Polyarylene sulfide resin composition, molded article, composite, and production methods therefor

Abstract

Provided are a resin composition that has excellent conductivity, toughness, workability, and long-term stability, a molded article, a composite, and production methods therefor. More specifically, the present invention provides: a polyarylene sulfide (PAS) resin composition obtained by combining, as essential ingredients, a PAS resin (A) and a carbonaceous material (B) that is not carbon fibers, the melt viscosity (V6) of the PAS resin (A) being no more than 200 Pa⋅s, the pH of the carbonaceous material (B) that is not carbon fibers being at least 6, there being 5–80 parts by mass of the carbonaceous material (B) that is not carbon fibers per 100 parts by mass of the PAS resin (A), and the flexural modulus of the PAS resin composition being no more than 18 GPa; a molded article; a composite; and production methods therefor.

Description

Polyarylene sulfide resin composition, molded article, composite, and method for producing the same

[0001] The present invention relates to a polyarylene sulfide resin composition, a polyarylene sulfide resin molded article, a resin-metal composite, and methods for producing the same.

[0002] In recent years, the demand for secondary batteries, such as lithium-ion batteries (LiBs), has increased with the advancement of vehicle electrification and the spread of renewable energy. Electrode components for LiBs must have adequate conductivity, minimal conductivity variation, toughness, and reliability during long-term use (long-term stability).

[0003] On the other hand, polyarylene sulfide (hereinafter sometimes abbreviated as "PAS") resins, typified by polyphenylene sulfide (hereinafter sometimes abbreviated as "PPS") resins, are excellent in mechanical strength, heat resistance, chemical resistance, moldability, dimensional stability, flame retardancy, etc., and are therefore widely used mainly in electrical and electronic equipment parts, automobile part materials, etc.

[0004] Since PAS resin is an insulating material, it needs to be made conductive in order to be used in safety components for the anode of LiBs, and the most common method is to compound it with conductive materials such as carbon fiber or carbon black.In addition, since it is used in conjunction with metal components, it is required to have high toughness from the viewpoint of adhesion between the components.

[0005] As a conventional PAS resin composition for LiB, for example, Patent Document 1 discloses a PPS resin composition containing PAS resin, graphite, carbon fiber, and polyolefin wax. Patent Document 2 discloses a resin composition blended with PPS, conductive carbon black, carbon fiber, and graphite.

[0006] Japanese Patent Application Laid-Open No. 2006-19227 International Publication No. 2002 / 093670 Pamphlet

[0007] However, the required properties are becoming increasingly high, and there are cases where conventional materials are not sufficient to meet these requirements. In particular, there is a demand for small variations in electrical conductivity and suppression of deterioration during long-term use, and it has been difficult to achieve these properties simultaneously with high electrical conductivity and toughness.

[0008] Therefore, an object of the present invention is to provide a PAS resin composition, a molded article, and a composite, which are excellent in electrical conductivity, toughness, processability, and long-term stability, as well as methods for producing the same.

[0009] As a result of intensive research to solve the above-mentioned problems, the present inventors discovered that a resin composition that solves the above-mentioned problems can be obtained by blending a specific amount of a carbon-based material other than carbon fiber having a specific pH with a PAS resin having a melt viscosity of 200 Pa·s or less, and thus completed the present invention.

[0010] That is, the present disclosure relates to a PAS resin composition comprising a PAS resin (A) and a carbon-based material (B) other than carbon fiber as essential components, wherein the PAS resin (A) has a melt viscosity (V6) of 200 Pa s or less, the carbon-based material (B) other than carbon fiber has a pH of 6 or more, the amount of the carbon-based material (B) other than carbon fiber is 5 to 80 parts by mass per 100 parts by mass of the PAS resin (A), and the PAS resin composition has a flexural modulus of 18 GPa or less.

[0011] The present disclosure also relates to a PAS resin molded article obtained by molding the above-described PAS resin composition.

[0012] The present disclosure also relates to a composite member obtained by joining the above-described molded article and a metal member.

[0013] The present disclosure also relates to a method for producing a PAS resin composition, comprising a step of blending a PAS resin (A) and a carbon-based material (B) other than carbon fiber as essential components, and melt-kneading the blended PAS resin at a temperature equal to or higher than the melting point of the PAS resin (A), wherein the PAS resin (A) has a melt viscosity (V6) of 200 Pa s or less, the carbon-based material (B) other than carbon fiber has a pH of 6 or more, the blending amount of the carbon-based material (B) other than carbon fiber is 5 to 80 parts by mass per 100 parts by mass of the PAS resin (A), and the flexural modulus of the PAS resin composition is 18 GPa or less.

[0014] The present disclosure also relates to a method for producing a molded article, comprising the steps of producing a PAS resin composition by the above-described production method and melt-molding the obtained PAS resin composition.

[0015] The present disclosure also relates to a method for producing a composite, comprising the steps of producing a molded article by the above-described production method and joining the obtained molded article to a metal member.

[0016] According to the present invention, it is possible to provide a resin composition, a molded article, and a composite, which are excellent in electrical conductivity, toughness, processability, and long-term stability, as well as methods for producing them.

[0017] Hereinafter, an embodiment of the present invention will be described in detail, but the scope of the present invention is not limited to the embodiment described here, and various modifications can be made without departing from the spirit of the present invention. Furthermore, when multiple upper and lower limit values ​​are specified for a specific parameter, any upper and lower limit values ​​can be combined to form a suitable numerical range.

[0018] The PAS resin composition according to this embodiment is a PAS resin composition obtained by blending a PAS resin (A) and a carbon-based material (B) other than carbon fiber as essential components, characterized in that the melt viscosity (V6) of the PAS resin (A) is 200 Pa s or less, the pH of the carbon-based material (B) other than carbon fiber is 6 or more, the blending amount of the carbon-based material (B) other than carbon fiber is 5 to 80 parts by mass per 100 parts by mass of the PAS resin (A), and the flexural modulus is 18 GPa or less. This will be explained below.

[0019] <PAS Resin (A)> The PAS resin composition according to this embodiment contains a PAS resin (A) as an essential component.

