Thermoplastic resin composition

Abstract

This thermoplastic resin composition includes a thermoplastic resin (A), a polyarylene ether (B) modified with a functional group, a coupling agent (C), and a carbon fiber (D).

Description

[Technical field]

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

[0002] In recent years, particularly in the field of automobiles, efforts have been made to improve fuel efficiency by reducing the weight of automobiles. For example, there has been a growing trend to replace conventional metal structural components with fiber-reinforced plastics, and fiber-reinforced plastics with superior strength are in demand. In particular, research is being conducted toward the practical application of carbon fiber composite materials (carbon fiber reinforced thermoplastic resin, hereafter sometimes abbreviated as CFRTP) that use a thermoplastic resin as a matrix, due to their ease of molding and recycling.

[0003] Patent Document 1 discloses a resin composition in which impact strength is increased by adding carbon fiber and an organic carboxylate magnesium salt to a resin component consisting of a polyphenylene ether resin and an aromatic vinyl resin.

[0004] Patent Document 2 discloses a resin composition having excellent mechanical strength and the like, which is obtained by mixing polyamide 6 with carbon fiber, a silane coupling agent, and a thermoplastic elastomer.

[0005] Patent Document 3 discloses a flame-retardant aromatic polycarbonate resin composition in which inorganic compound particles and a specific metal salt are added to an aromatic polycarbonate to remarkably improve the drip prevention effect of combustion products.

[0006] Patent Document 4 discloses that a thermoplastic resin composition containing a styrene-based resin having a syndiotactic structure and a styrene-based resin composition containing a glass filler can achieve both excellent hot water resistance, mold releasability, and low gas generation.

[0007] Patent Document 5 discloses that a resin composition containing a polystyrene resin having a syndiotactic structure, a polyamide, a compatibilizer, a specific hindered phenol compound, and an inorganic filler, and containing the polystyrene resin having a syndiotactic structure and the specific hindered phenol compound in a specific ratio, has excellent mechanical properties and excellent long-term heat resistance, such as high tensile strength retention and high tensile elongation retention. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 6-287438 [Patent Document 2] JP 2016-141809 A [Patent Document 3] JP 2004-10825 A [Patent Document 4] WO2019 / 107526 [Patent Document 5] JP 2020-105365 A Summary of the Invention

[0009] CFRTP requires further mechanical strength in order to be used in various applications. For example, in automobiles and aircraft used outdoors, where they are used for long periods in high temperature and high humidity environments, they are required to maintain their mechanical strength for a long period of time. An object of the present invention is to provide a thermoplastic resin composition having high mechanical strength and excellent resistance to moist heat.

[0010] According to the present invention, the following thermoplastic resin composition and the like are provided. 1. A thermoplastic resin composition comprising a thermoplastic resin (A), a polyarylene ether modified with a functional group (B), a coupling agent (C), and carbon fibers (D). 2. The thermoplastic resin composition according to 1, wherein the thermoplastic resin (A) comprises syndiotactic polystyrene. 3. The thermoplastic resin composition according to 1 or 2, wherein the coupling agent (C) comprises one or more selected from the group consisting of silane coupling agents, aluminate coupling agents, and titanate coupling agents. 4. The thermoplastic resin composition according to any one of 1 to 3, wherein the coupling agent (C) contains an isocyanate-based silane. 5. The thermoplastic resin composition according to any one of 1 to 4, further comprising a sizing agent (E). 6. The thermoplastic resin composition according to 5, wherein the sizing agent (E) has an epoxy group. 7. The thermoplastic resin composition according to any one of 1 to 6, wherein the polyarylene ether (B) modified with a functional group is a dicarboxylic acid-modified polyarylene ether. 8. The thermoplastic resin composition according to 7, wherein the dicarboxylic acid-modified polyarylene ether is a fumaric acid-modified polyarylene ether or a maleic anhydride-modified polyarylene ether. 9. A molded article made of the thermoplastic resin composition according to any one of 1 to 8. 10. The molded article according to 9, which has a strength retention rate of 80% or more after wet heat treatment at 120°C for 500 hours, as represented by the following formula (1):

number

[0011] According to the present invention, it is possible to provide a thermoplastic resin composition having high mechanical strength and excellent resistance to moist heat. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] [Thermoplastic resin composition] A thermoplastic resin composition according to one embodiment of the present invention includes a thermoplastic resin (A), a polyarylene ether modified with a functional group (B), a coupling agent (C), and carbon fibers (D). The combination of the components (A) to (D) improves the mechanical strength and enhances the moist heat resistance. The components of this embodiment will be described below.

[0013] <Thermoplastic resin (A)> The thermoplastic resin (A) used for the production of the thermoplastic resin composition according to one embodiment of the present invention is not particularly limited as long as it is a thermoplastic resin other than the polyarylene ether (B) modified with a functional group described below, and specifically includes polyamide resin, acrylic resin, polyphenylene sulfide resin, polyvinyl chloride resin, polystyrene resin, polyolefin, polyacetal resin, polycarbonate resin, polyurethane, polybutylene terephthalate, acrylonitrile butadiene styrene (ABS) resin, modified polyphenylene ether resin, phenoxy resin, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, aromatic polyester, epoxy resin, etc. Among them, at least one selected from the group consisting of polycarbonate resin, polystyrene resin, polyamide, and polyolefin is preferable, and polyamide resin, polyphenylene sulfide resin, polycarbonate resin, or polystyrene resin is more preferable. According to one embodiment of the present invention, the thermoplastic resin (A) is polyphenylene sulfide resin, polystyrene resin, or polyamide resin.

[0014] The polystyrene resin is not particularly limited, but examples thereof include homopolymers of styrene compounds, copolymers of two or more styrene compounds, and rubber-modified polystyrene resins (high impact polystyrene) in which rubber-like polymers are dispersed in particulate form in a matrix made of a polymer of a styrene compound. Examples of styrene compounds as raw materials include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, and p-tert-butylstyrene.

[0015] The polystyrene resin may be a copolymer obtained by using two or more styrene compounds in combination, but among them, polystyrene obtained by polymerizing styrene alone is preferable. For example, polystyrenes having stereoregular structures such as atactic polystyrene, isotactic polystyrene, and syndiotactic polystyrene can be mentioned. As the thermoplastic resin (A) contained in the resin composition of the present invention, syndiotactic polystyrene is preferable.

[0016] The syndiotactic polystyrene used in the production of the thermoplastic resin composition according to one embodiment of the present invention means a styrene-based resin having a high degree of syndiotactic structure (hereinafter, sometimes abbreviated as SPS). In this specification, "syndiotactic" means that the proportion of phenyl rings in adjacent styrene units that are alternately arranged with respect to the plane formed by the main chain of the polymer block (hereinafter, referred to as syndiotacticity) is high. Tacticity is a method to measure the molecular dynamics of the nucleus by using isotope carbon ( 13 Quantitative identification can be performed using the C-NMR method. 13 By C-NMR, the proportion of consecutive multiple 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.

