Thermoplastic resin composition

Abstract

Provided is a thermoplastic resin composition comprising a styrene-based resin composition, wherein: the styrene-based resin composition is obtained by melt-kneading (A) a styrene-based polymer having a syndiotactic structure, (B) a functional group-containing polyphenylene ether, and (C) a metal compound; the functional group of the (B) functional group-containing polyphenylene ether is a functional group derived from an acid and / or a derivative thereof; the blending amount of the (B) functional group-containing polyphenylene ether is 0.1-150 parts by mass with respect to 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure; and the blending amount of the (C) metal compound is 0.001-10 parts by mass with respect to 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure.

Description

thermoplastic resin composition

[0001] The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition containing a styrene-based resin composition.

[0002] Styrenic polymers having a syndiotactic structure have excellent heat resistance, chemical resistance, and electrical properties, and are therefore widely used in automobile parts, tableware and food containers, electrical and electronic parts, etc.

[0003] For example, Patent Document 1 discloses an impact-resistant polystyrene resin composition comprising 100 parts by weight of (A) a styrene polymer having a syndiotactic structure and 1 to 100 parts by weight of (B) a rubber-like elastomer having a polar group, the composition being aimed at providing a syndiotactic polystyrene resin composition having excellent heat resistance, elastic modulus, impact resistance, and elongation. Patent Document 2 discloses an impact-resistant polystyrene resin composition comprising 100 parts by weight of a mixture of 95.0 to 99.9% by weight of (A) a styrene polymer having a syndiotactic structure and 0.1 to 5.0% by weight of (B) a polyphenylene ether, and 1 to 100 parts by weight of (C) a rubber-like elastomer, the composition being aimed at providing a syndiotactic polystyrene resin composition having excellent heat resistance, elastic modulus, moldability, impact resistance, and elongation. Furthermore, Patent Document 3 discloses a thermoplastic resin composition that is intended to improve mechanical properties, particularly rigidity and heat resistance, and that comprises (A) 100 parts by weight of a styrene-based polymer having a high degree of syndiotactic structure, (B) 1 to 350 parts by weight of an inorganic filler, and (C) 0.1 to 3.5 parts by weight of a maleic anhydride-modified polyphenylene ether.

[0004] JP-A-6-256607 JP-A-7-053815 JP-A-5-209098

[0005] Although styrene-based polymers having a syndiotactic structure have various excellent physical properties, there is room for further improvement in the toughness of molded articles, particularly in tensile elongation at break. Patent documents 1 and 2 describe improving toughness by adding a rubber-like elastomer to a polystyrene-based resin composition. However, the inclusion of the rubber-like elastomer may result in a decrease in the elasticity of the polystyrene-based resin composition. Patent document 3 describes improving rigidity and heat resistance by blending an inorganic filler and a maleic anhydride-modified polyphenylene ether with a styrene-based polymer. However, there is room for further improvement in toughness. An object of the present invention is to provide a thermoplastic resin composition containing a styrene-based resin composition, which has improved flexural elongation at break or tensile elongation at break and excellent toughness.

[0006] As a result of extensive investigations, the present inventors have found that the above-mentioned problems can be solved by a thermoplastic resin composition containing a styrene-based resin composition in which a styrene-based polymer having a syndiotactic structure is combined with a functional group-containing polyphenylene ether and a metal compound. That is, the present invention relates to the following [1] to

[13] .

[0007] [1] A thermoplastic resin composition comprising a styrene-based resin composition, the styrene-based resin composition being obtained by melt-kneading (A) a styrene-based polymer having a syndiotactic structure, (B) a functional group-containing polyphenylene ether, and (C) a metal compound, wherein the functional group of the (B) functional group-containing polyphenylene ether is a functional group derived from an acid and / or a derivative thereof, the blending amount of the (B) functional group-containing polyphenylene ether is 0.1 to 150 parts by mass relative to 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure, and the blending amount of the (C) metal compound is 0.001 to 10 parts by mass relative to 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure. [2] The thermoplastic resin composition according to [1], wherein the functional group of the (B) functional group-containing polyphenylene ether derived from an acid and / or a derivative thereof is at least one selected from maleic anhydride, maleic acid, fumaric acid, maleic acid esters, fumaric acid esters, maleates, fumarates, acrylic acid, acrylic acid esters, acrylic acid amides, acrylic acid salts, methacrylic acid, methacrylic acid esters, methacrylic acid amides, methacrylic acid salts, and glycidyl methacrylate. [3] The thermoplastic resin composition according to [1] or [2], wherein the (C) metal compound is at least one selected from metal salts, metal oxides, metal hydroxides, and metal complexes. [4] The thermoplastic resin composition according to any one of [1] to [3], wherein the (C) metal compound is a metal salt. [5] The thermoplastic resin composition according to any one of [1] to [4], wherein the (C) metal compound is at least one selected from alkali metal salts, alkaline earth metal salts, and transition metal salts. [6] The thermoplastic resin composition according to any one of [1] to [5], wherein the styrene-based resin composition further contains a nucleating agent, and the amount of the nucleating agent is 0.1 to 3 parts by mass per 100 parts by mass of the styrene-based polymer (A) having a syndiotactic structure.[7] The thermoplastic resin composition according to any one of [1] to [6], wherein the styrene-based resin composition further contains a rubber-like elastomer, and the amount of the rubber-like elastomer is 5 to 25 parts by mass per 100 parts by mass of the styrene-based polymer (A) having a syndiotactic structure. [8] The thermoplastic resin composition according to any one of [1] to [7], wherein the styrene-based resin composition further contains a silicone oil, and the amount of the silicone oil is 0.1 to 10 parts by mass per 100 parts by mass of the styrene-based polymer (A) having a syndiotactic structure. [9] The thermoplastic resin composition according to any one of [1] to [8], further containing glass fiber.

[10] The thermoplastic resin composition according to [9], wherein the content of the glass fiber is 5 to 50% by mass of the total of the styrene-based resin composition and the glass fiber.

[11] A method for producing a thermoplastic resin composition containing a styrene-based resin composition, comprising the step of melt-kneading (A) a styrene-based polymer having a syndiotactic structure, (B) a functional group-containing polyphenylene ether, and (C) a metal compound to obtain the styrene-based resin composition, wherein the functional group of the (B) functional group-containing polyphenylene ether is a functional group derived from an acid and / or a derivative thereof, the blending amount of the (B) functional group-containing polyphenylene ether is 0.1 to 150 parts by mass per 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure, and the blending amount of the (C) metal compound is 0.001 to 10 parts by mass per 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure.

[12] The method for producing a thermoplastic resin composition according to

[11] , further comprising blending glass fiber in the step of obtaining the styrene-based resin composition.

[13] The method for producing a thermoplastic resin composition according to

[12] , wherein the blending amount of the glass fiber is 5 to 50 mass% of the total of the styrene-based resin composition and the glass fiber.

[0008] According to the present invention, it is possible to provide a thermoplastic resin composition containing a styrene-based resin composition, which has improved flexural elongation at break or tensile elongation at break and excellent toughness.