[0020] The PAS resin has a resin structure having a repeating unit in which an aromatic ring and a sulfur atom are bonded, and specifically, a PAS resin represented by the following general formula (1):

[0021] (In the formula, R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group, and, if necessary, a structural portion represented by the following general formula (2):

[0022] The trifunctional structural moiety represented by formula (2) is preferably present in an amount of 0.001 to 3 mol %, particularly preferably 0.01 to 1 mol %, based on the total number of moles of the trifunctional structural moiety and other structural moieties.

[0023] Here, the structural moiety represented by the general formula (1) is particularly R １ and R ２ is preferably a hydrogen atom from the viewpoint of the mechanical strength of the PAS resin, and in that case, examples include those bonded at the para position represented by the following formula (3) and those bonded at the meta position represented by the following formula (4).

[0024] Among these, a structure in which the bond between the sulfur atom and the aromatic ring in the repeating unit is at the para position represented by the general formula (3) is particularly preferred in terms of the heat resistance of the PAS resin.

[0025] The PAS resin may contain not only the structural moieties represented by the general formula (1) or (2) but also the structural moieties represented by the following structural formulae (5) to (8):

[0026] The structural moieties represented by the general formula (1) and the general formula (2) may be contained in an amount of 30 mol % or less of the total of the structural moieties represented by the general formula (1) and the general formula (2). In particular, in the present disclosure, it is preferable that the structural moieties represented by the general formulas (5) to (8) be 10 mol % or less from the viewpoint of the heat resistance and mechanical strength of the PAS. When the structural moieties represented by the general formulas (5) to (8) are contained in the PAS resin, the bonding mode thereof may be either a random copolymer or a block copolymer.

[0027] The PAS resin may also have naphthyl sulfide bonds or the like in its molecular structure, but the amount of such bonds is preferably 3 mol % or less, and particularly preferably 1 mol % or less, relative to the total number of moles including other structural moieties.

[0028] The physical properties of the PAS resin (A) are not particularly limited as long as they do not impair the effects of the present invention, but are as follows.

[0029] (Melt Viscosity) The melt viscosity (V6) of the PAS resin (A) used in this embodiment is in the range of 200 Pa s or less, as measured at 300°C, since a good balance between processability and toughness is achieved. It is also preferably in the range of 2 Pa s or more, more preferably in the range of 30 Pa s or more. It is also preferably in the range of 180 Pa s or less, more preferably in the range of 160 Pa s or less. The melt viscosity (V6) is measured using a flow tester, CFT-500D, manufactured by Shimadzu Corporation, at 300°C and a load of 1.96 x 10. ６ The melt viscosity is measured after holding the sample at a temperature of 10 Pa and L / D=10 (mm) / 1 (mm) for 6 minutes.

[0030] (Non-Newtonian Index) The non-Newtonian index of the PAS resin (A) used in this embodiment is not particularly limited, but is preferably in the range of 0.90 or more and 2.00 or less. When a linear PAS resin is used, the non-Newtonian index is preferably in the range of 0.90 or more, more preferably 0.95 or more, and preferably 1.50 or less, more preferably 1.20 or less. Such a PAS resin has excellent mechanical strength and fluidity. However, in this disclosure, the non-Newtonian index (N value) is a value calculated using the following formula after measuring the shear rate (SR) and shear stress (SS) using a capillograph under conditions of a melting point of +20°C and an orifice length (L) to orifice diameter (D) ratio of L / D = 40. The closer the non-Newtonian index (N value) is to 1, the more linear the structure, and the higher the non-Newtonian index (N value), the more branched the structure.

[0031] [where SR is the shear rate (sec －１ ), SS is the shear stress (dyne / cm ２ ), and K denotes a constant.

[0032] (Carboxyl group content) The carboxyl group content of the PAS resin (A) used in this embodiment is preferably in the range of 10 μmol / g or more to 200 μmol / g or less, more preferably in the range of 20 μmol / g or more to 180 μmol / g or less. Within this range, the resin composition can obtain a molded product having good processability and excellent long-term stability. In this disclosure, the carboxyl group content is a value measured by the method described in the examples.

[0033] (Zeta Potential) The PAS resin (A) used in this embodiment preferably has a zeta potential of -70 mV or higher, more preferably -50 mV or higher, measured by a streaming potential method under conditions of pH 7.8 to 8.2. The zeta potential of the PAS resin is a value measured using a film made of PAS resin as a test piece, in an electrolyte solution of 1 mmol / L KCl aqueous solution, using a SurPASS3 (Anton Paar), at a measurement temperature of 22 to 26°C. The zeta potential refers to the average value when the zeta potential of the test piece surface is measured three times.

[0034] (Production Method) The method for producing the PAS resin is not particularly limited, but examples thereof include (Production Method 1) a method in which a dihalogenoaromatic compound is polymerized in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogenoaromatic compound or other copolymerization component is added; (Production Method 2) a method in which a dihalogenoaromatic compound is polymerized in a polar solvent in the presence of a sulfidizing agent or the like, and if necessary, a polyhalogenoaromatic compound or other copolymerization component is added; (Production Method 3) a method in which p-chlorothiophenol is added, and if necessary, other copolymerization components are added, and then self-condensed; and (Production Method 4) a method in which a diiodoaromatic compound and elemental sulfur are melt-polymerized under reduced pressure in the presence of a polymerization inhibitor that may have a functional group such as a carboxyl group or an amino group. Of these methods, (Production Method 2) is preferred because it is versatile. During the reaction, an alkali metal salt of a carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above-mentioned (Production Method 2) methods, there is a method for producing a PAS resin by introducing a water-containing sulfidizing agent into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at a rate at which water can be removed from the reaction mixture, and then adding the dihalogeno aromatic compound and the sulfidizing agent, and optionally a polyhalogeno aromatic compound, in the organic polar solvent to react with each other, and controlling the amount of water in the reaction system to be in the range of 0.02 to 0.5 moles per mole of the organic polar solvent (see JP-A-07-228699). Particularly preferred is a copolymer obtained by a method in which a dihalogenoaromatic compound and, if necessary, a polyhalogenoaromatic compound or other copolymerization component are added in the presence of an alkali metal sulfide and an aprotic polar organic solvent, and an alkali metal hydrosulfide and an organic acid alkali metal salt are reacted while controlling the amount of organic acid alkali metal salt in the range of 0.01 to 0.9 mol per mol of the sulfur source and the amount of water in the reaction system to 0.02 mol or less per mol of the aprotic polar organic solvent (see WO 2010 / 058713 pamphlet).Specific examples of the dihalogeno aromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p,p'-dihalodiphenyl ether, 4,4'-dihalobenzophenone ... Examples of the polyhalogenoaromatic compounds include 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene, etc. The halogen atoms contained in the above compounds are preferably chlorine atoms or bromine atoms.