[0017] The term "styrene-based resin having a high degree of syndiotactic structure" refers to polystyrene, poly(hydrocarbon-substituted styrene), poly(halogenated styrene), poly(halogenated alkylstyrene), poly(alkoxystyrene), poly(vinyl benzoate), hydrogenated polymers or mixtures thereof, or copolymers having these as main components, each of which has a syndiotacticity of usually 75 mol % or more, preferably 85 mol % or more in racemic diad (r), or usually 30 mol % or more, preferably 50 mol % or more in racemic pentad (rrrr).

[0018] Examples of poly(hydrocarbon-substituted styrenes) include poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(tert-butylstyrene), poly(phenyl)styrene, 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).

[0019] Particularly preferred of the above styrene-based polymers are polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), poly(m-chlorostyrene), and poly(p-fluorostyrene). Further examples include a copolymer of styrene and p-methylstyrene, a copolymer of styrene and p-tert-butylstyrene, and a copolymer of styrene and divinylbenzene.

[0020] The molecular weight of the syndiotactic polystyrene is not particularly limited. However, from the viewpoint of the fluidity of the resin during molding and the mechanical properties of the obtained molded article, a weight average molecular weight of 1×10 4 More than 1×10 6The weight average molecular weight is preferably 1×10 or less, more preferably 50,000 or more and 500,000 or less, and even more preferably 50,000 or more and 300,000 or less. 4 If the weight average molecular weight is 1×10 or more, a molded product having sufficient mechanical properties can be obtained. 6 If it is below this value, there will be no problem with the flowability of the resin during molding. When the MFR of syndiotactic polystyrene is measured under conditions of a temperature of 300° C. and a load of 1.2 kgf, the MFR is preferably 2 g / 10 min or more, and more preferably 4 g / 10 min or more, and within this range, there is no problem with the fluidity of the resin during molding. If the MFR is 50 g / 10 min or less, preferably 40 g / min or less, and more preferably 30 g / min or less, a molded product having sufficient mechanical properties can be obtained.

[0021] Syndiotactic polystyrene can be produced, for example, by polymerizing styrene monomer in an inert hydrocarbon solvent or in the absence of a solvent using a titanium compound and a condensation product of water and trialkylaluminum (aluminoxane) as a catalyst (for example, JP 2009-068022 A, WO 2019 / 107525 A1).

[0022] The content of the thermoplastic resin (A) in the resin components contained in the thermoplastic resin composition is preferably from 80 to 97% by mass, and more preferably from 85 to 95% by mass. By setting the content of the thermoplastic resin (A) within the above range, the effects of excellent heat resistance, low water absorbency, and moldability can be obtained. In this specification, the resin components contained in the thermoplastic resin composition refer to the thermoplastic resin (A) and the polyarylene ether modified with a functional group (B).

[0023] <Polyarylene ether modified with functional groups (B)> The functional group-modified polyarylene ether used in the production of the thermoplastic resin composition according to one embodiment of the present invention can be obtained, for example, by reacting a polyarylene ether with a modifying agent.

[0024] There are no particular limitations on the polyarylene ether used as a raw material for the functional group-modified polyarylene ether used in the production of the thermoplastic resin composition according to one embodiment of the present invention. Examples of polyarylene ethers include 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-phenyl-1,4-phenylene ether), poly(2-chloro-1,4-phenylene ether), 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), poly(2,6-dimethyl-1,4-phenylene ether), and the like. Alternatively, the polymers and copolymers described in U.S. Patent Nos. 3,306,874, 3,306,875, 3,257,357 and 3,257,358 are also suitable. Further examples include graft copolymers and block copolymers of vinyl aromatic compounds such as polystyrene and the above-mentioned polyphenylene ethers. Among these, poly(2,6-dimethyl-1,4-phenylene ether) is particularly preferably used.

[0025] The degree of polymerization of the polyarylene ether is not particularly limited and can be appropriately selected depending on the purpose of use, and can usually be selected from the range of 60 to 400. If the degree of polymerization is 60 or more, the strength of the thermoplastic resin composition containing the functional group-modified polyarylene ether can be improved, as described in detail later. If the degree of polymerization is 400 or less, good moldability can be maintained.

[0026] Examples of the modifier for modifying the polyarylene ether include an acid modifier, an amino group-containing modifier, a phosphorus compound, a hydroxyl group-containing modifier, a halogen-containing modifier, an epoxy group-containing modifier, an unsaturated hydrocarbon group-containing modifier, etc. Examples of the acid modifier include dicarboxylic acids and their derivatives.

[0027] Examples of dicarboxylic acids used as modifiers include maleic anhydride and its derivatives, and fumaric acid and its derivatives. Derivatives of maleic anhydride are compounds having an ethylenic double bond and a polar group such as a carboxyl group or an acid anhydride group in the same molecule. Specific examples include maleic acid, maleic acid monoesters, maleic acid diesters, maleimides and their N-substituted derivatives (e.g., N-substituted maleimides, maleic acid monoamides, maleic acid diamides, etc.), ammonium salts of maleic acid, metal salts of maleic acid, acrylic acid, methacrylic acid, methacrylic acid esters, and glycidyl methacrylate. Specific examples of fumaric acid derivatives include fumaric acid diesters, fumaric acid metal salts, ammonium fumaric acid salts, and fumaric acid halides. Among these, fumaric acid or maleic anhydride is particularly preferably used.

[0028] The polyarylene ether modified with a functional group is preferably a dicarboxylic acid modified polyarylene ether, more preferably a fumaric acid modified polyarylene ether or a maleic acid modified polyarylene ether.Specific examples include modified polyphenylene ether-based polymers such as (styrene-maleic anhydride)-polyphenylene ether-graft polymer, maleic anhydride modified polyphenylene ether, fumaric acid modified polyphenylene ether, glycidyl methacrylate modified polyphenylene ether, and amine modified polyphenylene ether.Modified polyphenylene ether is preferred, maleic anhydride modified polyphenylene ether or fumaric acid modified polyphenylene ether is more preferred, and fumaric acid modified polyphenylene ether is particularly preferred.

[0029] The degree of modification (degree of modification or amount of modification) of the polyarylene ether modified with a functional group can be determined by infrared (IR) absorption spectroscopy or titration. When the degree of modification is determined by infrared (IR) absorption spectroscopy, it can be determined from the intensity ratio of the peak intensity showing the absorption of the compound used as a modifier to the peak intensity showing the absorption of the corresponding polyarylene ether. For example, in the case of fumaric acid-modified polyphenylene ether, the peak intensity at 1790 cm showing the absorption of fumaric acid is -1 Peak intensity (I A ) and polyphenylene ether (PPE) absorption at 1704 cm -1 The ratio of peak intensities (I B ) is calculated using the following formula: Degree of denaturation = (I A ) / (I B ) The degree of modification of the polyarylene ether modified with a functional group is preferably 0.05-20.

[0030] When the modification amount is determined by titration, it can be determined as an acid content from the neutralization titration amount measured in accordance with JIS K 0070-1992. ofThe modification amount is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, further preferably 1.0 to 10% by mass, and particularly preferably 1.0 to 5.0% by mass, based on the mass.

[0031] The polyarylene ether modified with a functional group can be prepared by reacting the above-mentioned polyarylene ether with a modifying agent in the presence or absence of a radical generator, optionally in the presence of a solvent or other resin. As the modification method, solution modification or melt modification is known.