[0009] [Thermoplastic Resin Composition] The thermoplastic resin composition of the present invention is a thermoplastic resin composition containing a styrene-based resin composition, wherein the styrene-based resin composition is obtained by melt-kneading (A) a styrene-based polymer having a syndiotactic structure, (B) a functional group-containing polyphenylene ether, and (C) a metal compound, wherein the functional group of the (B) functional group-containing polyphenylene ether is a functional group derived from an acid and / or a derivative thereof, the blending amount of the (B) functional group-containing polyphenylene ether is 0.1 to 150 parts by mass relative to 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure, and the blending amount of the (C) metal compound is 0.001 to 10 parts by mass relative to 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure.

[0010] <Styrene-based resin composition> The thermoplastic resin composition of the present invention includes a styrene-based resin composition, and the styrene-based resin composition is obtained by melt-kneading (A) a styrene-based polymer having a syndiotactic structure, (B) a functional group-containing polyphenylene ether, and (C) a metal compound.

[0011] ((A) Styrenic polymer having syndiotactic structure) (A) Styrenic polymer having syndiotactic structure (hereinafter also referred to as (A) SPS) is a styrene resin having a high degree of syndiotactic structure. In this specification, "syndiotactic" means that the phenyl rings in adjacent styrene units are arranged alternately with respect to the plane formed by the main chain of the polymer block (hereinafter referred to as syndiotacticity) at a high rate. Tacticity can be determined by nuclear magnetic resonance spectroscopy using carbon isotopes ( 13 Quantitative identification can be performed using 1C-NMR. 13 By C-NMR, the proportion of a plurality of consecutive structural units, for example, two consecutive monomer units as a diad, three consecutive monomer units as a triad, and five consecutive monomer units as a pentad, can be quantified.

[0012] In the present invention, the term "styrene-based resin having a highly syndiotactic structure" refers to a styrene-based polymer such as polystyrene, poly(hydrocarbon-substituted styrene), poly(halogenated styrene), poly(halogenated alkylstyrene), poly(alkoxystyrene), or poly(vinyl benzoate ester), a hydrogenated polymer or mixture thereof, or a copolymer containing any of these as a main component, having a syndiotacticity of typically 75 mol % or more, preferably 85 mol % or more in racemic diad (r), or typically 30 mol % or more, preferably 50 mol % or more in racemic pentad (rrrr).

[0013] Examples of poly(hydrocarbon-substituted styrenes) include poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(tert-butylstyrene), poly(phenylstyrene), poly(vinylnaphthalene), and poly(vinylstyrene). Examples of poly(halogenated styrenes) include poly(chlorostyrene), poly(bromostyrene), and poly(fluorostyrene), and examples of poly(halogenated alkylstyrenes) include poly(chloromethylstyrene). Examples of poly(alkoxystyrenes) include poly(methoxystyrene) and poly(ethoxystyrene).

[0014] Examples of comonomer components of copolymers containing the above-mentioned structural units include, in addition to the monomers of the styrene polymers, olefin monomers such as ethylene, propylene, butene, hexene, and octene; diene monomers such as butadiene and isoprene; and polar vinyl monomers such as cyclic olefin monomers, cyclic diene monomers, methyl methacrylate, maleic anhydride, and acrylonitrile. Copolymers that are preferably used as SPS include copolymers of styrene and p-methylstyrene, copolymers of styrene and p-tert-butylstyrene, and copolymers of styrene and divinylbenzene, with a copolymer of styrene and p-methylstyrene being preferred.

[0015] Among the (A) SPS, at least one selected from polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), poly(m-chlorostyrene), poly(p-fluorostyrene), and a copolymer of styrene and p-methylstyrene is preferred, at least one selected from polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), and a copolymer of styrene and p-methylstyrene is more preferred, polystyrene and a copolymer of styrene and p-methylstyrene are even more preferred, and polystyrene is most preferred.

[0016] The melt flow rate (MFR) of (A) SPS is preferably 3 to 50 g / 10 min, more preferably 5 to 40 g / 10 min, and even more preferably 8 to 35 g / 10 min, when measured under conditions of a temperature of 300° C. and a load of 1.2 kg. If the MFR of (A) SPS is 3 g / 10 min or more, the thermoplastic resin composition will have excellent fluidity when used in molding, etc., and if it is 50 g / 10 min or less, the thermoplastic resin composition will have sufficient strength.

[0017] The weight-average molecular weight of (A) SPS is preferably 10,000 to 300,000, more preferably 50,000 to 290,000, even more preferably 100,000 to 280,000, and still more preferably 150,000 to 270,000. When the weight-average molecular weight of (A) SPS is 10,000 or more, the flexural elongation at break or tensile elongation at break of the thermoplastic resin composition is further improved, and when the weight-average molecular weight of (A) SPS is 300,000 or less, the flowability of the thermoplastic resin composition when used in molding or the like is easily ensured. In this specification, unless otherwise specified, the weight-average molecular weight is a value measured by gel permeation chromatography at 145°C using a GPC apparatus (HLC-8321GPC / HT) manufactured by Tosoh Corporation and a GPC column (GMHHR-H(S)HTC / HT) manufactured by Tosoh Corporation, using 1,2,4-trichlorobenzene as an eluent, and converted using a calibration curve of standard polystyrene. Methods for adjusting the weight-average molecular weight of SPS include appropriately selecting the type, amount used, and polymerization temperature of each catalyst component, and introducing hydrogen.

[0018] The amount of (A) SPS blended per 100 parts by mass of the styrene-based resin composition is preferably 30 parts by mass or more, more preferably 35 to 99.5 parts by mass, even more preferably 45 to 99 parts by mass, and still more preferably 45 to 98.5 parts by mass. When the amount of (A) SPS blended is within the above range, the thermoplastic resin composition will have better mechanical properties, heat resistance, and chemical resistance.

[0019] In the thermoplastic resin composition of one embodiment of the present invention, the blending amount of (A) SPS in the thermoplastic resin composition is preferably 40% by mass or more but less than 100% by mass, more preferably 42 to 90% by mass, even more preferably 45 to 80% by mass, and still more preferably 45 to 70% by mass. When the blending amount of (A) SPS is within the above range, the thermoplastic resin composition has better mechanical properties, heat resistance, and chemical resistance.

[0020] (A) SPS can be produced, for example, by polymerizing a styrene-based monomer (a monomer corresponding to the above-mentioned styrene-based polymer) in an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product (aluminoxane) of water with trialkylaluminum as catalysts (for example, JP 2009-068022 A).

[0021] (B) Functional Group-Containing Polyphenylene Ether) In the thermoplastic resin composition of the present invention, the styrene-based resin composition is blended with (B) functional group-containing polyphenylene ether, and the functional group is a functional group derived from an acid and / or a derivative thereof. The blending amount of (B) functional group-containing polyphenylene ether is 0.1 to 150 parts by mass per 100 parts by mass of (A) SPS. In this specification, "acid and / or a derivative thereof" means "at least one of an acid and a derivative thereof." In other words, it means "acid," "acid derivative," or "acid and a derivative thereof."