[0035] The method for post-treating the reaction mixture containing the PAS resin obtained by the polymerization step is not particularly limited, and examples thereof include: (post-treatment 1) after the completion of the polymerization reaction, first, distilling off the solvent from the reaction mixture either as is or after adding an acid or a base under reduced pressure or normal pressure, and then washing the solid obtained after the solvent distillation once or twice or more times with a solvent such as water, the reaction solvent (or an organic solvent having a similar solubility to the low-molecular-weight polymer), acetone, methyl ethyl ketone, or alcohols, followed by neutralization, washing with water, filtering, and drying; or (post-treatment 2) after the completion of the polymerization reaction, adding a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, or aliphatic hydrocarbons (soluble in the polymerization solvent used and poorly soluble in at least the PAS) to the reaction mixture. Examples of such methods include: (1) adding a solvent (which is a solvent for polymerization) as a precipitant to the reaction mixture, allowing solid products such as PAS and inorganic salts to precipitate, followed by filtration, washing, and drying; (2) adding a reaction solvent (or an organic solvent having equivalent solubility to the low-molecular-weight polymer) to the reaction mixture after the polymerization reaction is complete, stirring the mixture, filtering to remove the low-molecular-weight polymer, washing once or twice or more times with a solvent such as water, acetone, methyl ethyl ketone, or an alcohol, followed by neutralization, washing with water, filtering, and drying; (3) adding water to the reaction mixture after the polymerization reaction is complete, washing with water, filtering, and optionally adding an acid during the water washing step to perform an acid treatment, followed by drying; and (4) filtering the reaction mixture after the polymerization reaction is complete, and optionally washing once or twice or more times with the reaction solvent, followed by further washing with water, filtering, and drying. Among these methods, (4) is preferred because it enables the production of a PAS resin having carboxyl groups at the molecular terminals of the PAS resin.

[0036] In the post-treatment methods exemplified above in (Post-treatment 1) to (Post-treatment 5), the PAS resin may be dried in a vacuum, in air, or in an inert gas atmosphere such as nitrogen.

[0037] In the PAS resin composition according to the present embodiment, the blending amount of the PAS resin (A) is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and preferably 80 parts by mass or less, more preferably 70 parts by mass or less, based on 100 parts by mass of the resin composition. This range is preferable because the resin composition has good processability and the molded article has excellent chemical resistance, toughness, etc.

[0038] The PAS resin (A) used in this embodiment can be a PAS resin newly polymerized by the above method, or a recycled PAS resin. For example, PAS resin recovered from a PAS resin composition or a PAS resin molded article can be used. Specifically, a PAS resin obtained by heating a PAS resin composition or a PAS resin molded article in an organic polar solvent to dissolve the PAS contained therein and then performing the above-described post-treatment can be used. Mechanically pulverized PAS resin compositions or PAS resin molded articles can also be used as PAS resins. Specifically, sprues or runners generated during the production of molded articles, recovered non-standard molded articles, or pulverized molded articles once used as products can be used. In this case, pulverized PAS resin compositions or PAS resin molded articles containing components other than PAS resin can also be used. However, from the perspective of mechanical strength, the PAS resin content is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, and even more preferably 98 parts by mass or more.

[0039] <Carbon-based material (B) other than carbon fiber> The PAS resin composition according to this embodiment is composed of a carbon-based material (B) other than carbon fiber as an essential component. In the present disclosure, carbon fiber is included in the fibrous filler (C) but is not included in the carbon-based material (B).

[0040] The carbon-based material (B) other than carbon fiber that can be applied to this embodiment is not particularly limited as long as it is a carbon-based material other than carbon fiber, and known materials can be used. Examples include carbon black such as furnace black, thermal black, channel black, ketjen black, gas black, oil black, and acetylene black; graphite such as amorphous graphite, spherical graphite, flake graphite, scaly graphite, swollen graphite, and expanded graphite; carbon nanotubes such as single-wall nanotubes and multi-wall nanotubes; and fullerenes. The graphite may be either natural graphite or artificial graphite, and its shape is not limited. Furthermore, carbon nanotubes can generally be produced by laser ablation, arc thermal CVD, plasma CVD, gas-phase processes, combustion processes, etc., but carbon nanotubes produced by any method can be used in the present disclosure. Furthermore, the surfaces and ends of carbon nanotubes may be modified with functional groups to increase their affinity with resins, as long as the effects of the present invention are not impaired. For example, they may be functionalized with hydroxyl groups, carboxyl groups, or amino groups using an acid or alkali. Furthermore, carbon nanotubes may be pre-treated with a coupling agent, such as an isocyanate compound, an organic silane compound, an organic titanate compound, or an epoxy compound. Among these, carbon black is preferred from the viewpoint of stable conductivity, and furnace black is particularly preferred.

[0041] The carbon-based material (B) other than carbon fiber that can be applied to this embodiment has a pH of 6 or more, preferably greater than 6. This range is preferred because the resin composition or molded article is less likely to corrode objects in contact with it (excellent corrosion resistance). The upper limit of the pH is not particularly limited, but is preferably 12 or less, more preferably 10 or less. The pH of the carbon-based material (B) other than carbon fiber is a value measured using a glass electrode pH meter in accordance with JIS K 6221 for a mixed solution of the carbon-based material (B) other than carbon fiber and distilled water.