[0032] When the above-mentioned fumaric acid or a derivative thereof is used as a modifier, polyarylene ether and fumaric acid or a derivative thereof are reacted in the presence or absence of a radical generator, optionally in the presence of an aromatic hydrocarbon solvent and other resin, to obtain a fumaric acid-modified polyarylene ether. The aromatic hydrocarbon solvent is not particularly limited as long as it dissolves polyarylene ether, fumaric acid or a derivative thereof, and the optionally used radical generator, and is inactive against the generated radicals. Specifically, for example, benzene, toluene, ethylbenzene, xylene, chlorobenzene, tert-butylbenzene, etc. can be mentioned as suitable solvents. Among them, it is preferable to use benzene, toluene, chlorobenzene, and tert-butylbenzene, which have small chain transfer constants. The solvent may be used alone or in a mixture of two or more kinds. The ratio of the aromatic hydrocarbon solvent to be used is not particularly limited, and may be appropriately selected according to the situation. In general, it may be determined in the range of 1 to 20 times (mass ratio) the polyarylene ether to be used.

[0033] The proportion of fumaric acid or its derivative used as a modifying agent is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, based on 100 parts by mass of polyarylene ether. If it is 1 part by mass or more, a sufficient modification amount (degree of modification) can be obtained. If it is 20 parts by mass or less, post-treatment such as purification after modification can be appropriately performed.

[0034] The radical generator optionally used in the solution modification of polyarylene ether is not particularly limited. It is preferable that the radical generator has a decomposition temperature suitable for the reaction temperature and has a large hydrogen abstraction ability in order to effectively graft the modifier to the polyarylene ether. Specific examples include di-tert-butyl peroxide, dicumyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, benzoyl peroxide, and decanoyl peroxide. The proportion of the radical generator used is preferably 15 parts by mass or less relative to 100 parts by mass of polyarylene ether. If the radical generator is 15 parts by mass or less, it is preferable that insoluble components are not easily generated. When the above modification is performed in the absence of a radical generator, a polyarylene ether with a low modification amount (modification degree) (for example, a modification amount of 0.3 to 0.5% by mass) is obtained.

[0035] When polyarylene ether is solution-modified, specifically, polyarylene ether and a modifier such as fumaric acid or a derivative thereof are dissolved in an aromatic hydrocarbon solvent to become homogeneous, and then, when a radical generator is used, the radical generator is added at any temperature at which the half-life of the radical generator is 1 hour or less, and the reaction is carried out at that temperature. A temperature at which the half-life of the radical generator used exceeds 1 hour is not preferred because a long reaction time is required. The reaction time can be appropriately selected, but in order to allow the radical generator to act effectively, it is preferable to carry out the modification reaction at a predetermined reaction temperature for a time that is at least three times the half-life of the radical generator. After the reaction is completed, the reaction solution is added to a poor solvent for the polyarylene ether such as methanol, and the precipitated modified polyarylene ether is recovered and dried to obtain the desired polyarylene ether modified with a functional group.

[0036] When melt-modifying polyarylene ether, the polyarylene ether and, for example, fumaric acid or its derivative as a modifier are melt-kneaded using an extruder in the presence or absence of a radical generator to obtain a polyarylene ether modified with a functional group. The proportion of fumaric acid or its derivative used is preferably 1 to 5 parts by mass, more preferably 2 to 4 parts by mass, relative to 100 parts by mass of polyarylene ether. If it is 1 part by mass or more, a sufficient amount of modification (degree of modification) is obtained, and if it is 5 parts by mass or less, the modification efficiency of fumaric acid or its derivative is kept good and the amount of fumaric acid, etc. remaining in the pellets can be suppressed.

[0037] The radical generator used for melt modification of polyarylene ether is preferably one having a half-life temperature of 1 minute (1-minute half-life temperature) of 300° C. or higher. Those having a 1-minute half-life temperature of less than 300° C., such as peroxides and azo compounds, do not have a sufficient effect of modifying polyarylene ether. Specific examples of radical generators include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylhexane, 2,3-dimethyl-2,3-di(p-methylphenyl)butane, etc. Among them, 2,3-dimethyl-2,3-diphenylbutane, which has a one-minute half-life temperature of 330° C., is preferably used. The proportion of the radical generator used is preferably selected within the range of 0.1 to 3 parts by mass, more preferably 0.5 to 2 parts by mass, relative to 100 parts by mass of polyarylene ether. If it is 0.1 part by mass or more, a high modification effect can be obtained, and if it is 3 parts by mass or less, the polyarylene ether can be efficiently modified and insoluble components are unlikely to be generated.

[0038] An example of a method for melt-modifying a polyarylene ether is a method in which the polyarylene ether, fumaric acid or a derivative thereof, and a radical generator are uniformly dry-blended at room temperature, and then a melt reaction is carried out at a temperature substantially equal to the kneading temperature of the polyarylene ether, in the range of 300 to 350° C. 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 polyarylene ether can be suppressed.

[0039] Among the polyarylene ethers modified with functional groups obtained by the method described above in detail, in the case of the particularly preferred fumaric acid-modified polyarylene ether, the modification amount (modifier content) determined by the titration method described above is preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, further preferably 1 to 10 mass%, and particularly preferably 1.0 to 5.0 mass%. If the modification amount is 0.1 mass% or more, a polyarylene ether having sufficient mechanical properties and heat resistance can be obtained. The modification amount of 20 mass% or less is sufficient.

[0040] In order to increase the interfacial shear strength between the resin component and the carbon fiber (D), the content of the functional group-modified polyarylene ether (B) in the resin component contained in the thermoplastic resin composition is preferably 3 to 20 mass %, more preferably 5 to 15 mass %. When the amount of the functional group-modified polyarylene ether (B) is 3% by mass or more, excellent interfacial shear strength can be obtained. When the amount of the polyarylene ether (B) is 20% by mass or less, the mechanical strength and heat resistance of the obtained molded article can be kept good.

[0041] <Coupling agent (C)> Examples of the coupling agent used in the production of the thermoplastic resin composition according to one embodiment of the present invention include a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, etc. The coupling agents may be used alone or in combination of two or more.

[0042] The coupling agent used in the production of the thermoplastic resin composition according to one embodiment of the present invention preferably includes one or more selected from the group consisting of a silane coupling agent, an aluminate coupling agent, and a titanate coupling agent.

[0043] Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and the like.

[0044] Examples of the aluminate coupling agent include alkyl acetoacetate aluminum diisopropylate.

[0045] Examples of titanate coupling agents include isopropyl triisostearoyl titanate, tetraoctyl bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, and isopropyl tridodecyl benzene sulfonyl titanate.

[0046] The coupling agent used in the production of the thermoplastic resin composition according to one embodiment of the present invention preferably contains one or more selected from the group consisting of silane coupling agents, aluminate coupling agents, and titanate coupling agents, and more preferably contains an isocyanate-based silane (e.g., tris-(trimethoxysilylpropyl)isocyanurate, 3-isocyanatepropyltriethoxysilane). This provides the effect of improving the resistance to moist heat.