[0022] Incorporation of the (B) functional group-containing polyphenylene ether in a thermoplastic resin composition is believed to result in the formation of ionic and / or coordinate bonds between the functional groups of the (B) functional group-containing polyphenylene ether and the metal ions of the (C) metal compound described below, thereby ionomerizing the (B) functional group-containing polyphenylene ether. This is believed to result in improved flexural elongation at break or tensile elongation at break of the thermoplastic resin composition. Furthermore, the (B) functional group-containing polyphenylene ether improves the compatibility between the (A) SPS and other components, thereby improving the interfacial strength between the components. As a result, the flexural elongation at break or tensile elongation at break of the thermoplastic resin composition is further improved, thereby improving toughness. Furthermore, when the thermoplastic resin composition of one embodiment of the present invention contains the glass fiber described below, the functional groups derived from the acid and / or a derivative thereof of the (B) functional group-containing polyphenylene ether react with the glass fiber, thereby further improving the flexural elongation at break or tensile elongation at break of the thermoplastic resin composition, thereby improving toughness.

[0023] From the viewpoint of improving the bending elongation at break or tensile elongation at break of the thermoplastic resin composition, the blending amount of (B) functional group-containing polyphenylene ether is 0.1 to 150 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of (A) SPS.

[0024] The functional group of the (B) functional group-containing polyphenylene ether is a functional group derived from an acid and / or a derivative thereof. The functional group derived from an acid and / or a derivative thereof improves the compatibility between (A) SPS and other components, thereby improving the interfacial strength between the components and further improving the flexural elongation at break or tensile elongation at break of the thermoplastic resin composition. The acid and / or a derivative thereof, which is the functional group derived from an acid and / or a derivative thereof, is preferably at least one selected from maleic anhydride, maleic acid, fumaric acid, maleic acid esters, fumaric acid esters, maleates, fumarates, acrylic acid, acrylic acid esters, acrylic acid amides, acrylic acid salts, methacrylic acid, methacrylic acid esters, methacrylic acid amides, methacrylic acid salts, and glycidyl methacrylate, more preferably at least one selected from maleic anhydride, maleic acid, fumaric acid, and glycidyl methacrylate, and even more preferably fumaric acid. The functional group derived from an acid and / or a derivative thereof is preferably at least one selected from an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid halide group, and a carboxylic acid amide group, and more preferably a carboxylic acid group.

[0025] The functional group-containing polyphenylene ether (B) is preferably at least one selected from fumaric acid-modified polyphenylene ether and maleic anhydride-modified polyphenylene ether, and more preferably fumaric acid-modified polyphenylene ether.

[0026] From the viewpoint of improving the bending elongation at break or the tensile elongation at break, the modification rate (modifier content) of the (B) functional group-containing polyphenylene ether is preferably 0.1 to 20.0 mass%, more preferably 0.2 to 15.0 mass%, even more preferably 0.3 to 10.0 mass%, and still more preferably 0.5 to 5.0 mass%. The modification rate (modifier content) of the modified polyphenylene ether can be determined from the neutralization titer measured in accordance with JIS K 0070-1992.

[0027] (B) Functional group-containing polyphenylene ether can be obtained by reacting the polyphenylene ether described below with the acid and / or a derivative thereof, thereby modifying the polyphenylene ether described below with the acid and / or a derivative thereof. There are no particular limitations on the modification method, and known methods can be used. Preferred modification methods include melt modification and solution modification, with melt modification being more preferred because a higher degree of modification can be achieved and productivity is high. That is, the modified polyphenylene ether is preferably a modified polyphenylene ether produced by melt modification or a modified polyphenylene ether produced by solution modification, and more preferably a modified polyphenylene ether produced by melt modification.

[0028] Examples of polyphenylene ethers include poly(2,6-dimethyl-1,4-phenylene ether), poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4'-methylphenyl)-1,4-phenylene ether], poly(2-bromo-6-phenyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2-phenyl- 1,4-phenylene ether), poly(2-chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly(2-chloro-6-ethyl-1,4-phenylene ether), poly(2-chloro-6-bromo-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4-phenylene ether), poly(2-methyl-6-isopropyl-1,4-phenylene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dibromo-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether) is preferred, and poly(2,6-dimethyl-1,4-phenylene ether) is more preferred.

[0029] Melt modification is a method of obtaining a modified polyphenylene ether by melt-kneading polyphenylene ether and a modifier in the presence or absence of a radical generator. Specifically, this is a method of melt-kneading and reacting at a temperature in the range of 150 to 350°C using a roll mill, Banbury mixer, extruder, or the like. Specifically, a method is preferred in which polyphenylene ether, a modifier, and an optional radical generator are uniformly dry-blended at room temperature, and then the melt reaction is carried out at a temperature in the range of 300 to 350°C, which is essentially the kneading temperature of polyphenylene ether. If the temperature is 300°C or higher, the melt viscosity can be appropriately maintained, and if the temperature is 350°C or lower, decomposition of the polyphenylene ether can be suppressed.

[0030] The amount of the modifier used in the melt modification is preferably 0.1 to 22.0 parts by mass, more preferably 0.2 to 17.0 parts by mass, even more preferably 0.3 to 12.0 parts by mass, and still more preferably 0.5 to 7.0 parts by mass, relative to 100 parts by mass of polyphenylene ether. When the amount of the modifier used is within this range, the modification rate of the polyphenylene ether can be improved while the amount of modifier remaining in the melt-modified product can be reduced.

[0031] The radical generator used for melt modification is preferably one having a temperature showing a half-life of 1 minute of 300°C or higher. Specific examples include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylhexane, and 2,3-dimethyl-2,3-di(p-methylphenyl)butane. Of these, 2,3-dimethyl-2,3-diphenylbutane, which has a temperature showing a half-life of 1 minute of 330°C, is preferably used. The proportion of the radical generator used is preferably selected from the range of 0.1 to 3.0 parts by mass, more preferably 0.5 to 2.0 parts by mass, per 100 parts by mass of polyphenylene ether. If the amount is 0.1 part by mass or more, a high modification effect can be obtained, and if the amount is 3.0 parts by mass or less, the polyphenylene ether can be efficiently modified and insoluble components are less likely to be produced.

[0032] (C) Metal Compound In the thermoplastic resin composition of the present invention, the styrene-based resin composition is blended with a (C) metal compound. The blending amount of the (C) metal compound is 0.001 to 10 parts by mass per 100 parts by mass of the (A) SPS. The blending of the (C) metal compound in the thermoplastic resin composition is believed to form ionic bonds and / or coordinate bonds between the functional groups of the (B) functional group-containing polyphenylene ether and the metal ions of the (C) metal compound, thereby ionomerizing the (B) functional group-containing polyphenylene ether. This is believed to result in improved flexural elongation at break or tensile elongation at break of the thermoplastic resin composition. Ionomerization causes intermolecular crosslinking, improving the viscosity of the resulting composition. The formation of an ionomer can also be estimated by observing this phenomenon.

