganese violet. Examples of organic pigments include madder lake, pink madder, dragon's blood, cochineal, sepia, permanent red, fast yellow, naphthol red, and phthalocyanine blue.
[0061] Examples of metal chlorides include iron chloride and calcium chloride.
[0062] In one aspect, the thermoplastic resin composition according to this embodiment further contains at least one selected from the group consisting of calcium carbonate and carbon black.
[0063] The content of other additives is preferably 40% by mass or less relative to 100% by mass of the total mass of the thermoplastic resin composition.
[0064] Each component contained in the thermoplastic resin composition according to this embodiment may contain carbon-14 (C) as a constituent element, may be material recycled, or may be chemically recycled.
[0065] The concentration of carbon-14 (14C) contained in each component of the thermoplastic resin composition is determined as pMC (percentage of moderate carbon: unit %) by the AMS (Accelerator mass spectrometry) method specified in ISO 16620-2:2019.
[0066] Carbon dioxide in the atmosphere contains a certain proportion of carbon-14 (14C), and it is known that plants that grow by absorbing carbon dioxide from the atmosphere, such as corn and trees, contain 14C. It is also known that fossil resources such as petroleum, which are thought to have been stored underground for long periods of time, contain almost no carbon-14 (14C). Therefore, by using plant-derived substances as raw materials for the monomers used to manufacture each component contained in the thermoplastic resin composition, it is possible to incorporate carbon-14 (14C) into the constituent elements of the ethylene-α-olefin-non-conjugated diene copolymer.
[0067] Fossil resource-derived monomers are derived from underground carbon resources such as petroleum, coal, and natural gas, and generally contain very little carbon-14 (14C). Methods for producing fossil resource-derived monomers include well-known methods, such as cracking petroleum-derived naphtha and ethane, and producing olefins by dehydrogenating ethane and propane.
[0068] Plant-derived monomers are derived from carbon circulating on the earth's surface as plants and animals, and generally contain a certain proportion of carbon-14 (14C). Methods for producing plant-derived monomers include known methods, such as cracking bionaphtha, vegetable oil, animal oil, etc., dehydrogenation of biopropane, separation of alcohol from fermented products such as sugars extracted from plant materials such as sugarcane and corn, and dehydration of the alcohol (JP Patent Publication Nos. 2010-511634, 2011-506628, 2013-503647, etc.), and metathesis reaction of ethylene obtained from plant-derived ethanol with n-butene (WO 2007 / 055361, etc.).
[0069] Chemically recycled monomers are derived from carbon generated by the decomposition and combustion of waste, and their carbon-14 (14C) content varies depending on the waste. Methods for producing chemically recycled monomers include known methods, such as thermal decomposition of waste plastics (e.g., JP 2017-512246), cracking of waste vegetable oil, waste animal oil, etc. (e.g., JP 2018-522087), and gasification, alcohol conversion, and dehydration of waste materials such as food waste, biomass waste, food waste, waste oil, waste wood, paper waste, and waste plastics (e.g., JP 2019-167424, WO 2021 / 006245).
[0070] The thermoplastic resin composition according to this embodiment is extruded at a temperature of 220°C and a shear rate of 1216 sec -1 The shear viscosity at is preferably 50 Pa·sec or more and 600 Pa·sec or less, more preferably 70 Pa·sec or more and 400 Pa·sec or less, and even more preferably 100 Pa·sec or more and 350 Pa·sec or less.
[0071] The thermoplastic resin composition according to this embodiment can be obtained by melt-kneading the components.
[0072] Examples of melt-kneading devices include open-type mixing rolls, closed-type Banbury mixers, extruders, kneaders, continuous mixers, etc. The melt-kneading device is preferably a closed-type device. All of the components to be kneaded may be melt-kneaded all at once, or some of the components may be kneaded and then the remaining components may be added and melt-kneaded, or melt-kneading may be performed once or twice or more times. The temperature during melt-kneading is preferably 150°C or higher and 250°C or lower, and the time is preferably 30 seconds or higher and 30 minutes or lower. The components to be kneaded may be added in any order or simultaneously.
[0073] [Molded body] The molded article according to this embodiment contains the above-described thermoplastic resin composition.