[0047] The content of the coupling agent (C) is preferably 0.3 to 3.0 parts by mass, and more preferably 0.5 to 1.5 parts by mass, based on 100 parts by mass of the total of the resin components contained in the thermoplastic resin composition. The coupling agent may exist in a form different from that at the time of compounding due to the reaction of the functional groups.

[0048] <Carbon fiber (D)> The carbon fiber contained in the thermoplastic resin composition according to one embodiment of the present invention is not particularly limited, and various carbon fibers such as PAN-based carbon fibers made from polyacrylonitrile, pitch-based carbon fibers made from coal tar pitch in petroleum or coal, and phenol-based carbon fibers made from thermosetting resins, such as phenolic resins, can be used. The carbon fiber may be obtained by a vapor growth method or may be recycled carbon fiber (RCF). Thus, the carbon fiber is not particularly limited, but it is preferable that the carbon fiber is at least one type of carbon fiber selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, thermosetting carbon fiber, phenolic carbon fiber, vapor-grown carbon fiber, and recycled carbon fiber (RCF). Although the degree of graphitization of carbon fibers varies depending on the raw material quality and the sintering temperature during production, carbon fibers of any degree of graphitization can be used. The shape of the carbon fibers is not particularly limited, and carbon fibers having at least one shape selected from the group consisting of milled fibers, chopped strands, short fibers, rovings, filaments, tows, whiskers, nanotubes, etc. can be used. In the case of chopped strands, those having an average fiber length of 0.1 to 50 mm and an average fiber diameter of 5 to 20 μm are preferably used. The density of the carbon fiber is not particularly limited, but is preferably 1.75 to 1.95 g / cm 3 is preferred.

[0049] The form of the carbon fiber may be a single fiber or a fiber bundle, or both single fibers and fiber bundles may be mixed. The number of single fibers in each fiber bundle may be substantially uniform or may be different. The average fiber diameter of the carbon fiber varies depending on the form, and for example, carbon fibers having an average fiber diameter of preferably 0.0004 to 15 μm, more preferably 3 to 15 μm, and even more preferably 5 to 10 μm can be used.

[0050] The content of the carbon fiber (D) is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, based on 100 parts by mass of the total of the resin components contained in the thermoplastic resin composition. When the amount of the carbon fiber (D) is within the above range, the molded article or composite material containing the thermoplastic resin composition of this embodiment has excellent mechanical strength.

[0051] As described above, in this specification, the thermoplastic resin composition according to one embodiment of the present invention may contain a thermoplastic resin (A), a functional group-modified polyarylene ether (B), a coupling agent (C), and a carbon fiber (D), and the method of inclusion is not important. A material (composite material) in which a member containing carbon fiber (D) is immersed in a mixture containing a thermoplastic resin (A), a functional group-modified polyarylene ether (B), and a coupling agent (C) is also included in the "composition" and "molded body containing the composition" in the present invention. Examples of the material include a carbon fiber member having a form of a woven fabric, nonwoven fabric, or unidirectional material immersed in a mixture containing a thermoplastic resin (A), a functional group-modified polyarylene ether (B), and a coupling agent (C). Alternatively, the carbon fibers (D) may be added in advance to the polyarylene ether (B) modified with a functional group, and then the thermoplastic resin (A) and the coupling agent (C) may be added to prepare a thermoplastic resin composition.

[0052] When the member containing carbon fibers is a woven fabric, a nonwoven fabric, or a unidirectional material, a single fiber having an average fiber diameter of preferably 3 to 15 μm, more preferably 5 to 7 μm, can be used. When the member containing carbon fibers has the form of a woven fabric, a nonwoven fabric, or a unidirectional material, a bundle of carbon fibers in one direction (fiber bundle) can be used. For the member containing carbon fibers, a product in which 6,000 (6K), 12,000 (12K), 24,000 (24K), or 60,000 (60K) carbon fiber single fibers are bundled as a fiber bundle supplied by a carbon fiber manufacturer may be used as it is, or a product further bundled with these may be used. The fiber bundle may be any of non-twisted yarn, twisted yarn, and untwisted yarn. The fiber bundle may be included in the molded body in an opened state, or may be included as a fiber bundle without being opened. When the component containing carbon fibers is a woven fabric, a nonwoven fabric, or a unidirectional material, a molded body can be obtained by immersing the component in a mixture containing a thermoplastic resin (A), a polyarylene ether modified with a functional group (B), and a coupling agent (C).

[0053] The carbon fiber-containing member, particularly the woven fabric, nonwoven fabric, and unidirectional material, is preferably thin. From the viewpoint of obtaining a thin carbon fiber composite material, the thickness of the carbon fiber-containing member is preferably 3 mm or less. In particular, in the case of a unidirectional material, the thickness is preferably 0.2 mm or less. The lower limit of the thickness of the carbon fiber-containing member is not particularly limited, but it is preferably 7 μm or more, and from the viewpoint of stable quality, it is preferably 10 μm or more, more preferably 20 μm or more.

[0054] <Convergence Agent (E)> The thermoplastic resin composition according to one embodiment of the present invention may further include a sizing agent. The sizing agent is not particularly limited as long as it is capable of sizing the carbon fibers. The carbon fibers included in the thermoplastic resin composition of this embodiment may have a sizing agent attached to the surface. When using carbon fibers to which a sizing agent is attached, the type of the sizing agent can be appropriately selected according to the types of carbon fibers and thermoplastic resin, and is not particularly limited. Carbon fibers are commercially available in various types, such as those treated with an epoxy-based sizing agent, a urethane-based sizing agent, or a polyamide-based sizing agent, or those that do not contain a sizing agent, but in this embodiment, they can be used regardless of the type of sizing agent or the presence or absence of the sizing agent. Among them, it is preferable to include a sizing agent having an epoxy group from the viewpoint of the tensile strength of the molded body after the wet heat treatment.

[0055] The sizing agent may cover a part or the whole of the surface of the carbon fibers. The sizing agent does not necessarily have to be entirely attached to the carbon fibers in the thermoplastic resin composition, and may be detached from the carbon fibers and dispersed in the thermoplastic resin composition.

[0056] Examples of commercially available carbon fibers (D) having a binder having an epoxy group attached thereto include Tenax (registered trademark) Chopped Fiber HTC261 manufactured by Teijin Ltd. and Pyrofil (registered trademark) Chopped Fiber TR066A manufactured by Mitsubishi Chemical Corp. (both of which are treated with an epoxy-based binder). In addition, Pyrofil (registered trademark) Chopped Fiber TR06Q manufactured by Mitsubishi Chemical Corp. (treated with a special epoxy-based binder) may also be used.

[0057] The content of the sizing agent is preferably 0.3 to 5.0 mass %, more preferably 1.0 to 3.0 mass %, based on the total of the carbon fibers (D) and the sizing agent. In addition, in calculating the blending amount of the thermoplastic resin composition, the mass of the sizing agent is included in the mass of the carbon fibers, that is, the total mass of the sizing agent and the carbon fibers is calculated as the mass of the carbon fibers (D).