[0042] Examples of commercially available carbon-based materials (B) other than carbon fibers include "CNP15" manufactured by Ito Graphite Industries Co., Ltd., "Denka Black" manufactured by Denka Co., Ltd., "3400B" manufactured by Mitsubishi Chemical Corporation, and "Ketjen Black" manufactured by Lion Specialty Chemicals Co., Ltd.

[0043] When furnace black is used as the carbon-based material (B) other than the carbon fiber, the DBP absorption is 100 cm ３ / 100g or more is preferable, and 110cm ３ It is more preferable that the DBP absorption of furnace black is 100 or more. This range is preferable because it provides an excellent balance between conductivity and fluidity. The DBP absorption of furnace black is a value measured in accordance with the method described in JIS K6221.

[0044] When furnace black is used as the carbon-based material (B) other than carbon fiber, the primary particle diameter is preferably 60 nm or less, more preferably 50 nm or less. This range is preferred because it provides an excellent balance between conductivity and fluidity. The primary particle diameter is an average value measured for at least five samples by observation using a transmission electron microscope.

[0045] When graphite is used as the carbon-based material (B) other than carbon fiber, the average particle size is preferably 5 to 400 μm. Within this range, the resin composition can exhibit excellent dispersibility. From the same viewpoint, the average particle size is more preferably 10 μm or more, even more preferably 15 μm or more, and more preferably 350 μm or less, even more preferably 300 μm or less. The average particle size is the average particle size (D ５０ )

[0046] In the PAS resin composition according to the present embodiment, the blending amount of the carbon-based material (B) other than carbon fiber is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 80 parts by mass or less, more preferably 60 parts by mass or less, relative to 100 parts by mass of the PAS resin (A). This range is preferable because the resin composition has good processability and the molded article has excellent electrical conductivity, mechanical strength, and dimensional stability.

[0047] <Fibrous Filler (C)> The PAS resin composition according to this embodiment can further contain a fibrous filler (C) as an optional component for the purpose of improving mechanical strength and processability during molding. The fibrous filler (C) applicable to this embodiment is not particularly limited, and known fillers can be used. For example, fibrous fillers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, and natural fibers can be used.

[0048] The fibrous filler (C) used in the present invention can also be treated with a surface treatment agent or a sizing agent, if necessary. This is preferable because it improves adhesion to the PAS resin (A) and improves the mechanical strength of the resulting resin composition and molded article. Examples of the surface treatment agent or sizing agent include at least one polymer selected from the group consisting of silane compounds having functional groups such as amino groups, epoxy groups, isocyanate groups, and vinyl groups, titanate compounds, acrylic resins, urethane resins, polyether resins, and epoxy resins. In particular, when glass fibers are used, a urethane resin is preferred in order to prevent excessive defibration during processing. When the surface treatment agent or sizing agent contains a urethane resin, its content is not particularly limited, but is preferably in the range of 35% by mass or less, and more preferably 20% by mass or less, in terms of moist heat resistance, etc.

[0049] When the fibrous filler (C) is blended into the PAS resin composition according to the present embodiment, the blending amount is not particularly limited, but is preferably in the range of 20 parts by mass or more, more preferably 35 parts by mass or more, to 80 parts by mass or less, more preferably 60 parts by mass or less, relative to 100 parts by mass of the PAS resin (A). In such a range, the resin composition has good processability and the molded article has excellent mechanical strength, which is preferable.

[0050] <Silane Coupling Agent (D)> The PAS resin composition according to this embodiment may further contain a silane coupling agent (D) as an optional component for the purpose of improving mechanical strength and reducing burrs during molding.

[0051] The silane coupling agent (D) applicable to this embodiment is not particularly limited as long as it does not impair the effects of the present invention. However, preferred examples include silane coupling agents having a functional group that reacts with a carboxyl group, such as an epoxy group, an isocyanato group, an amino group, or a hydroxyl group. Examples of such silane coupling agents include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane; amino group-containing alkoxysilane compounds such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane; and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane.

[0052] In this embodiment, the silane coupling agent (D) is not an essential component, but when it is added, its amount is not particularly limited as long as it does not impair the effects of the present invention. For example, it is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of the PAS resin (A). Within this range, the resin composition has good moldability, particularly releasability, and the molded article exhibits excellent adhesion to the epoxy resin while also improving mechanical strength, which is preferable.

[0053] <Thermoplastic elastomer (E)> The PAS resin composition according to this embodiment may further contain a thermoplastic elastomer (E) as an optional component for the purpose of improving mechanical strength.

[0054] Examples of the thermoplastic elastomer (E) applicable to this embodiment include polyolefin elastomers, fluorine elastomers, and silicone elastomers, among which polyolefin elastomers are preferred. When these elastomers are added, their amount is not particularly limited as long as it does not impair the effects of the present invention, but is preferably in the range of 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, to preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of the PAS resin (A). This range is preferred because it improves the impact resistance of the resulting PAS resin composition.

[0055] Examples of the polyolefin elastomer include a homopolymer of an α-olefin, a copolymer of two or more α-olefins, and a copolymer of one or more α-olefins with a vinyl polymerizable compound having a functional group. Examples of the α-olefin include α-olefins having 2 or more to 8 carbon atoms, such as ethylene, propylene, and 1-butene. Examples of the functional group include a carboxyl group, an acid anhydride group (—C(═O)OC(═O)—), an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, and an oxazoline group. Examples of the vinyl polymerizable compound having a functional group include one or more of vinyl acetate; α,β-unsaturated carboxylic acids such as (meth)acrylic acid; alkyl esters of α,β-unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, and butyl acrylate; metal salts of α,β-unsaturated carboxylic acids such as ionomers (metals include alkali metals such as sodium, alkaline earth metals such as calcium, and zinc); glycidyl esters of α,β-unsaturated carboxylic acids such as glycidyl methacrylate; α,β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and derivatives of the above α,β-unsaturated dicarboxylic acids (monoesters, diesters, and acid anhydrides). The above-mentioned thermoplastic elastomers may be used alone or in combination of two or more.