[0074] The molded article can be molded by a known molding method such as extrusion molding using a conventional apparatus used for molding thermoplastic resin compositions.
[0075] The molded article according to this embodiment can be used, for example, for bathroom and bathtub parts, rubber-related parts, automobile parts, electrical parts, home appliance parts, furniture components, building components, footwear parts, sports equipment parts, medical and nursing care-related products, and other industrial materials.
[0076] The thermoplastic resin composition and molded article according to this embodiment are not limited to the above embodiment, and various modifications are possible without departing from the spirit of the present invention. In addition, the configurations of embodiments other than those described above may be arbitrarily adopted and combined, and the configurations of one embodiment described above may be applied to the configurations of other embodiments described above.
[0077] The present invention includes the following aspects. [1] A composition comprising (A) an ethylene-α-olefin-non-conjugated diene copolymer, (B) a mineral oil, and (C) a phthalate ester; (C) A thermoplastic resin composition having a phthalate ester content of 5 ppm or more and 10,000 ppm or less per 100 parts by mass of (A) the ethylene-α-olefin-non-conjugated diene copolymer. [2] The thermoplastic resin composition according to [1], wherein the content of (B) mineral oil is 30 parts by mass or more and 200 parts by mass or less per 100 parts by mass of (A) ethylene-α-olefin-non-conjugated diene copolymer. [3] The thermoplastic resin composition according to [1] or [2], further comprising at least one selected from the group consisting of calcium carbonate and carbon black. [4] The thermoplastic resin composition according to any one of [1] to [3], further comprising (D) an olefin-based polymer (excluding (A) an ethylene-α-olefin-non-conjugated diene copolymer). [5] The thermoplastic resin composition according to [4], wherein the olefin polymer (D) is at least one selected from the group consisting of an ethylene polymer and a propylene polymer. [6] The thermoplastic resin composition according to any one of [1] to [5], wherein the content of (C) phthalate ester is 50 ppm or more and 5,000 ppm or less per 100 parts by mass of (A) ethylene-α-olefin-non-conjugated diene copolymer. [7] The thermoplastic resin composition according to any one of [1] to [6], wherein the content of (B) mineral oil is 50 parts by mass or more and 150 parts by mass or less per 100 parts by mass of (A) ethylene-α-olefin-non-conjugated diene copolymer. [8] The thermoplastic resin composition according to any one of [1] to [7], wherein the phthalate ester (C) is diisononyl phthalate. [9] (A) The thermoplastic resin composition according to any one of [1] to [8], wherein the content of monomer units derived from non-conjugated dienes in the ethylene-α-olefin-non-conjugated diene copolymer is 4% by mass or more and 15% by mass or less.
[10] (A) Mooney viscosity (ML 1+4 100°C) is 40 or more.
[11] Temperature: 220°C, shear rate: 1216 sec -1The thermoplastic resin composition according to any one of [1] to
[10] , wherein the shear viscosity at 1000 kJ / min is 50 Pa·sec or more and 600 Pa·sec or less.
[12] A molded article comprising the thermoplastic resin composition according to any one of [1] to
[11] . [Example]
[0078] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The measured values of each item in the examples and comparative examples were measured by the following methods.
[0079] (Physical property measurement method) [Mooney viscosity (ML 1+4 100℃)] Measurement was carried out in accordance with JIS K6300. When components (A) and (B) were mixed in advance, the Mooney viscosity (ML 1+4 100°C) was calculated using the following formula (1). log(ML1 / ML2)=0.0066(△PHR) (1) ML1: Mooney viscosity of component (A) ML2: Mooney viscosity of the mixture of component (A) and component (B) △PHR: Content of component (B) per 100 parts by mass of component (A)
[0080] [Content of monomer units derived from ethylene and monomer units derived from 5-ethylidene-2-norbornene (unit: mass%)] Measurement was carried out by infrared spectroscopy (IR method). Specifically, the measurement was carried out by the following method. An ethylene-propylene-5-ethylidene-2-norbornene copolymer was formed into a film with a thickness of approximately 0.5 mm. Using an infrared spectrophotometer, the peak (1688 cm) derived from 5-ethylidene-2-norbornene of the obtained film was measured. -1The intensity of the absorption peak (absorption peak) was measured to calculate the content of the monomer derived from 5-ethylidene-2-norbornene in the copolymer. Next, a new ethylene-propylene-5-ethylidene-2-norbornene copolymer was formed into a film approximately 0.1 mm thick. The infrared absorption spectrum of the resulting film was measured using an infrared spectrophotometer, and the content of the monomer unit derived from ethylene was calculated according to the method described in the literature (Characterization of Polyethylene by Infrared Absorption Spectroscopy, Takayama, Usami et al., or Die Makromolekulare Chemie, 177, 461 (1976), McRae, MA, Madam S, WF et al.).