[0058] <Other ingredients> To the thermoplastic resin composition according to one embodiment of the present invention, other components such as commonly used rubber-like elastomers, antioxidants, the above-mentioned carbon fibers or fillers other than carbon fibers, crosslinking agents, crosslinking assistants, nucleating agents, mold release agents, plasticizers, compatibilizers, colorants, and / or antistatic agents can be added within the scope of not impairing the object of the present invention. Some of the other components are exemplified below.

[0059] Various rubber-like elastic bodies can be used, for example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, chloroprene rubber, polysulfide rubber, thiokol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, 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 Examples of the core-shell type particulate elastomer include styrene-propylene random copolymers, styrene-ethylene-butylene random copolymers, ethylene propylene rubbers (EPR), ethylene propylene diene rubbers (EPDM), or core-shell type particulate elastomers such as acrylonitrile-butadiene-styrene-core-shell rubbers (ABS), methyl methacrylate-butadiene-styrene-core-shell rubbers (MBS), methyl methacrylate-butyl acrylate-styrene-core-shell rubbers (MAS), octyl acrylate-butadiene-styrene-core-shell rubbers (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubbers (AABS), butadiene-styrene-core-shell rubbers (SBR), and siloxane-containing core-shell rubbers such as methyl methacrylate-butyl acrylate siloxane, or modified rubbers thereof. Of these, SBR, SBS, SEB, SEBS, SIR, SEP, SIS, SEPS, core-shell rubber, or modified rubbers thereof are particularly preferably used.

[0060] Examples of modified rubber-like elastomers include rubbers obtained by modifying styrene-butyl acrylate copolymer rubber, 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, styrene-ethylene-butylene random copolymer, ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), etc., with a modifier having a polar group.

[0061] As the filler, carbon fiber or an organic filler can be added in addition to carbon fiber. Examples of the organic filler include organic synthetic fiber and natural plant fiber. Specific examples of the organic synthetic fiber include fully aromatic polyamide fiber, polyimide fiber, polyparaphenylene benzoxazole fiber, and the like. The organic filler may be used alone or in combination of two or more kinds, and the amount of the organic filler added is preferably 1 to 350 parts by mass, more preferably 5 to 200 parts by mass, relative to a total of 100 parts by mass of the resin components contained in the thermoplastic resin composition. If the amount is 1 part by mass or more, the effect of the filler can be sufficiently obtained, and if the amount is 350 parts by mass or less, the dispersibility is not inferior and there is no adverse effect on the moldability.

[0062] There are various antioxidants, and phosphorus-based antioxidants such as monophosphites and diphosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite and tris(mono- and di-nonylphenyl)phosphite, and phenol-based antioxidants are particularly preferred. The diphosphite is represented by the general formula: [ka] (In the formula, R 30 and R 31 each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0063] Specific examples of the phosphorus-based compound represented by the above general formula include distearyl pentaerythritol diphosphite, dioctyl pentaerythritol diphosphite, diphenyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

[0064] Known phenol-based antioxidants can be used, and specific examples thereof include 2,6-di-tert-butyl-4-methylphenol, 2,6-diphenyl-4-methoxyphenol, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 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, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, and the like. 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, tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, and the like. In addition to the above phosphorus-based antioxidants and phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, etc. can be used alone or in combination.

[0065] The antioxidant is usually present in an amount of 0.005 to 5 parts by mass relative to 100 parts by mass of the total of the resin components contained in the thermoplastic resin composition. If the antioxidant is present in an amount of 0.005 parts by mass or more, the molecular weight of the thermoplastic resin (A) can be suppressed from decreasing. If the amount is 5 parts by mass or less, the mechanical strength can be well maintained. When a plurality of types of antioxidants are contained in the composition as antioxidants, it is preferable to adjust the total amount to be within the above range. The amount of the antioxidant is more preferably 0.01 to 4 parts by mass, and even more preferably 0.02 to 3 parts by mass, relative to 100 parts by mass of the total of the resin components contained in the thermoplastic resin composition.

[0066] The nucleating agent can be arbitrarily selected from known nucleating agents such as metal salts of carboxylic acids such as aluminum di(p-tert-butylbenzoate), metal salts of phosphoric acids such as sodium methylene bis(2,4-di-tert-butylphenol) acid phosphate, talc, phthalocyanine derivatives, etc. Specific product 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. These nucleating agents can be used alone or in combination of two or more. The amount of the nucleating agent is not particularly limited, but is preferably 0.01 to 5 parts by mass, more preferably 0.04 to 2 parts by mass, based on 100 parts by mass of the total resin components contained in the thermoplastic resin composition.

[0067] The release agent can be arbitrarily selected from known agents such as polyethylene wax, silicone oil, long-chain carboxylic acid, and long-chain carboxylic acid metal salt. These release agents can be used alone or in combination of two or more. The amount of the release agent is not particularly limited, but is preferably 0.1 to 3 parts by mass, more preferably 0.2 to 1 part by mass, based on 100 parts by mass of the total resin components contained in the thermoplastic resin composition.

[0068] The thermoplastic resin composition according to one embodiment of the present invention may essentially consist of the above-mentioned thermoplastic resin (A), functional group-modified polyarylene ether (B), coupling agent (C) and carbon fiber (D), or may essentially consist of the above-mentioned (A) to (D) and sizing agent (E). "Substantially consisting of (A) to (D)" or (A) to (E) means, for example, that the proportion of (A) to (D) or (A) to (E) in the entire thermoplastic resin composition is 80 mass% or more, 90 mass% or more, or 95 mass% or more.

[0069] <Preparation of Thermoplastic Resin Composition> The method for preparing the thermoplastic resin composition according to one embodiment of the present invention is not particularly limited, but may be mixing with a known mixer, or melt kneading with an extruder or the like. A member containing carbon fibers may be immersed in a molten resin. Alternatively, the carbon fibers may be treated in advance with a predetermined amount of a coupling agent and then kneaded or impregnated. For example, a composition containing a thermoplastic resin (A), a functional group-modified polyarylene ether (B), a coupling agent (C), carbon fiber (D), and, if necessary, the above various components, can be molded and injection molded. In the injection molding, a mold having a predetermined shape can be used for molding, and in the extrusion molding, a film or sheet can be molded using a T-die, and the obtained film or sheet can be heated and melted and extruded into a predetermined shape. A method of side-feeding carbon fibers using a twin-screw kneader or a method of producing so-called long fiber pellets in which carbon fiber rovings are immersed in a molten resin and cut into a desired pellet length after pultrusion molding is preferably used because breakage of the carbon fibers can be suppressed. The thermoplastic resin composition can also be press-molded, and known methods such as a cold press method and a hot press method can be used. When a composite member is obtained by immersing a member containing carbon fiber (D) in a mixture containing thermoplastic resin (A), functional group-modified polyarylene ether (B), and coupling agent (C), specifically, a member containing carbon fiber (D) (woven fabric, nonwoven fabric, UD material, etc.) is immersed in a mixture containing thermoplastic resin (A), functional group-modified polyarylene ether (B), and coupling agent (C). The member to be immersed in the resin may be one sheet, or may be a laminate of two or more sheets.