[0033] From the viewpoint of improving the bending elongation at break or the tensile elongation at break, the (C) metal compound is preferably at least one selected from metal salts, metal oxides, metal hydroxides, and metal complexes, and more preferably metal salts. Furthermore, the (C) metal compound is preferably at least one selected from alkali metal salts, alkaline earth metal salts, and transition metal salts. Examples of the metal species in the (C) metal compound include at least one selected from alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as magnesium, calcium, and barium; and transition metals such as aluminum, zinc, cobalt, chromium, and copper. Among these, from the viewpoint of improving the bending elongation at break or the tensile elongation at break, at least one selected from sodium, potassium, magnesium, calcium, and zinc is preferred, at least one selected from potassium, magnesium, and zinc is more preferred, and potassium is even more preferred.

[0034] The metal salt is preferably at least one selected from organic metal salts and inorganic metal salts. The organic metal salt is preferably at least one selected from formates, acetates, and stearates of the above metal species, more preferably at least one selected from acetates and stearates, and even more preferably acetates. The inorganic metal salt is preferably at least one selected from carbonates, bicarbonates, and halide salts of the above metal species, and more preferably carbonates.

[0035] Specifically, the (C) metal compound is preferably at least one selected from potassium acetate, magnesium acetate, zinc acetate, potassium stearate, magnesium stearate, zinc stearate, potassium carbonate, potassium bicarbonate, and magnesium carbonate, and more preferably at least one selected from potassium acetate, zinc acetate, potassium stearate, magnesium stearate, potassium carbonate, and potassium bicarbonate.

[0036] In the thermoplastic resin composition of one embodiment of the present invention, the blending amount of the (C) metal compound is preferably 0.001 to 10 parts by mass, more preferably 0.003 to 5 parts by mass, even more preferably 0.005 to 2 parts by mass, and still more preferably 0.01 to 1 part by mass, per 100 parts by mass of the (A) SPS, from the viewpoint of improving the bending elongation at break or the tensile elongation at break.

[0037] In the thermoplastic resin composition of one embodiment of the present invention, the mass ratio of the content of the metal compound to the content of the (B) functional group-containing polyphenylene ether [(C) metal compound / (B) functional group-containing polyphenylene ether] is preferably 0.001 to 0.50, more preferably 0.003 to 0.10, even more preferably 0.005 to 0.05, and still more preferably 0.01 to 0.025. When the mass ratio [(C) metal compound / (B) functional group-containing polyphenylene ether] is 0.001 or more, a large amount of the (B) functional group-containing polyphenylene ether is ionomerized, thereby further improving the flexural elongation at break or tensile elongation at break of the thermoplastic resin composition and further improving toughness. Furthermore, by making the mass ratio [(C) metal compound / (B) functional group-containing polyphenylene ether] 0.50 or less, the ionomerized (B) functional group-containing polyphenylene ether is prevented from becoming excessive, and a decrease in melt fluidity and a decrease in moldability are suppressed.

[0038] (Other Components) In the thermoplastic resin composition of one embodiment of the present invention, the styrene-based resin composition may contain, in addition to the above-mentioned components, any other components within the scope that does not impair the object of the present invention. Examples of other components include a crystal nucleating agent, a rubber-like elastomer, a silicone oil, an antioxidant, a flame retardant, a flame retardant assistant, a colorant, a crosslinking agent, a crosslinking assistant, a dispersant, a plasticizer, an antifouling agent, an ultraviolet absorber, a light stabilizer, and an antistatic agent.

[0039] <<Nucleating Agent>> In the reinforced thermoplastic resin composition of one embodiment of the present invention, the styrene-based resin composition preferably further contains a nucleating agent. By adding the nucleating agent, the crystallization temperature can be increased, allowing a wider range of temperature conditions for crystallization to be set, and productivity can be further improved.

[0040] The crystal nucleating agent is preferably at least one selected from the group consisting of inorganic crystal nucleating agents and organic crystal nucleating agents. Of these, organic crystal nucleating agents are preferred. Examples of organic crystal nucleating agents include alkali metal salts of organic carboxylic acids, alkaline earth metal salts of organic carboxylic acids, organic compounds of phosphoric acid or phosphorous acid and their metal salts, phthalocyanine derivatives, and sorbitol derivatives. More specific examples include metal salts of carboxylic acids such as aluminum di(p-tert-butylbenzoate), sodium salt of benzoic acid, hydroxyaluminum salt of p-tert-butylbenzoic acid, and aluminum hydroxy-di(p-tert-butylbenzoate), sodium methylenebis(2,4-di-tert-butylphenyl)phosphate, sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, and [2,2'-methylenebis(4,6-di-tert-butylphenyl)]phosphate. Metal salts of phosphoric acid such as lithium, [2,2'-methylenebis(4,6-di-tert-butylphenyl)]]phosphate, potassium bis(4-tert-butylphenyl)phosphate, sodium methylene(2,4-tert-butylphenyl)phosphate, aluminum bis(4,6',6,6'-tetra-tert-butyl-2,2'-methylenediphenyl phosphate) hydroxide, and ammonium [2,2'-methylenebis(4,6-di-tert-butylphenyl)]]phosphate can be selected and used. Complexes containing these can also be used. Among these, from the viewpoint of increasing the crystallization temperature, it is preferable to use a lithium salt of an organic compound of phosphoric acid or phosphorous acid, and it is more preferable to use lithium [2,2'-methylenebis(4,6-di-tert-butylphenyl)]]phosphate. Specific trade names include ADK STAB NA-10, ADK STAB NA-11, ADK STAB NA-21, ADK STAB NA-30, ADK STAB NA-35, and ADK STAB NA-70 manufactured by ADEKA Corporation, and PTBBA-AL manufactured by Dainippon Ink and Chemicals, Inc.

[0041] In the thermoplastic resin composition of one embodiment of the present invention, the amount of the nucleating agent is preferably 0.1 to 3 parts by mass, more preferably 0.3 to 2 parts by mass, and even more preferably 0.5 to 1.5 parts by mass, per 100 parts by mass of (A) SPS. When the amount of the nucleating agent (C) is 0.1 parts by mass or more, a wider range of temperature conditions for crystallization can be set, further improving productivity. When the amount is 3.0 parts by mass or less, the amount of gas components generated when the thermoplastic resin composition is used for molding or the like is suppressed, resulting in a better appearance.

[0042]

[0033] In the thermoplastic resin composition of one embodiment of the present invention, the styrene-based resin composition may further contain a rubber-like elastomer. By incorporating the rubber-like elastomer, the flexural elongation at break or tensile elongation at break of the thermoplastic resin composition is further improved, and the toughness is further improved.

[0043] The rubber-like elastomer includes, but is not limited to, an olefin-based elastomer or an elastomer containing a structural unit derived from styrene. Examples of the olefin-based elastomer include elastomers whose main component is ethylene or propylene. The rubber-like elastomer is preferably an elastomer containing a structural unit derived from styrene, and more preferably at least one selected from the group consisting of a styrene-diene block copolymer, a hydrogenated styrene-diene block copolymer, a styrene-diene random copolymer, a hydrogenated styrene-diene random copolymer, and a styrene-olefin random copolymer. Examples of dienes copolymerizable with styrene include butadiene and isoprene, and examples of olefins copolymerizable with styrene include ethylene, propylene, and butylene.