[0056] The PAS resin composition according to this embodiment may contain fillers (hereinafter referred to as "other fillers") other than the carbon-based material (B) other than carbon fiber and the fibrous filler (C) as optional components, provided that the effects of the present invention are not impaired. Examples of such fillers include fillers of various shapes, such as plate-like and powder-like. Specific examples include glass flakes, clay, pyrophyllite, bentonite, sericite, mica, attapulgite, ferrite, calcium silicate, zeolite, boehmite, silica, quartz powder, glass beads, glass powder, silicates such as calcium silicate, aluminum silicate, and diatomaceous earth, metal oxides such as iron oxide, titanium oxide, zinc oxide, and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, fumed silica, silicon carbide, silicon nitride, boron nitride, various metal powders, and plant-derived fillers such as cocoa husk.

[0057] In this embodiment, other fillers are not essential components, but when blended, the blending amount is not particularly limited as long as it does not impair the effects of the present invention. The blending amount of other fillers is, for example, preferably 1 part by mass or more, more preferably 5 parts by mass or more, to preferably 600 parts by mass or less, more preferably 200 parts by mass or less, per 100 parts by mass of the PAS resin (A). Within such a range, the resin composition exhibits good moldability and the molded product has excellent mechanical strength, which is preferable.

[0058] Furthermore, in addition to the above components, the PAS resin composition according to this embodiment may further contain synthetic resins (hereinafter simply referred to as synthetic resins) such as polyester resins, polyamide resins, polyimide resins, polyetherimide resins, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, polyetherketone resins, polyarylate resins, polyethylene resins, polypropylene resins, polyethylenetetrafluoroethylene resins, polyethylenedifluoroethylene resins, polystyrene resins, ABS resins, epoxy resins, phenolic resins, urethane resins, and liquid crystal polymers as optional components depending on the application. In particular, the incorporation of fluorine-based resins is preferred because it further improves sliding properties. Although the synthetic resin is not an essential component in the present invention, when it is incorporated, its incorporation ratio is not particularly limited as long as it does not impair the effects of the present invention. Furthermore, since the ratio varies depending on the respective purposes and cannot be generally defined, the ratio of the synthetic resin incorporated into the resin composition according to this embodiment may be, for example, in the range of 5 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the PAS resin (A). In other words, the ratio of the PAS resin to the total of the PAS resin (A) and the synthetic resin is preferably in the range of (100 / 115) or more, more preferably in the range of (100 / 105) or more, on a mass basis.

[0059] The PAS resin composition according to the present embodiment may also contain other known and commonly used additives as optional components, as needed, such as colorants, antistatic agents, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, foaming agents, flame retardants, flame retardant assistants, rust inhibitors, mold release agents (metal salts or esters of fatty acids having 18 to 30 carbon atoms, including stearic acid or montanic acid, and polyolefin waxes such as polyethylene), antibacterial agents, and antiviral agents. These additives are not essential components, and may be used in an amount, for example, preferably 0.01 part by mass or more, and preferably 1,000 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the PAS resin (A), as appropriate for the purpose and application so as not to impair the effects of the present invention.

[0060] The PAS resin composition of the present disclosure is characterized by a flexural modulus of 18 GPa or less. A flexural modulus of 16 GPa or less is preferable, and a flexural modulus of 15 GPa or less is even more preferable. Within this range, PAS resin molded articles exhibit excellent adhesion when combined with metal components, resulting in composite materials with excellent electrical conductivity. To achieve this flexural modulus within this range, for example, a method can be used in which the melt viscosity (V6) of the PAS resin is adjusted to within a range of 50 to 2000 Pa·s depending on the PAS resin content in the resin composition. For example, when a large amount of components other than PAS resin is blended, the thermal conductivity of the resin composition tends to increase, thereby increasing the crystallization rate. Therefore, the melt viscosity of the PAS resin can be increased to adjust the crystallization behavior. Note that the method for adjusting the weld strength is not limited to the above-described method. The flexural modulus in the present disclosure refers to the flexural modulus measured in accordance with the ISO 178 measurement method using a dumbbell-shaped injection-molded article conforming to the Type A test piece specified in ISO 20753, and can be measured by the method described in the Examples.

[0061] <Method for producing PAS resin composition> The method for producing a PAS resin composition according to this embodiment is a method for producing a PAS resin composition, comprising a step of blending a PAS resin (A) and a carbon-based material (B) other than carbon fiber as essential components, and melt-kneading the blended PAS resin (A) at a temperature equal to or higher than the melting point of the PAS resin (A), characterized in that the melt viscosity (V6) of the PAS resin (A) is 200 Pa s or less, the pH of the carbon-based material (B) other than carbon fiber is 6 or more, the blending amount of the carbon-based material (B) other than carbon fiber is 5 to 80 parts by mass per 100 parts by mass of the PAS resin (A), and the flexural modulus is 18 GPa or less. These are described in detail below.

[0062] The method for producing a PAS resin composition according to this embodiment includes a step of blending the essential components and melt-kneading them in a temperature range equal to or higher than the melting point of the PAS resin (A). More specifically, the PAS resin composition according to this embodiment is obtained by blending the essential components and, if necessary, other optional components. The method for producing the resin composition used in the present invention is not particularly limited, but examples thereof include a method of blending the essential components and, if necessary, optional components, and melt-kneading them, and more specifically, a method of uniformly dry-mixing them in a tumbler or Henschel mixer, if necessary, and then feeding them into a twin-screw extruder and melt-kneading them.

[0063] The melt-kneading can be carried out by heating to a temperature range in which the resin temperature is equal to or higher than the melting point of the PAS resin (A), preferably equal to or higher than the melting point + 10°C, more preferably equal to or higher than the melting point + 10°C, even more preferably equal to or higher than the melting point + 20°C, to a temperature range in which the resin temperature is equal to or lower than the melting point + 100°C, more preferably equal to or lower than the melting point + 50°C.