[0070] <Method of manufacturing molded body> As described above, the molded article made of the thermoplastic resin composition according to one embodiment of the present invention can be obtained by molding the composition by mixing, melt-kneading, or immersing the thermoplastic resin (A), the functional group-modified polyarylene ether (B), the coupling agent (C), and the carbon fiber (D). As another method, the molded article can also be molded by a method including a step of preparing a carbon member containing the functional group-modified polyarylene ether (B) and the carbon fiber (D), and a step of adding the thermoplastic resin (A) and the coupling agent (C) to the carbon member.

[0071] The means for producing the carbon member containing the thermoplastic resin (A), the functional group-modified polyarylene ether (B) and the carbon fiber (D) is not particularly limited. For example, a method of immersing the carbon fiber (D) in the functional group-modified polyarylene ether (B) in a suitable solvent, a method of applying a mixture of the polyarylene ether (B) mixed with a suitable vehicle to the carbon fiber (D), a method of mixing the functional group-modified polyarylene ether (B) with a sizing material and adding it to the carbon fiber (D), etc. can be mentioned. When using this method, the form of the carbon fiber (D) can be at least one form selected from chopped strands, woven fabric, nonwoven fabric, and unidirectional material.

[0072] In the next step, the thermoplastic resin (A) and the coupling agent (C) are added to the carbon member obtained by the above step. The method of adding the thermoplastic resin (A) and the coupling agent (C) to the carbon member is not limited, and the thermoplastic resin (A) may be in a solution state or in a molten state. Specifically, there can be mentioned a method of immersing the carbon member in a mixture containing the thermoplastic resin (A) and the coupling agent (C) in an appropriate solvent, a method of laminating a film containing the thermoplastic resin (A) and the coupling agent (C) and performing melt pressing, a method of directly adding powders of the thermoplastic resin (A) and the coupling agent (C) to the carbon member and then melting the powders to add the thermoplastic resin (A) and the coupling agent (C), and the like. The carbon member may contain the functional group-modified polyarylene ether (B) and the carbon fiber (D), and the thermoplastic resin (A) and the coupling agent (C) may be added in the form of a woven fabric, a nonwoven fabric, or a unidirectional material, or the carbon member having the form of a woven fabric or the like may be cut into short pieces to form a chopped material, and then the thermoplastic resin (A) and the coupling agent (C) may be added. After adding the thermoplastic resin (A) and the coupling agent (C) to the carbon member, a molded body can be produced by various molding methods described below.

[0073] <Molded body> The shape of the molded product made of the thermoplastic resin composition according to one embodiment of the present invention is not particularly limited, and examples thereof include sheets, films, fibers, woven fabrics, nonwoven fabrics, unidirectional materials (UD materials), containers, injection molded products, and blow molded products. The molded product made of the thermoplastic resin composition according to one embodiment of the present invention may be an injection molded product as described above. Depending on the form of the carbon fiber used, the molded product may be a molded product containing at least one member selected from unidirectional fiber reinforcement, woven carbon fiber, and nonwoven carbon fiber. A plurality of such molded products may be laminated to form a laminate. This laminate is also included in the "molded product" in this specification.

[0074] The molded article according to one embodiment of the present invention has high strength retention in a high temperature and high humidity environment. For example, the molded article according to this embodiment has a strength retention calculated using the following formula (1) for the tensile strength after molding and the tensile strength after wet heat treatment at 120°C for 500 hours of 80% or more, and more preferably 90% or more. The wet heat treatment can be carried out by the method described in the Examples.

number

[0075] In the molded article of this embodiment obtained by molding the thermoplastic resin composition, the coupling agent (C) may not be detectable. Also, due to the reaction of the functional groups, the coupling agent (C) may exist in a form different from that at the time of blending. Therefore, the molded article according to one aspect of the present invention may be a molded article made of a thermoplastic resin composition containing a thermoplastic resin (A), a polyarylene ether (B) modified with a functional group, and a carbon fiber (D), and has a strength retention rate of 80% or more after wet heat treatment at 120° C. for 500 hours, as shown in the above formula (1). In this aspect, atoms presumed to be derived from the coupling agent (C), such as Si, Al, and Ti, may be detected by a known method such as inductively coupled plasma atomic emission spectrometry (ICP-AES).

[0076] The molded article made of the thermoplastic resin composition according to one embodiment of the present invention is suitable for industrial materials such as electric / electronic materials (connectors, printed circuit boards, etc.), industrial construction materials, automobile parts (vehicle-mounted connectors, wheel caps, cylinder head covers, etc.), home appliances, various machine parts, pipes, sheets, trays, and films.

[0077] Specifically, the molded article made of the thermoplastic resin composition according to one embodiment of the present invention can be used as a thermoplastic carbon fiber reinforced plastic (CFRTP) in a wide range of applications, such as automobiles, aircraft, and sporting goods, which require further weight reduction. The molded article for this application can also be applied to the improvement of engineering plastics, which require resistance under high load environments such as high loads and high temperatures. The molded article made of the thermoplastic resin composition according to one embodiment of the present invention has a short molding time, is excellent in recyclability, is easy to immerse in resin during molding, and has sufficient mechanical strength, making it practical for a wide range of applications.

[0078] Specific examples include applications in automobiles, motorcycles and bicycles, water heaters and eco-cutes, home appliances and electronic devices, building materials, and daily necessities. Examples of automotive applications include automotive parts such as sliding parts such as gears, automotive panel components, millimeter wave radomes, IGBT housings, radiator grilles, meter hoods, fender supports, front engine covers, front strut tower panels, transmission center tunnels, radiator core supports, front dashes, door inners, rear luggage back panels, rear luggage side panels, rear luggage floors, rear luggage partitions, roofs, door frame pillars, seat backs, headrest supports, engine parts, crash boxes, front floor tunnels, front floor panels, under covers, under support rods, impact beams, front cowls, and front strut tower bars.

[0079] A molded article made of a thermoplastic resin composition according to one embodiment of the present invention can be suitably used to form, for example, a power electronic unit, a quick-charging plug, an on-board charger, a lithium-ion battery, a battery control unit, a power electronic control unit, a three-phase synchronous motor, a home charging plug, and the like.

[0080] The molded article made of the thermoplastic resin composition according to one embodiment of the present invention can further be suitably used to form, for example, a solar twilight sensor, an alternator, an EDU (electronic injector driver unit), an electronic throttle, a tumble control valve, a throttle opening sensor, a radiator fan controller, a stick coil, an A / C pipe joint, a diesel particulate filter, a headlight reflector, a charge air duct, a charge air cooling head, an intake air temperature sensor, a gasoline fuel pressure sensor, a cam / crank position sensor, a combination valve, an engine oil pressure sensor, a transmission gear angle sensor, a continuously variable transmission oil pressure sensor, an ELCM (evaporative leak check module) pump, a water pump impeller, a steering roll connector, an ECU (engine computer unit) connector, an ABS (anti-lock brake system) reservoir piston, an actuator cover, and the like.