[0044] The rubber-like elastomer is more preferably at least one selected from the group consisting of styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, and styrene-ethylene-butylene random copolymer, and even more preferably styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEPS). styrene-isoprene-styrene block copolymer (SBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-isoprene-styrene block copolymer (SEPS), even more preferably at least one selected from the group consisting of styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-isoprene-styrene block copolymer (SEPS), even more preferably at least one selected from the group consisting of hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-isoprene-styrene block copolymer (SEPS), and even more preferably hydrogenated styrene-butadiene-styrene block copolymer (SEBS).

[0045] The mass ratio of the structural units derived from styrene to the sum of the structural units derived from diene, hydrogenated diene, and olefin constituting the rubbery elastomer [(styrene) / (diene, hydrogenated diene, olefin)] is preferably 20 / 80 to 70 / 30, more preferably 25 / 75 to 60 / 40, and even more preferably 25 / 75 to 45 / 55. The styrene content of the rubbery elastomer is preferably in the range of 25 to 60 mass%, and more preferably 25 to 45 mass%. This mass ratio improves compatibility with (A) SPS, further improving the flexural elongation at break or tensile elongation at break of the thermoplastic resin composition, and further improving toughness.

[0046] The amount of the rubber-like elastomer blended per 100 parts by mass of the styrene-based resin composition is preferably 5 to 25 parts by mass, more preferably 6 to 20 parts by mass, and even more preferably 7 to 15 parts by mass. When the amount of the rubber-like elastomer blended is within the above range, the flexural elongation at break or tensile elongation at break of the thermoplastic resin composition is further improved, and the toughness is further improved.

[0047] Silicone Oil In the thermoplastic resin composition of one embodiment of the present invention, the styrene-based resin composition preferably further contains a silicone oil, which improves the flexural elongation at break or tensile elongation at break of the thermoplastic resin composition and the toughness thereof.

[0048] Examples of silicone oils include dimethyl silicone oil, phenylmethyl silicone oil, and diphenyl silicone oil, among which dimethyl silicone oil is preferred. In the present invention, dimethyl silicone oil includes silicone oils based on a dimethyl silicone structure and modified products thereof (hereinafter also referred to as "modified dimethyl silicone oil"). Modified dimethyl silicones, regardless of whether they are reactive or non-reactive, can be side chain type, both terminal type, one terminal type, or both terminal type of side chain, depending on the position of the modifying group. Specific examples of modified dimethyl silicone oils include amino-modified dimethyl silicone oil, epoxy-modified dimethyl silicone oil, carboxy-modified dimethyl silicone oil, carbinol-modified dimethyl silicone oil, methacrylic-modified dimethyl silicone oil, mercapto-modified dimethyl silicone oil, phenol-modified dimethyl silicone oil, polyether-modified dimethyl silicone oil, methylstyryl-modified dimethyl silicone oil, alkyl-modified dimethyl silicone oil, higher fatty acid ester-modified dimethyl silicone oil, and fluorine-modified dimethyl silicone oil. These silicone oils may be used in combination.

[0049] From the viewpoint of improving the bending elongation at break or the tensile elongation at break, the viscosity of the silicone oil at 25°C is preferably 1 to 1,200,000 cSt, more preferably 5 to 100,000 cSt, even more preferably 10 to 50,000 cSt, still more preferably 20 to 25,000 cSt, still more preferably 30 to 15,000 cSt, still more preferably 50 to 1,000 cSt, and still more preferably 100 to 500 cSt. In the present invention, the viscosity of the silicone oil refers to the kinematic viscosity measured by a method in accordance with JIS K 2283.

[0050] In the thermoplastic resin composition of one embodiment of the present invention, the amount of silicone oil blended is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 7 parts by mass, even more preferably 0.4 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass. By blending the amount of silicone oil within the above range, the flexural elongation at break or tensile elongation at break of the thermoplastic resin composition is further improved, and the toughness is further improved.

[0051] <<Antioxidant>> In the thermoplastic resin composition of one embodiment of the present invention, the styrene-based resin composition preferably further contains an antioxidant from the viewpoint of durability. The antioxidant is preferably at least one selected from a phenol-based compound (phenol-based antioxidant), a phosphorus-based compound (phosphorus-based antioxidant), and a sulfur-based compound (sulfur-based antioxidant), and from the viewpoint of heat resistance, a phenol-based compound (phenol-based antioxidant) is more preferred.

[0052] Specific examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,6-diphenyl-4-methoxyphenol, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, and 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane. ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate], 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-3-(n-dodecylthio)-butane, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid dioctadecyl ester, n-octadecyl-3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, pentaerythritol tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, and the like. In particular, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is preferred.

[0053] Examples of the phosphorus-based antioxidant include monophosphites and diphosphites such as 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(2,4-di-tert-butylphenyl)phosphite, and tris(mono- and di-nonylphenyl)phosphite.

[0054] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], di(tridecyl) 3,3'-thiodipropionate, and 3,3'-thiodipropionate.

[0055] In the thermoplastic resin composition of one embodiment of the present invention, the blending amount of the antioxidant is preferably 0.05 to 2.0 parts by mass, more preferably 0.1 to 1.8 parts by mass, even more preferably 0.3 to 1.5 parts by mass, and still more preferably 0.5 to 1.2 parts by mass, per 100 parts by mass of (A) SPS. When the blending amount of the antioxidant is within this range, the durability of the thermoplastic resin is further improved, the heat discoloration resistance during processing is good, bleeding of the antioxidant is suppressed, and no adverse effects on the appearance are caused.

[0056] <Glass Fiber> The thermoplastic resin composition of one embodiment of the present invention preferably further contains glass fiber. By containing glass fiber, the flexural elongation at break or tensile elongation at break of the thermoplastic resin composition is further improved, and the toughness is further improved.

[0057] In the present invention, the glass fiber may be a glass fiber having a circular cross section or a glass fiber having a flat cross section. Among these, from the viewpoint of suppressing a decrease in the tensile modulus of the thermoplastic resin composition and ensuring flowability, a glass fiber having a circular cross section is preferred. In addition, a glass fiber having a circular cross section is preferred because it has no anisotropy derived from the cross-sectional direction of the glass fiber in a direction perpendicular to the direction of resin flow in the obtained molded product, and therefore has little variation in physical properties.

[0058] In this specification, glass fibers having a flat cross section refer to glass fibers whose cross section perpendicular to the fiber axis is flat. The flat shape refers to a shape in which the modification ratio of glass fibers having a flat cross section is greater than 1. In this specification, the modification ratio is the ratio of the major axis to the minor axis, where the length of the long side of a rectangle having the smallest area circumscribing the cross section perpendicular to the longitudinal direction of the glass fiber is the major axis and the length of the short side of this rectangle is the minor axis. When glass fibers having a flat cross section are used, the modification ratio of the glass fibers having a flat cross section is preferably 2.0 to 6.0, more preferably 3.0 to 5.0, and even more preferably 3.5 to 4.5, from the viewpoints of suppressing a decrease in the tensile modulus of the thermoplastic resin composition and ensuring flowability. The minor axis is preferably 3 to 10 μm, more preferably 5 to 8 μm.