[0064] From the viewpoint of dispersibility and productivity, the melt-kneading machine is preferably a twin-screw kneading extruder. For example, it is preferable to melt-knead while appropriately adjusting the resin component discharge rate in the range of 5 to 500 (kg / hr) and the screw rotation speed in the range of 50 to 500 (rpm). It is even more preferable to melt-knead under conditions where the ratio (discharge rate / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). Furthermore, the addition and mixing of the components to the melt-kneading machine may be carried out simultaneously or in portions. For example, when adding the essential component PA fiber (B) or other fibrous fillers as needed, it is preferable from the viewpoint of dispersibility to feed them into the twin-screw kneading extruder through a side feeder. The position of the side feeder is preferably such that the ratio of the distance from the extruder's resin input section (top feeder) to the side feeder to the total screw length of the twin-screw kneading extruder is 0.1 or more, more preferably 0.3 or more. Moreover, the ratio is preferably 0.9 or less, and more preferably 0.7 or less.

[0065] The PAS resin composition according to the present embodiment obtained by melt-kneading in this manner is a molten mixture containing the essential components, optional components added as needed, and components derived therefrom. Therefore, the PAS resin composition according to the present embodiment has a morphology in which the PAS resin (A) forms a continuous phase and the other essential components and optional components are dispersed.

[0066] After the melt-kneading, the PAS resin composition according to the present embodiment is preferably processed into a form such as pellets, chips, granules, or powder by a known method, for example, by extruding the molten resin composition into a strand shape, and then pre-dried at a temperature in the range of 100 to 150°C as needed.

[0067] <PAS resin molded article, manufacturing method of PAS resin molded article> The molded article according to this embodiment is obtained by melt-molding a PAS resin composition. Furthermore, the manufacturing method of the molded article according to this embodiment includes a step of melt-molding the PAS resin composition. Therefore, the molded article according to this embodiment has a morphology in which the PAS resin (A) forms a continuous phase and other essential components and optional components are dispersed. Because the PAS resin composition has such a morphology, a molded article having excellent thermal conductivity and mechanical strength can be obtained.

[0068] The PAS resin composition according to this embodiment can be subjected to various molding processes, such as injection molding, compression molding, extrusion molding of composites, sheets, and pipes, pultrusion molding, blow molding, and transfer molding. However, due to its excellent mold releasability, it is particularly suited to injection molding applications. When molding by injection molding, the molding conditions are not particularly limited, and molding can be performed using a typical method. For example, the PAS resin composition can be melted in an injection molding machine at a resin temperature in a range equal to or higher than the melting point of the PAS resin (A), preferably in a range of 10°C above the melting point, more preferably in a range of 10°C to 100°C above the melting point, and even more preferably in a range of 20°C to 50°C above the melting point, and then the resulting resin can be injected into a mold through a resin discharge port and molded. The mold temperature can also be set within a known temperature range, for example, from room temperature (23°C) to 300°C, preferably 130°C to 190°C.

[0069] The method for producing a molded article according to this embodiment may include a step of annealing the molded article. The optimal conditions for the annealing treatment are selected depending on the application or shape of the molded article. The annealing temperature is in a temperature range above the glass transition temperature of the PAS resin (A), preferably in a temperature range above the glass transition temperature + 10°C, and more preferably in a temperature range above the glass transition temperature + 30°C. The annealing time is preferably in the range of 260°C or less, and more preferably in the range of 240°C or less. The annealing time is not particularly limited, but is preferably in the range of 0.5 hours or more, more preferably in the range of 1 hour or more. The annealing time is preferably in the range of 10 hours or less, and more preferably in the range of 8 hours or less. This range is preferable because it not only reduces distortion in the resulting molded article and improves the crystallinity of the resin, but also further improves thermal conductivity, mechanical strength, and other properties. The annealing treatment may be performed in air, but is preferably performed in an inert gas such as nitrogen gas.

[0070] The molded article according to this embodiment includes a remolded article obtained by reusing a molded article obtained by melt-molding the PAS resin composition. Specifically, the molded article includes, for example, a sprue or runner generated during the production of a molded article, a recovered non-standard molded article, or a molded article once used as a product, which is cleaned as necessary, pulverized, and then melt-molded again at a temperature equal to or higher than the melting point of the PAS resin. When reusing, it is preferable to mix the pulverized molded article with the PAS resin composition from the viewpoint of mechanical strength. The size of the molded article to be pulverized is not particularly limited, but from the viewpoints of mixability and processability, it is preferable that the size be approximately the same as that of the PAS resin composition to be mixed. Furthermore, the mixing ratio of the pulverized molded article to 100 parts by mass of the PAS resin composition is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 20 parts by mass or less. Within this range, recyclability can be improved without impairing the effects of the PAS resin composition of the present disclosure.

[0071] <Composite and method for manufacturing the composite> The composite according to this embodiment is formed by joining the molded article described above to a metal member. The method for manufacturing the composite according to this embodiment includes the steps of manufacturing the molded article by the method described above and joining the obtained molded article to a metal member.

[0072] The metal member applicable to this embodiment is not particularly limited as long as it does not impair the effects of the present invention, and known metal members can be used, such as aluminum, copper, stainless steel, magnesium, iron, titanium, or alloys containing any of these. More specifically, examples of the alloy include iron and alloys containing iron as the main component, such as stainless steel and steel, i.e., 20% by mass or more, more preferably 50% by mass or more, and even more preferably 80% by mass, with carbon, silicon, manganese, chromium, tungsten, molybdenum, phosphorus, titanium, vanadium, nickel, zirconium, boron, etc. (hereinafter referred to as iron alloys); aluminum and alloys containing aluminum as the main component and also containing copper, manganese, silicon, magnesium, zinc, nickel, etc. (hereinafter referred to as aluminum alloys); magnesium and alloys containing magnesium as the main component and also containing zinc, aluminum, zirconium, etc. (hereinafter referred to as magnesium alloys); copper and alloys containing copper as the main component and also containing zinc, tin, phosphorus, nickel, magnesium, silicon, chromium, etc. (hereinafter referred to as copper alloys); and titanium and alloys containing titanium as the main component and also containing copper, manganese, silicon, magnesium, zinc, nickel, etc. (hereinafter referred to as titanium alloys). Among these, iron, iron alloys, aluminum alloys, magnesium alloys, copper alloys, and titanium alloys are more preferred, and iron alloys, aluminum alloys, and magnesium alloys are even more preferred. The shape of the metal member is not particularly limited, and examples include those processed into, for example, a flat plate, curved plate, rod, cylinder, or block shape by plastic processing such as pressing, punching, cutting, polishing, or thinning processing such as electric discharge machining. Alternatively, it may be a film-like material such as a metal foil.