[0081] The molded article made of the thermoplastic resin composition according to one embodiment of the present invention can also be suitably used as a sealant for sealing a sensor included in an in-vehicle sensor module. The sensor is not particularly limited, and specific examples thereof include an atmospheric pressure sensor (for example, for altitude correction), a boost pressure sensor (for example, for fuel injection control), an (IC) atmospheric pressure sensor, an acceleration sensor (for example, for airbags), a gauge pressure sensor (for example, for seat condition control), a tank internal pressure sensor (for example, for fuel tank leak detection), a refrigerant pressure sensor (for example, for air conditioner control), a coil driver (for example, for ignition coil control), an EGR (exhaust gas recirculation) valve sensor, an air flow sensor (for example, for fuel injection control), an intake manifold pressure (MAP) sensor (for example, for fuel injection control), an oil pan, a radiator cap, and an intake manifold.

[0082] The molded article made of the thermoplastic resin composition according to one embodiment of the present invention is not limited to the above-mentioned automotive parts, and can also be suitably used for, for example, high-voltage (harness) connectors, millimeter-wave radomes, IGBT (insulated gate bipolar transistor) housings, battery fuse terminals, radiator grilles, meter hoods, inverter cooling water pumps, battery monitoring units, structural parts, intake manifolds, high-voltage connectors, motor control ECUs (engine computer units), inverters, piping parts, canister purge valves, power units, bus bars, motor reducers, canisters, and the like. The molded article made of the thermoplastic resin composition according to one embodiment of the present invention is also suitable for use in motorcycle parts and bicycle parts, and more specifically, examples of the molded article include motorcycle parts, motorcycle cowls, bicycle parts, etc. Examples of the motorcycle / bicycle applications include motorcycle parts, motorcycle cowls, and bicycle parts.

[0083] The molded article made of the thermoplastic resin composition according to one embodiment of the present invention is also excellent in chemical resistance and can be used in various electrical appliances. For example, it is also preferable to configure a part of a water heater, specifically, a natural refrigerant heat pump water heater known as "Ecocute (registered trademark)" or the like. Examples of the part include shower parts, pump parts, and piping parts, and more specifically, single-mouth circulation connection fittings, relief valves, mixing valve units, heat-resistant traps, pump casings, composite water valves, water inlet fittings, resin joints, piping parts, resin pressure reducing valves, and elbows for water faucets.

[0084] The molded article made of the thermoplastic resin composition according to one embodiment of the present invention is also suitable for use in home appliances and electronic devices. More specifically, examples of the molded article may include components for telephones, mobile phones, microwave ovens, refrigerators, vacuum cleaners, office equipment, power tool parts, electrical component applications, static electricity prevention applications, high frequency electronic components, high heat dissipation electronic components, high voltage parts, electromagnetic wave shielding parts, communication equipment products, AV equipment, personal computers, cash registers, electric fans, ventilating fans, sewing machines, ink peripheral parts, ribbon cassettes, air cleaner parts, warm water washing toilet seat parts, toilet seats, toilet covers, rice cooker parts, optical pickup devices, lighting equipment parts, DVDs, DVD-RAMs, DVD pickup parts, DVD pickup boards, switch parts, sockets, displays, video cameras, filaments, plugs, high speed color copiers (laser printers), inverters, air conditioners, keyboards, converters, televisions, facsimiles, optical connectors, semiconductor chips, LED parts, washing machines / washer / dryer parts, dishwasher / dish dryer parts, and the like. The molded article made of the thermoplastic resin composition according to one embodiment of the present invention is also suitable for use as a building material, and more specifically, examples of such building materials include components for exterior wall panels, back panels, partition wall panels, signal lights, emergency lights, and wall materials.

[0085] The molded article made of the thermoplastic resin composition according to one embodiment of the present invention is also suitable for use in miscellaneous goods, daily necessities, and the like. More specifically, examples of such products include chopsticks, lunch boxes, tableware containers, food trays, food packaging materials, aquariums, tanks, toys, sporting goods, surfboards, door caps, door steps, pachinko machine parts, remote control cars, remote control cases, stationery, musical instruments, tumblers, dumbbells, helmet box products, shutter blade members used in cameras, etc., racket members for table tennis, tennis, etc., and board members for skis, snowboards, etc. Each of the various parts described above may be constituted in whole or in part by a molded article made of a thermoplastic resin composition according to one aspect of the present invention. EXAMPLES

[0086] The present invention will be explained more specifically with reference to examples, but the present invention is not limited to these in any way.

[0087] The components used in the examples and comparative examples are as follows. [Thermoplastic resin (A)] Thermoplastic resin 1: SPS (syndiotactic polystyrene resin, racemic pentad: 98 mol%, MFR: 13 g / 10 min, melting point: 270°C) Polymerization was carried out in the same manner as in Production Example 1 of JP-A No. 2009-068022, except that the temperature was raised to 80°C. Thermoplastic resin 2: PPS (polyphenylene sulfide resin, manufactured by DIC Corporation: T-1G)

[0088] [Polyarylene ether modified with functional groups (B)] Fumaric acid modified PPE (manufactured by melt modification, modification amount 1.7% by mass, glass transition point 220°C) 100 parts by mass of polyarylene ether [BLUESTAR NEW CHEMICAL MATERIALS Co.LTD.: LXR040; poly(2,6-dimethyl-1,4-phenyl ether)], 4 parts by mass of radical generator (NOF Corp.: Nofumer BC90; 2,3-dimethyl-2,3-diphenylbutane), and 2 parts by mass of modifier (fumaric acid) were dry blended, and melt-kneaded at a screw speed of 200 rpm and a set temperature of 300° C. using a twin-screw kneader (Coperion: ZSK32MC) having a cylinder diameter of 32 mm. The strand was cooled and then pelletized to obtain a fumaric acid-modified polyarylene ether. The amount of modification was calculated as the acid content from the amount of neutralization titer measured in accordance with JIS K0070-1992.

[0089] [Coupling agent (C)] Silane coupling agent (isocyanate-based silane, Shin-Etsu Chemical Co., Ltd.: KBE-9007N)

[0090] [Carbon fiber (D), binder (E)] Carbon fiber 1 (Mitsubishi Chemical Corporation: TR066A, chopped carbon fiber, sizing agent (epoxy-based) amount 3.0% by mass) Carbon fiber 2 (Mitsubishi Chemical Corporation: TR06U, chopped carbon fiber, sizing agent (urethane-based) amount: 2.5% by mass)

[0091] [Other ingredients] Rubber-like elastic body (Kuraray Co., Ltd.: SEPTON8006) Antioxidant 1 (BASF Japan: Irganox 1076) Antioxidant 2 (ADEKA Corporation: PEP36) Nucleating agent (ADEKA Corporation: NA-70)