[0081] [Measurement of average shear viscosity and average die swell ratio] The average shear viscosity and average die swell ratio were measured using a Toyo Seiki CAPILOGRAPH F1 capillary die with a capillary length of 40 mm and a capillary diameter of 1.0 mm. The test temperature was 220°C, the preheating time was 5 minutes, and the residence time was 5 minutes, resulting in a viscosity of 364.8 seconds. -1 , 1216sec -1 Measurements were performed at two shear rates: 1216 sec -1 Shear viscosity at 364.8sec -1 , 1216sec -1 The average values of the die swell ratio at the two shear rates were calculated. The shear viscosity and die swell ratio were measured twice, and the average values of the two measurement results were used as the average shear viscosity and average die swell ratio.
[0082] (Thermoplastic resin composition) (A1+B1): SK Corporation EPDM product name "S6800WF" (a mixture of 100 parts by mass of A1 (ethylene-propylene-5-ethylidene-2-norbornene copolymer) and 100 parts by mass of paraffinic mineral oil), Mooney viscosity (ML 1+4 100°C) = 57, content of monomer units derived from ethylene in (A1) = 69 mass%, content of monomer units derived from 5-ethylidene-2-norbornene in (A1) = 9 mass% (A2+B2): EPDM manufactured by Sumitomo Chemical Co., Ltd., trade name "Esprene 670F" (a mixture of 100 parts by mass of A2 (ethylene-propylene-5-ethylidene-2-norbornene copolymer) and 100 parts by mass of paraffinic mineral oil), Mooney viscosity (ML 1+4 100°C) = 61, content of monomer units derived from ethylene in (A2) = 66 mass%, content of monomer units derived from 5-ethylidene-2-norbornene in (A2) = 4 mass% (A3+B3): SK Corporation EPDM product name "S6090WF" (a mixture of 100 parts by mass of A3 (ethylene-propylene-5-ethylidene-2-norbornene copolymer) and 50 parts by mass of paraffinic mineral oil), Mooney viscosity (ML 1+4 100°C) = 75, content of monomer units derived from ethylene in (A3) = 66 mass%, content of monomer units derived from 5-ethylidene-2-norbornene in (A3) = 6 mass% (A4): Dow EPDM product name "Keltan Eco5470" (A4 (ethylene-propylene-5-ethylidene-2-norbornene copolymer 100 parts by mass), Mooney viscosity (ML 1+4 100°C) = 76, content of monomer units derived from ethylene in (A4) = 69 mass%, content of monomer units derived from 5-ethylidene-2-norbornene in (A4) = 5 mass%, biomass degree of (A4) analyzed by ASTM D6866 = 71% (B4): Paraffinic mineral oil manufactured by Idemitsu Kosan Co., Ltd., product name "Diana Process Oil PW380" (C1): Diisononyl phthalate manufactured by Tokyo Chemical Industry Co., Ltd., product name "Diisononyl phthalate (branched chain isomer mixture)" (D1): Low-density polyethylene, melting point 112°C, density 920 kg / m 3 , content of monomer units derived from ethylene = more than 98% by mass (D1 + E1): Sumika Color Co., Ltd. carbon black masterbatch product name "PEM-8080" (a mixture of 100 parts by mass of D1 (low-density polyethylene) and 100 parts by mass of E1 (carbon black)) (F1): Calcium carbonate manufactured by Nitto Funka Kogyo Co., Ltd. Product name "NS#100"
[0083] [Example 1] The raw materials (A1+B1) 100% by mass and (C1) 0.1% by mass were melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill at a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 1.