[0059] The fiber diameter of the glass fiber is preferably 8 to 20 μm, more preferably 9 to 15 μm, and even more preferably 10 to 12 μm. When the fiber diameter of the glass fiber is 8 μm or more, the bending elongation at break or tensile elongation at break of the thermoplastic resin composition is further improved, and when the fiber diameter is 20 μm or less, the flowability of the thermoplastic resin composition when used in molding or the like is ensured. In the present invention, the fiber diameter of the glass fiber means, in the case of a glass fiber having a circular cross section, the diameter of a circle in a cross section perpendicular to the fiber axis. In the case of a glass fiber having a flat cross section, the diameter means the diameter of a circle having the same area as the area of ​​the cross section perpendicular to the fiber axis.

[0060] The fiber length of the glass fiber is preferably 1 to 30 mm, more preferably 1.5 to 10 mm, and even more preferably 2 to 5 mm, from the viewpoint of ensuring the fluidity and handling of the thermoplastic resin composition when used in molding, etc. Furthermore, the fiber length of the glass fiber contained in the thermoplastic resin composition is preferably 200 to 600 μm due to breakage during extrusion kneading, etc.

[0061] In order to enhance adhesion to the (A) SPS, the glass fiber is preferably surface-treated with a coupling agent, more preferably with a silane-based coupling agent or a titanium-based coupling agent, and even more preferably with a silane-based coupling agent from the viewpoint of compatibility with the resin component.

[0062] Specific examples of silane coupling agents include triethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(1,1-epoxycyclohexyl)ethyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane. Examples of suitable silanes include hydroxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltris(2-methoxyethoxy)silane, N-methyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-4,5-dihydroimidazolepropyltriethoxysilane, hexamethyldisilazane, N,N-bis(trimethylsilyl)urea, and 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine. Among these, aminosilanes and epoxysilanes such as γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferred.

[0063] Specific examples of titanium-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(1,1-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, and bis(dioctyl pyrophosphate)oxyacetate. titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate)titanate, isopropyl tricumyl phenyl titanate, isopropyl tri(N-amidoethyl, aminoethyl)titanate, dicumyl phenyloxyacetate titanate, diisostearoyl ethylene titanate, etc. Among these, isopropyl tri(N-amidoethyl, aminoethyl)titanate is preferred.

[0064] When the thermoplastic resin composition of one embodiment of the present invention contains glass fibers, the content of the glass fibers in the thermoplastic resin composition is preferably 5 to 50 mass%, more preferably 10 to 45 mass%, and even more preferably 25 to 40 mass%, of the total of the styrene-based resin composition and the glass fibers. A glass fiber content of 5 mass% or more further improves the mechanical strength of the thermoplastic resin composition, while a glass fiber content of 50 mass% or less ensures the flowability of the thermoplastic resin composition when used in molding, etc.

[0065] [Method for producing thermoplastic resin composition] The method for producing a thermoplastic resin composition of the present invention is a method for producing a thermoplastic resin composition containing a styrene-based resin composition, and includes a step of melt-kneading (A) a styrene-based polymer having a syndiotactic structure, (B) a functional group-containing polyphenylene ether, and (C) a metal compound to obtain the styrene-based resin composition, wherein the functional group of the (B) functional group-containing polyphenylene ether is a functional group derived from an acid and / or a derivative thereof, the blending amount of the (B) functional group-containing polyphenylene ether is 0.1 to 150 parts by mass relative to 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure, and the blending amount of the (C) metal compound is 0.001 to 10 parts by mass relative to 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure.

[0066] The melt-kneading method can be carried out by premixing using a commonly used device such as a ribbon blender, a drum tumbler, or a Henschel mixer, followed by using a Banbury mixer, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a co-kneader, or the like.

[0067] In the step of obtaining the styrene-based resin composition, it is preferable to dry-blend the raw materials (A) styrene-based polymer having a syndiotactic structure, (B) functional group-containing polyphenylene ether, (C) metal compound, and other components before melt-kneading them. The (C) metal compound may be dissolved in a solvent such as water or alcohol and then mixed. In the step of obtaining the styrene-based resin composition, the (C) metal compound may be dry-blended with the (A) styrene-based polymer having a syndiotactic structure, (B) functional group-containing polyphenylene ether, and other compounds, as described above, and then fed together with glass fibers. When the (C) metal compound and glass fibers are fed together, the (C) metal compound and glass fibers may be mixed, and then the mixture of the (C) metal compound and glass fibers may be fed by a side feed during the melt-kneading of the raw materials (A) styrene-based polymer having a syndiotactic structure, (B) functional group-containing polyphenylene ether, and other components. Furthermore, when the (C) metal compound and the glass fibers are supplied together, the mixture of the (C) metal compound and the glass fibers may be obtained by dry blending the (C) metal compound and the glass fibers, or by dissolving the (C) metal compound in a small amount of water or alcohol and mixing it with the glass fibers, or by spraying the (C) metal compound dissolved in a small amount of water or alcohol onto the glass fibers.

[0068] In the production method of one embodiment of the present invention, the (A) styrene-based polymer having a syndiotactic structure, the (B) functional group-containing polyphenylene ether, and the (C) metal compound are the same as those in the thermoplastic resin composition of the present invention described above. Furthermore, in the production method of one embodiment of the present invention, in addition to the above components, the styrene-based resin composition may contain any other components shown in the thermoplastic resin composition of the present invention described above, as long as the object of the present invention is not impaired. In particular, among the other components, the crystal nucleating agent, rubber-like elastomer, and silicone oil are the same as those in the thermoplastic resin composition of the present invention described above.

[0069] In addition, in the production method of one aspect of the present invention, it is preferable that glass fibers are further blended in the step of obtaining the styrene-based resin composition. By blending glass fibers, the flexural elongation at break or tensile elongation at break of the obtained thermoplastic resin composition is further improved, and the toughness is further improved. In the production method of one aspect of the present invention, the embodiment of the glass fibers is the same as that of the thermoplastic resin composition of the present invention described above.

[0070] In the production method of one embodiment of the present invention, the glass fibers may be supplied together with the raw materials (A) styrene-based polymer having a syndiotactic structure, (B) functional group-containing polyphenylene ether, (C) metal compound, and other components, or by side feeding during melt-kneading of the raw materials (A) styrene-based polymer having a syndiotactic structure, (B) functional group-containing polyphenylene ether, (C) metal compound, and other components, and side feeding is preferred from the viewpoint of productivity. Furthermore, when the (C) metal compound and the glass fibers are supplied together, after mixing the (C) metal compound and the glass fibers, a mixture of the (C) metal compound and the glass fibers may be supplied by side feeding during melt-kneading of the raw materials (A) styrene-based polymer having a syndiotactic structure, (B) functional group-containing polyphenylene ether, and other components.

[0071] In the production method of one aspect of the present invention, when glass fibers are blended in the step of obtaining the styrene-based resin composition, the blending amount of the glass fibers is preferably 5 to 50 mass %, more preferably 10 to 45 mass %, and even more preferably 25 to 40 mass %, of the total of the styrene-based resin composition and the glass fibers, similar to the above-described thermoplastic resin composition of the present invention.