[0092] Example 1 <Production of Molded Product> The resin components (SPS: 95% by mass, fumaric acid modified PPE: 5% by mass) contained in the thermoplastic resin composition were mixed with 100 parts by mass of carbon fiber 1: 28 parts by mass, silane coupling agent: 1 part by mass, antioxidant 1: 0.2 parts by mass, antioxidant 2: 0.2 parts by mass, and crystal nucleating agent: 0.3 parts by mass using a twin-screw mixer (Coperion: ZSK32MC) with a cylinder diameter of 32 mm, with the carbon fiber being side-fed. The obtained pellets were injection molded using an injection molding machine (Niigata Machine Techno Co., Ltd.: MD100) under conditions of a cylinder temperature of 300°C and a mold temperature of 150°C to obtain a test piece. An ISO mold was used. <Evaluation of mechanical strength> Using this test piece, a tensile test was performed in accordance with ISO 527-1:2012 (2nd edition) using a tensile tester (Shimadzu Corporation: Autograph AG5000B) at room temperature with an initial chuck distance of 100 mm and a tensile speed of 5 mm / min to measure the tensile strength (MPa) after molding. The results are shown in Table 1. <Evaluation of mechanical strength after wet heat treatment> The test piece was treated by immersing it in water at 120° C. for 500 hours (wet heat treatment). After the treatment, the above-mentioned tensile strength (MPa) of the test piece was measured. Furthermore, the strength retention rate of the tensile strength after molding and the tensile strength after the wet heat treatment was calculated using the following formula (1), and the result was that the strength retention rate was 90%.

number

[0093] Comparative Example 1 Except for not using the silane coupling agent, a molded body was obtained in the same manner as in Example 1. The mechanical strength of the obtained molded body and the mechanical strength after the wet heat treatment were measured in the same manner as in Example 1. The results are shown in Table 1. The strength retention rate was 70%.

[0094] [Table 1]

[0095] Example 2 With respect to a total of 100 parts by mass of resin components (SPS: 95% by mass, fumaric acid modified PPE: 5% by mass) contained in the thermoplastic resin composition, 31 parts by mass of carbon fiber 1, 1 part by mass of silane coupling agent, 11 parts by mass of rubber-like elastomer, 0.2 parts by mass of antioxidant 1, 0.2 parts by mass of antioxidant 2, and 0.3 parts by mass of crystal nucleating agent were kneaded by side feeding the carbon fiber using a twin-screw kneader (manufactured by Coperion: ZSK32MC) with a cylinder diameter of 32 mm. The obtained pellets were injection molded using an injection molding machine (manufactured by Niigata Machine Techno Co., Ltd.: MD100) under conditions of a cylinder temperature of 300°C and a mold temperature of 150°C to obtain a test piece. The mold was an ISO mold. The mechanical strength of the obtained molded body and the mechanical strength after wet heat treatment were measured in the same manner as in Example 1. The results are shown in Table 2. The strength retention was 90%.

[0096] Comparative Example 2 A molded body was obtained in the same manner as in Example 2, except that no silane coupling agent was used. The mechanical strength of the obtained molded body and the mechanical strength after the wet heat treatment were measured in the same manner as in Example 1. The results are shown in Table 2. The strength retention rate was 67%.

[0097] [Table 2]

[0098] Reference example 3 A molded body was obtained in the same manner as in Example 1, except that carbon fiber 2 was used instead of carbon fiber 1. The mechanical strength of the obtained molded body and the mechanical strength after the wet heat treatment were measured in the same manner as in Example 1. The results are shown in Table 3.

[0099] Comparative Example 3 Except that no silane coupling agent was used. reference A molded article was obtained in the same manner as in Example 3. The mechanical strength of the obtained molded article and the mechanical strength after the wet heat treatment were measured in the same manner as in Example 1. The results are shown in Table 3.

[0100] [Table 3]

[0101] Reference example 4 A molded body was obtained in the same manner as in Example 2, except that carbon fiber 2 was used instead of carbon fiber 1. The mechanical strength of the obtained molded body and the mechanical strength after the wet heat treatment were measured in the same manner as in Example 1. The results are shown in Table 4.

[0102] Comparative Example 4 Except that no silane coupling agent was used. reference A molded article was obtained in the same manner as in Example 4. The mechanical strength of the obtained molded article and the mechanical strength after the wet heat treatment were measured in the same manner as in Example 1. The results are shown in Table 4.

[0103] [Table 4]

[0104] Example 5 The resin components (PPS: 95% by mass, fumaric acid modified PPE: 5% by mass) contained in the thermoplastic resin composition were mixed with 1:28 parts by mass of carbon fiber and 1 part by mass of silane coupling agent by side feeding the carbon fiber using a twin-screw mixer (Coperion: ZSK32MC) with a cylinder diameter of 32 mm. The obtained pellets were injection molded using an injection molding machine (Niigata Machine Techno Co., Ltd.: MD100) under the conditions of a cylinder temperature of 320°C and a mold temperature of 150°C to obtain a test piece. The mold was an ISO mold. The mechanical strength of the obtained molded body and the mechanical strength after the wet heat treatment were measured in the same manner as in Example 1. The results are shown in Table 5. The strength retention was 80%.

[0105] Comparative Example 5 A molded body was obtained in the same manner as in Example 5, except that no silane coupling agent was used. The mechanical strength of the obtained molded body and the mechanical strength after the wet heat treatment were measured in the same manner as in Example 1. The results are shown in Table 5. The strength retention rate was 70%.

[0106] [Table 5]

[0107] From Examples 1 and 2, it can be seen that the molded body made of the thermoplastic resin composition using the coupling agent has excellent tensile strength after molding and tensile strength after moist heat treatment, and in particular, has excellent strength retention rate of 80% or more after moist heat treatment. Also, reference From Examples 3 and 4, it can be seen that molded articles made of thermoplastic resin compositions using a coupling agent have excellent tensile strength after molding and tensile strength after wet heat treatment, even when carbon fibers different from those used in Examples 1 and 2 are used.

[0108] Although some embodiments and / or examples of the present invention have been described in detail above, those skilled in the art can easily make many modifications to these exemplary embodiments and / or examples without substantially departing from the novel teachings and advantages of the present invention, and therefore many such modifications are within the scope of the present invention. The contents of all documents cited in this specification and of the application from which this application claims priority under the Paris Convention are incorporated by reference in their entirety.

Claims

1. A thermoplastic resin composition comprising: a thermoplastic resin (A) which is a polyphenylene sulfide resin, a polystyrene-based resin, or a polyamide resin; a polyarylene ether (B) modified with a functional group; a coupling agent (C); carbon fibers (D); and a sizing agent (E); the content of the thermoplastic resin (A) is 80 to 97 mass% in the resin components contained in the thermoplastic resin composition, and the content of the functional group-modified polyarylene ether (B) is 3 to 20 mass% in the resin components contained in the thermoplastic resin composition; The sizing agent (E) has an epoxy group, The thermoplastic resin composition, wherein the functional group-modified polyarylene ether (B) is a dicarboxylic acid-modified polyarylene ether.

2. The thermoplastic resin composition according to claim 1 , wherein the thermoplastic resin (A) comprises syndiotactic polystyrene.

3. The thermoplastic resin composition according to claim 1 or 2, wherein the coupling agent (C) comprises at least one selected from the group consisting of a silane coupling agent, an aluminate coupling agent, and a titanate coupling agent.

4. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the coupling agent (C) comprises an isocyanate-based silane.

5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the dicarboxylic acid-modified polyarylene ether is a fumaric acid-modified polyarylene ether or a maleic anhydride-modified polyarylene ether.

6. A molded article made of the thermoplastic resin composition according to any one of claims 1 to 5.

7. The molded article according to claim 6, which has a strength retention rate of 80% or more after wet heat treatment at 120°C for 500 hours, as represented by the following formula (1): [0045]

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