[0084] [Comparative Example 1] 100% by mass of the raw materials (A1 + B1) was melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill at a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the composition obtained by melt-kneading were measured. The measurement results and the amounts of each component are shown in Table 1.
[0085] [Example 2] As raw materials, 10% by mass of the composition obtained in Example 1 and 90% by mass of (A1 + B1) were melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill under conditions of a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the composition obtained by melt-kneading were measured. The measurement results and the blending amounts of each component are shown in Table 1.
[0086] Comparative Example 2 As raw materials, 100% by mass of (A1 + B1) and 1% by mass of (C1) were melt-kneaded in a 100cc Toyo Seiki Seisakusho Laboplastomill under conditions of a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the composition obtained by melt-kneading were measured. The measurement results and the blending amounts of each component are shown in Table 1.
[0087] [Table 1]
[0088] [Example 3] The raw materials (A2+B2) 100% by mass and (C1) 0.1% by mass were melt-kneaded in a 100cc Toyo Seiki Seisakusho Laboplastomill at a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 2.
[0089] Comparative Example 3 100% by mass of the raw materials (A2 + B2) was melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill at a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the composition obtained by melt-kneading were measured. The measurement results and the amounts of each component are shown in Table 2.
[0090] [Example 4] As raw materials, 10% by mass of the composition obtained in Example 3 and 90% by mass of (A2 + B2) were melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill under conditions of a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the composition obtained by melt-kneading were measured. The measurement results and the blending amounts of each component are shown in Table 2.
[0091] Comparative Example 4 As raw materials, 100% by mass of (A2+B2) and 1% by mass of (C1) were melt-kneaded in a 100cc Toyo Seiki Seisakusho Laboplastomill under conditions of a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the composition obtained by melt-kneading were measured. The measurement results and the blending amounts of each component are shown in Table 2.
[0092] [Table 2]
[0093] [Example 5] The raw materials (A3 + B3) 100% by mass and (C1) 0.1% by mass were melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill at a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 3.
[0094] [Example 6] As raw materials, 10% by mass of the composition obtained in Example 5 and 90% by mass of (A3 + B3) were melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill under conditions of a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the blending amounts of each component are shown in Table 3.
[0095] [Example 7] As raw materials, 10% by mass of the composition obtained in Example 6 and 90% by mass of (A3 + B3) were melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill under conditions of a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the blending amounts of each component are shown in Table 3.
[0096] Comparative Example 5 As raw materials, 100% by mass of (A3 + B3) and 1% by mass of (C1) were melt-kneaded in a 100cc Toyo Seiki Seisakusho Laboplastomill under conditions of a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the composition obtained by melt-kneading were measured. The measurement results and the blending amounts of each component are shown in Table 3.
[0097] [Table 3]
[0098] [Example 8] The raw materials (A2 + B2) 50% by mass, (C1) 0.1% by mass, (D1 + E1) 40% by mass, and (F1) 10% by mass were melt-kneaded in a 100cc Toyo Seiki Seisakusho Laboplastomill at a rotor temperature of 120±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 4.
[0099] [Example 9] The raw materials, 10% by mass of the composition obtained in Example 8, 45% by mass of (A2 + B2), 36% by mass of (D1 + E1), and 9% by mass of (F1), were melt-kneaded in a 100cc Toyo Seiki Seisakusho Laboplastomill at a rotor temperature of 120±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 4.
[0100] [Example 10] The raw materials, 10% by mass of the composition obtained in Example 9, 45% by mass of (A2 + B2), 36% by mass of (D1 + E1), and 9% by mass of (F1), were melt-kneaded in a 100cc Toyo Seiki Seisakusho Laboplastomill at a rotor temperature of 120±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 4.
[0101] Comparative Example 6 The raw materials (A2 + B2) 50% by mass, (C1) 1% by mass, (D1 + E1) 40% by mass, and (F1) 10% by mass were melt-kneaded in a 100cc Toyo Seiki Seisakusho Laboplastomill at a rotor temperature of 120±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 4.
[0102] [Table 4]
[0103] Comparative Example 7 As raw materials, 100% by mass of (A4) and 0.1% by mass of (C1) were melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill under conditions of a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the composition obtained by melt-kneading were measured. The measurement results and the blending amounts of each component are shown in Table 5.