[0073] The metal member may also be surface-roughened. Known surface roughening methods can be used, including (1) immersion in an aggressive aqueous solution or suspension, (2) anodizing, and (3) mechanical cutting using blasting or laser processing. Among these, (1) immersion in an aggressive aqueous solution or suspension or (2) anodizing is particularly preferred as a surface roughening method for metal members. When surface-treating the metal member, it is preferable to process the metal member into a desired shape by cutting, plastic processing using a press, or other such processing, such as punching, cutting, grinding, or electrical discharge machining, before forming the finely textured surface.

[0074] A primer layer may be formed on the surface of a metal member that has undergone a metal surface treatment. The material constituting the primer layer is not particularly limited, but it is typically a primer resin material containing a resin component. The primer resin material is not particularly limited, and known materials can be used. Specific examples include known polyolefin-based primers, epoxy-based primers, and urethane-based primers. The primer layer can be formed by applying a solution or emulsion of the primer resin material to the metal member that has undergone the surface treatment. Examples of solvents used to prepare the solution include toluene, methyl ethyl ketone (MEK), and dimethylphosphoramide (DMF). Examples of emulsion media include aliphatic hydrocarbon media and water.

[0075] The method for joining the resin molded article of the present disclosure to a metal member is not particularly limited as long as it does not impair the effects of the present invention, and known methods and devices can be used. Examples include a method of joining the resin composition of the present disclosure to a metal member by melt-molding it, a method of welding the molded article of the present disclosure to a metal member, a method of caulking the molded article of the present disclosure to a metal member, and a method of mechanically joining the molded article of the present disclosure to a metal member.

[0076] As a method for joining a metal member by melt molding the resin composition of the present disclosure, a so-called insert molding method can be used, in which the metal member is inserted into a mold of an injection molding machine and then injection molded onto the metal member using the resin composition of the present disclosure. The apparatus and manufacturing method for the insert molding method are not particularly limited, and commercially available apparatus can be used, or the method can be carried out according to a conventional method.

[0077] The method for welding the molded article of the present disclosure to a metal member includes contacting the molded article of the present disclosure with the metal member and heating them to bond them, or heating them, bringing them into contact, bonding them, and then cooling them. Specific examples include hot plate welding, vibration welding, infrared welding, infrared vibration welding, ultrasonic welding, high-frequency welding, induction heating welding, rotary welding, laser welding, hot pressing, hot embossing, and friction stir welding. Commercially available equipment and manufacturing methods can be used for these joining methods, or conventional methods can be used.

[0078] A method for crimping the molded article of the present disclosure and a metal member includes passing a rivet through a hole in the molded article of the present disclosure and a hole in the metal member, and deforming the rivet to fix them. Specific examples include press crimping, spin crimping, and heat crimping. Commercially available equipment and manufacturing methods for these joining methods can be used, or they can be performed according to conventional methods. Examples of methods for mechanically joining the molded article of the present disclosure and a metal member include mechanical fastening using screws, pins, shafts, bolts, nuts, clamps, etc., and fixing using a fitting structure.

[0079] <Applications> The PAS resin molded article according to this embodiment has excellent toughness, and therefore when combined with a metal member or another resin member, it has high adhesion, can reduce heat and electrical conduction losses at the interface, and furthermore, the interface has excellent long-term stability. Therefore, it is suitable for use as a component that constitutes a composite with a metal member or a resin member. Furthermore, the composite according to this embodiment is characterized by excellent conductivity and long-term stability, and is therefore particularly suitable for use in conductive parts and electromagnetic wave shielding parts. Specifically, it can be used for conductive parts such as electrode peripheral parts for lithium-ion batteries, carrier trays, battery parts, conductive reels, and conductive pallets, as well as electromagnetic wave shielding parts such as electronic device cases, inverter cases, ECU housings, and medical device cases. Furthermore, the molded article and composite according to this embodiment can be used not only for conductive parts and electromagnetic wave shielding parts, but also for general applications such as the following. For example, protective and supporting members for box-shaped integrated modules of electric and electronic components, multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystal displays, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, electric and electronic components such as computer-related parts; VTR parts, television parts, irons, headsets Home and office electrical appliance parts such as air dryers, rice cooker parts, microwave oven parts, audio parts, audio / visual equipment parts such as laser discs, compact discs, DVD discs, and Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, and plumbing equipment parts such as water heaters, bath water volume and temperature sensors; machine-related parts such as office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, and typewriters; optical equipment and precision machinery-related parts such as microscopes, binoculars, cameras, and watches;Alternator terminals, alternator connectors, brush holders, slip rings, IC regulators, light dimmer potentiometer bases, relay blocks, inhibitor switches, exhaust gas valves and other valves, fuel-related, exhaust system and intake system pipes, air intake nozzle snorkels, intake manifolds, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, temperature sensors, air flow meters, brake pad wear sensors, air conditioner thermostat bases, heating hot air flow control valves, radiators Examples of automotive and vehicle related parts include brush holders for motor motors, water pump impellers, turbine vanes, wiper motor related parts, distributors, starter switches, ignition coils and bobbins, motor insulators, motor rotors, motor cores, starter relays, transmission wire harnesses, windshield washer nozzles, air conditioner panel switch boards, fuel-related electromagnetic valve coils, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and various other applications are also possible;

[0080] The present invention will be described below using examples and comparative examples, but is not limited to these examples. Unless otherwise specified, "%" and "parts" are based on mass.

[0081] Examples 1 to 10 and Comparative Examples 1 to 6: Each material was blended according to the composition and blending amounts listed in Table 1. These blended materials were then fed into a vented twin-screw extruder "TEX-30α (product name)" manufactured by The Japan Steel Works, Ltd., and melt-kneaded at a resin component discharge rate of 30 kg / hr, a screw rotation speed of 200 rpm, and a set resin temperature of 310°C to obtain pellets of the resin composition. Glass fiber and polyamide fiber were fed through a side feeder (S / T ratio 0.5), while the other materials were pre-mixed uniformly in a tumbler and then fed through the top feeder. The resulting pellets of the resin composition were dried in a gear oven at 140°C for 2 hours and then injection-molded to prepare various test pieces, which were then subjected to the following tests.