[0072] The present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples.

[0073] The raw materials used in the examples and comparative examples are as follows. <(A) SPS> Syndiotactic polystyrene resin, weight average molecular weight: 180,000, MFR (temperature 300°C, load 1.2 kgf): 13 g / 10 min, manufactured by Idemitsu Kosan Co., Ltd. <(B) Functional group-containing polyphenylene ether> FAPPE-1 (produced by the method of Production Example 1): fumaric acid-modified polyphenylene ether, modification rate: 1.45 mass% <(C) Metal compounds> Mg stearate: "magnesium stearate" (manufactured by Kanto Chemical Co., Ltd.) Potassium stearate: "potassium stearate" (manufactured by Kanto Chemical Co., Ltd.) Potassium acetate: "potassium acetate" (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) Zn acetate: "zinc acetate" (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) Potassium carbonate: "potassium carbonate" (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) <Crystal nucleating agent> NA-70: "ADK STAB NA-70", lithium [2,2'-methylenebis(4,6-di-tert-butylphenyl)] phosphate, manufactured by ADEKA Corporation <Rubber-like elastomer> SEPTON 8006: hydrogenated styrene-butadiene-styrene block copolymer, styrene content 33 wt%, manufactured by Kuraray Co., Ltd. <Silicone oil> SH200-350: "DOWSIL SH 200 Fluid 350 cSt", dimethyl silicone oil, viscosity at 25°C: 350 cSt, manufactured by Dow-Toray Industries, Inc. <Antioxidant> Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Japan Ltd. <Glass fiber> T-330H: "ECS03T-330H", average fiber diameter 10.5 μm, average fiber length 3 mm, irregularity ratio = 1, manufactured by Nippon Electric Glass Co., Ltd.

[0074] Production Example 1 (Production of FAPPE-1 (fumaric acid-modified polyphenylene ether)) 1 kg of polyphenylene ether (poly(2,6-dimethyl-1,4-phenylene ether), intrinsic viscosity 0.45 dL / g in chloroform, 25°C), 30 g of fumaric acid, and 20 g of 2,3-dimethyl-2,3-diphenylbutane (NOFMER BC, NOFAM, NOFAM) as a radical generator were dry-blended, and the mixture was melt-kneaded using a 30 mm twin-screw extruder at a screw rotation speed of 200 rpm and a set temperature of 300°C. The resin temperature at this time was approximately 331°C. The strand was water-cooled and pelletized to obtain FAPPE-1. To measure the modification rate, 1 g of the resulting FAPPE-1 was dissolved in ethylbenzene and reprecipitated in methanol. The recovered polymer was subjected to Soxhlet extraction with methanol, dried, and the modification rate was determined from the carbonyl absorption intensity in the IR spectrum and by titration. At this time, the modification rate was 1.45% by weight.

[0075] Examples 1-1 to 1-7 and Comparative Example 1-1 (Production of Thermoplastic Resin Composition) The raw materials were dry-blended in the proportions shown in Table 1. The dry-blended raw materials were supplied to a twin-screw kneader (Process 11, manufactured by Thermo Fisher Scientific) and melt-kneaded at a screw rotation speed of 200 rpm and a set temperature of 300°C to obtain thermoplastic resin pellets. Note that Comparative Example 1-1 is a comparative example that does not contain a metal compound.

[0076] (Evaluation) <MFR> Using pellets of the obtained thermoplastic resin composition, measurements were made at a temperature of 300°C and a load of 2.16 kgf in accordance with JIS K7210-1:2014. <Flexural Modulus and Bending Strain at Break> The obtained pellets of the thermoplastic resin composition were injection molded using an injection molding machine (MiniJetPro, manufactured by Thermo Fisher Scientific) at a cylinder temperature of 300°C and a mold temperature of 150°C to obtain test specimens. The test specimens were dumbbell-shaped and 4 mm thick in accordance with ISO 527-2-1BA. Using the test specimens, a three-point bending test was performed at room temperature under conditions of a bending speed of 1 mm / min and a support span of 35 mm to measure the flexural modulus and bending strain at break. The measurement results are shown in Table 1. An improvement in melt viscosity (a decrease in MFR) was observed due to the addition of the metal compound, suggesting that ionomerization occurred.

[0077]

[0078] Examples 2-1 to 2-2 (Production of Thermoplastic Resin Composition) Each raw material except the (C) metal compound and glass fiber was blended in the proportions shown in Table 2 and dry-blended using a Henschel mixer. Furthermore, the (C) metal compound and glass fiber shown in Table 2 were mixed together so that the blending amount of the (C) metal compound in the styrene-based resin composition was the proportion shown in Table 2, thereby obtaining a mixture of the (C) metal compound and glass fiber. The dry-blended raw materials were fed into a twin-screw extruder ("TEM37SS," manufactured by Shibaura Machine Co., Ltd.) at a screw rotation speed of 250 rpm and a cylinder temperature of 290°C, and melt-kneaded while side-feeding the mixture of the (C) metal compound and glass fiber so that the glass fiber content was the proportion shown in Table 2. The resulting strand was water-cooled and pelletized to obtain pellets of the thermoplastic resin composition. The obtained thermoplastic resin composition pellets were dried at 120°C for 5 hours using a hot air dryer and used for evaluation. In Examples 2-1 to 2-2, the (C) metal compound was side-fed together with the glass fiber.

[0079] Example 2-3 (Production of Thermoplastic Resin Composition) Each raw material (including (C) a metal compound) other than glass fiber was blended in the proportions shown in Table 2 and dry-blended in a Henschel mixer. The dry-blended raw materials were fed into a twin-screw extruder ("TEM37SS", manufactured by Shibaura Machine Co., Ltd.) and melt-kneaded at a screw rotation speed of 250 rpm and a cylinder temperature of 290°C while side-feeding glass fiber so that the glass fiber content was in the proportion shown in Table 2. The resulting strand was water-cooled and pelletized to obtain pellets of a thermoplastic resin composition. The obtained thermoplastic resin composition pellets were dried at 120°C for 5 hours using a hot air dryer and used for evaluation. Note that Example 2-3 is an example in which (C) a metal compound was dry-blended with a raw material for a styrene-based resin composition such as SPS and then fed.

[0080] Comparative Example 2-1 (Production of Thermoplastic Resin Composition) The raw materials other than glass fiber were blended in the proportions shown in Table 2 and dry-blended in a Henschel mixer. The dry-blended raw materials were fed into a twin-screw extruder ("TEM37SS", manufactured by Shibaura Machine Co., Ltd.) and melt-kneaded at a screw rotation speed of 250 rpm and a cylinder temperature of 290°C while side-feeding glass fiber so that the glass fiber content was in the proportion shown in Table 2. The resulting strand was water-cooled and pelletized to obtain pellets of the thermoplastic resin composition. The obtained thermoplastic resin composition pellets were dried at 120°C for 5 hours using a hot air dryer and used for evaluation. Note that Comparative Example 2-1 is a comparative example that does not contain (C) the metal compound.