[0104] [Comparative Example 8] As raw materials, 10% by mass of the composition obtained in Comparative Example 7 and 90% by mass of (A4) were melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill under conditions of a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 5 minutes. The average shear viscosity and average die swell ratio of the composition obtained by melt-kneading were measured. The measurement results and the blending amounts of each component are shown in Table 5.
[0105] [Table 5]
[0106] Comparative Example 9 The raw materials, 65% by mass of (A4) and 35% by mass of (B4), were melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill at a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 15 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 6.
[0107] [Example 11] The raw materials, 65% by mass of (A4), 35% by mass of (B4), and 0.1% by mass of (C1), were melt-kneaded in a 100cc Toyo Seiki Seisakusho Laboplastomill at a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 15 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 6.
[0108] [Example 12] The raw materials, 10% by mass of the composition obtained in Example 11, 58.5% by mass of (A4), and 31.5% by mass of (B4), were melt-kneaded in a 100cc Toyo Seiki Seisakusho Laboplastomill at a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 15 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 6.
[0109] [Example 13] The raw materials, 10% by mass of the composition obtained in Example 12, 58.5% by mass of (A4), and 31.5% by mass of (B4), were melt-kneaded in a 100cc Toyo Seiki Seisakusho Laboplastomill at a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 15 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 6.
[0110] [Comparative Example 10] The raw materials, 65% by mass of (A4), 35% by mass of (B4), and 1% by mass of (C1), were melt-kneaded in a 100cc Toyo Seiki Seisakusho Labo Plastomill at a rotor temperature of 70±10°C, a rotation speed of 60 rpm, and a kneading time of 15 minutes. The average shear viscosity and average die swell ratio of the melt-kneaded composition were measured. The measurement results and the amounts of each component are shown in Table 6.
[0111] [Table 6]
[0112] As can be seen from the results in Tables 1 to 6, the thermoplastic resin compositions of the examples that satisfy all of the constituent requirements of the present invention have a relatively small die swelling ratio during extrusion molding.
Claims
1. (A) an ethylene / α-olefin / non-conjugated diene copolymer, (B) a mineral oil, and (C) a phthalate ester; (C) A thermoplastic resin composition having a phthalate ester content of 5 ppm or more and 10,000 ppm or less relative to 100 parts by mass of (A) the ethylene / α-olefin / non-conjugated diene copolymer.
2. 2. The thermoplastic resin composition according to claim 1, wherein the content of the mineral oil (B) is 30 parts by mass or more and 200 parts by mass or less per 100 parts by mass of the ethylene-α-olefin-non-conjugated diene copolymer (A).
3. The thermoplastic resin composition according to claim 1, further comprising at least one selected from the group consisting of calcium carbonate and carbon black.
4. The thermoplastic resin composition according to claim 1, further comprising (D) an olefin-based polymer (excluding (A) an ethylene-α-olefin-non-conjugated diene copolymer).
5. 5. The thermoplastic resin composition according to claim 4, wherein the olefin polymer (D) is at least one selected from the group consisting of ethylene polymers and propylene polymers.
6. 2. The thermoplastic resin composition according to claim 1, wherein the content of the phthalate ester (C) is 50 ppm or more and 5,000 ppm or less relative to 100 parts by mass of the ethylene / α-olefin / non-conjugated diene copolymer (A).
7. 2. The thermoplastic resin composition according to claim 1, wherein the content of the mineral oil (B) is 50 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the ethylene-α-olefin-non-conjugated diene copolymer (A).
8. The thermoplastic resin composition according to claim 1, wherein the phthalate ester (C) is diisononyl phthalate.
9. The thermoplastic resin composition according to claim 1, wherein the content of monomer units derived from non-conjugated dienes in the ethylene-α-olefin-non-conjugated diene copolymer (A) is 4% by mass or more and 15% by mass or less.
10. (A) Mooney viscosity (ML 1+4 100°C) is 40 or more.
11. Temperature: 220°C, shear rate: 1216 sec -1 2. The thermoplastic resin composition according to claim 1, wherein the shear viscosity at 2000 kJ / min is 50 Pa·sec or more and 600 Pa·sec or less.
12. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 11.
Citation Information
Patent Citations
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