[0081] (Evaluation) <MFR> Using pellets of the obtained thermoplastic resin composition, measurements were performed in accordance with JIS K7210:1999 at a temperature of 300°C and a load of 2.16 kgf. <Tensile Modulus, Tensile Strength, and Tensile Elongation at Break> Using pellets of the obtained thermoplastic resin composition, a dumbbell-shaped tensile test piece (Type A) was molded in accordance with JIS K 7139:2015 using an injection molding machine [SE100EV manufactured by Sumitomo Heavy Industries, Ltd.] at a cylinder temperature of 290°C and a mold temperature of 150°C. Using the test piece, the tensile modulus, tensile strength, and tensile elongation at break were measured in accordance with ISO 527-1,2:2012 at a tension speed of 5 mm / min and a measurement temperature of 23°C. The measurement results are shown in Table 2.

[0082]

[0083] Examples 3-1 to 3-3 (Production of Thermoplastic Resin Compositions) Each raw material except for the (C) metal oxide and glass fiber was blended in the proportions shown in Table 3 and dry-blended in a Henschel mixer. Furthermore, the metal compound shown in Table 3 was mixed with glass fiber so that the blending amount of the (C) metal compound in the styrene-based resin composition was the proportion shown in Table 3, thereby obtaining a mixture of the (C) metal compound and glass fiber. The dry-blended raw materials were fed into a twin-screw extruder ("TEM37SS," manufactured by Shibaura Machine Co., Ltd.) and melt-kneaded at a screw rotation speed of 250 rpm and a cylinder temperature of 290°C while side-feeding the mixture of the (C) metal compound and glass fiber so that the glass fiber content was the proportion shown in Table 3. The resulting strand was water-cooled and pelletized to obtain pellets of the thermoplastic resin composition. The resulting thermoplastic resin composition pellets were dried for 5 hours at 120°C using a hot air dryer and used for evaluation.

[0084] Comparative Examples 3-1 to 3-3 (Production of Thermoplastic Resin Composition) The raw materials other than glass fiber were blended in the proportions shown in Table 3 and dry-blended in a Henschel mixer. The dry-blended raw materials were fed into a twin-screw extruder ("TEM37SS", manufactured by Shibaura Machine Co., Ltd.) and melt-kneaded at a screw rotation speed of 250 rpm and a cylinder temperature of 290°C while side-feeding glass fiber so that the glass fiber content was in the proportion shown in Table 3. The resulting strands were water-cooled and pelletized to obtain pellets of the thermoplastic resin composition. The obtained thermoplastic resin composition pellets were dried at 120°C for 5 hours using a hot air dryer and used for evaluation. Note that Comparative Examples 3-1 to 3-3 are comparative examples that do not contain (C) the metal compound.

[0085] (Evaluation) <Tensile Modulus, Tensile Strength, and Tensile Elongation at Break> Using pellets of the obtained thermoplastic resin composition, a dumbbell-shaped tensile test piece (Type A) was molded in accordance with JIS K 7139:2015 using an injection molding machine [SE100EV manufactured by Sumitomo Heavy Industries, Ltd.] at a cylinder temperature of 290°C and a mold temperature of 150°C. Using the test piece, the tensile modulus, tensile strength, and tensile elongation at break were measured in accordance with ISO 527-1,2:2012 at a tension speed of 5 mm / min and a measurement temperature of 23°C. The measurement results are shown in Table 3. <Flexural Modulus and Flexural Strength> Using the test piece obtained under the above molding conditions, the flexural modulus and flexural strength were measured in accordance with ISO 178:2010 at a temperature of 23°C and a bending speed of 2 mm / min. The measurement results are shown in Table 3.

[0086]

[0087] From the results in Tables 1 to 3, it is clear that the thermoplastic resin composition of the present invention has improved flexural elongation at break or tensile elongation at break and is excellent in toughness.

Claims

1. A thermoplastic resin composition comprising a styrene-based resin composition, wherein the styrene-based resin composition is obtained by melt-kneading (A) a styrene-based polymer having a syndiotactic structure, (B) a functional group-containing polyphenylene ether, and (C) a metal compound, wherein the functional group of the (B) functional group-containing polyphenylene ether is a functional group derived from an acid and / or a derivative thereof, the blending amount of the (B) functional group-containing polyphenylene ether is 0.1 to 150 parts by mass per 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure, and the blending amount of the (C) metal compound is 0.001 to 10 parts by mass per 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure.

2. The thermoplastic resin composition according to claim 1, wherein the functional groups of the functional group-containing polyphenylene ether (B) derived from an acid and / or a derivative thereof are at least one selected from maleic anhydride, maleic acid, fumaric acid, maleic acid esters, fumaric acid esters, maleate salts, fumarate salts, acrylic acid, acrylic acid esters, acrylic acid amides, acrylic acid salts, methacrylic acid, methacrylic acid esters, methacrylic acid amides, methacrylate salts, and glycidyl methacrylate.

3. The thermoplastic resin composition according to claim 1 or 2, wherein the metal compound (C) is at least one selected from the group consisting of metal salts, metal oxides, metal hydroxides, and metal complexes.

4. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the metal compound (C) is a metal salt.

5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the metal compound (C) is at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, and transition metal salts.

6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the styrene-based resin composition further contains a nucleating agent, and the amount of the nucleating agent is 0.1 to 3 parts by mass per 100 parts by mass of the styrene-based polymer (A) having a syndiotactic structure.

7. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the styrene-based resin composition further contains a rubber-like elastomer, and the amount of the rubber-like elastomer contained is 5 to 25 parts by mass per 100 parts by mass of the styrene-based polymer (A) having a syndiotactic structure.

8. The thermoplastic resin composition according to any one of claims 1 to 7, wherein the styrene-based resin composition further contains a silicone oil, and the amount of the silicone oil contained is 0.1 to 10 parts by mass per 100 parts by mass of the styrene-based polymer (A) having a syndiotactic structure.

9. The thermoplastic resin composition according to any one of claims 1 to 8, further comprising glass fibers.

10. The thermoplastic resin composition according to claim 9, wherein the content of the glass fiber is 5 to 50 mass % of the total of the styrene-based resin composition and the glass fiber.

11. A method for producing a thermoplastic resin composition containing a styrene-based resin composition, comprising: a step of melt-kneading (A) a styrene-based polymer having a syndiotactic structure, (B) a functional group-containing polyphenylene ether, and (C) a metal compound to obtain the styrene-based resin composition, wherein the functional group of the (B) functional group-containing polyphenylene ether is a functional group derived from an acid and / or a derivative thereof, the blending amount of the (B) functional group-containing polyphenylene ether is 0.1 to 150 parts by mass per 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure, and the blending amount of the (C) metal compound is 0.001 to 10 parts by mass per 100 parts by mass of the (A) styrene-based polymer having a syndiotactic structure.

12. The method for producing a thermoplastic resin composition according to claim 11, wherein glass fibers are further blended in the step of obtaining the styrene-based resin composition.

13. The method for producing a thermoplastic resin composition according to claim 12, wherein the blending amount of the glass fiber is 5 to 50 mass % of the total of the styrene-based resin composition and the glass fiber.

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