[0082] <Evaluation>

[0083] (1) Measurement of Charpy Impact Strength The pellets obtained in each Example and Comparative Example were fed into a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) set at a cylinder temperature of 310°C, and injection molding was carried out using an ISO Type 1A dumbbell specimen molding die with the die temperature adjusted to 140°C to obtain ISO Type-A dumbbell specimens. The resin was injected from a single gate so that the test specimens did not include welds. The central portion of the dumbbell-shaped test specimen was cut into a rod shape of 80 mm in length, 10 mm in width, and 4 mm in thickness, and notched to prepare an impact resistance test specimen. A Charpy impact test was carried out in accordance with ISO179-1 / 1eA to measure the impact strength (kJ / mm ２ The results are shown in Tables 1 and 2.

[0084] (2) Measurement of flexural modulus Using the same ISO Type-A dumbbell specimens as in (1) as test specimens, the flexural modulus (GPa) was measured in accordance with ISO 178. The results are shown in Tables 1 and 2.

[0085] (3) Volume resistivity measurement The volume resistivity was measured using the "Loresta AX MCP-T370" manufactured by Nitto Seiko Analytech Co., Ltd. (upper limit of measurement: 10 ６The volume resistivity of each test piece was measured using a resistivity tester (Ω cm) under conditions of room temperature 21°C and humidity 67% RH in accordance with JIS K 7194 "Test method for resistivity of conductive plastics by the four-probe method." The test pieces were prepared by feeding the pellets obtained in each example and comparative example into an injection molding machine (SE-75D-HP) manufactured by Sumitomo Heavy Industries, Ltd., with a cylinder temperature set to 310°C, and injection molding using a plate molding mold whose mold temperature was adjusted to 140°C, and molding them into a plate shape (80 mm x 50 mm x 2 mmt). The results are shown in Tables 1 and 2.

[0086] (4) Measurement of Electrical Resistance of Molded Articles The pellets obtained in each Example and Comparative Example were fed into a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) with a cylinder temperature set to 310 ° C., and injection molding was performed using a molding die with a mold temperature controlled at 140 ° C. to obtain a molded article measuring 20 mm long x 40 mm wide x 1 mm thick. The obtained molded article was stacked in the thickness direction with two 30 mm x 50 mm x 1 mm aluminum alloy (A1050) plates, and pressed with a pressure of 30 kPa in a state where the entire molded article was in contact with the aluminum plate. Electrodes were attached to each aluminum alloy plate, and the electrical resistance value (kΩ) when a current of 0.1 mA was applied was measured using a Hioki EE RM3545 resistance meter. 30 plates were measured, and the average of the measured resistance values ​​was taken as the electrical resistance value (kΩ) of the molded article, and the standard deviation divided by the average value was evaluated as the variation. The results are shown in Tables 1 and 2.

[0087] (5) Long-term stability evaluation value: The same molded article as in (4) and an aluminum plate were pressed and fixed at 10 kPa and left to stand for 6 months in a thermo-hygrostat at 85°C and 95% RH. After standing, the aluminum plate was subjected to a method using nitric acid according to the chemical corrosion product removal method of JIS Z 2371 to remove corrosion products, and the maximum pit depth on the contact surface with the molded article was measured using a three-dimensional measuring machine (Keyence VR-6000). The smaller the maximum pit depth, the better the long-term stability. The results are shown in Tables 1 and 2.

[0088] (6) Determination of Carboxyl Group Content of PPS Resin Each PPS resin used in each Example and Comparative Example was pressed at 350°C under a load of 10 MPa for 60 seconds, and then rapidly cooled to 25°C over 60 seconds to prepare an amorphous film. The obtained amorphous film was measured using a Fourier transform infrared spectrometer (hereinafter abbreviated as "FT-IR device"). In the infrared absorption spectrum, the carboxyl group content at 630.6 cm －１ Absorbance of 1705 cm －１ The relative intensity of absorbance at each wavelength was determined, and the carboxyl group content in the measurement sample (hereinafter abbreviated as "total carboxyl group content") was determined using a calibration curve prepared by a method described separately below. The results are shown in Tables 1 and 2. The carboxyl group content is expressed as the number of moles per 1 g of resin mixture, and its unit is μmol / g. The calibration curve was prepared as follows. First, a predetermined amount of 4-chlorophenylacetic acid was added to a PAS resin prepared without acid treatment so as to contain carboxylate salts at the molecular ends, and the mixture was thoroughly mixed. Then, a film similar to that described above was prepared and measured using an FT-IR device. A calibration curve was prepared by plotting the relative intensity ratio of absorbance at the two wavelengths against the carboxyl group content calculated from the amount of 4-chlorophenylacetic acid added.

[0089]

[0090]

[0091] The blending ratios of the blending components in Tables 1 and 2 were as follows: PPS resin A-1: ​​PPS resin (melt viscosity (V6) 10 Pa s, zeta potential -58 mV, carboxyl group amount 30 μmol / g) A-2: PPS resin (melt viscosity (V6) 50 Pa s, zeta potential -64 mV, carboxyl group amount 30 μmol / g) A-3: PPS resin (melt viscosity (V6) 200 Pa s, zeta potential -63 mV, carboxyl group amount 30 μmol / g) A-4: PPS resin (melt viscosity (V6) 400 Pa s, zeta potential -60 mV, carboxyl group amount 20 μmol / g)

[0092] Carbon-based material b-1: carbon black, "MA-100" manufactured by Mitsubishi Chemical Corporation, pH 3.5, DBP absorption capacity 100 cm３ / 100g, average primary particle diameter 24nm B-2: Carbon black, "#4400" manufactured by Tokai Carbon Co., Ltd., pH 6, DBP absorption 138cm ３ / 100g, average primary particle diameter 38nm B-3: Carbon black, "Ketjenblack" manufactured by Lion Specialty Chemicals Co., Ltd., pH 9, DBP absorption 360cm ３ / 100g, average primary particle size 40nm B-4: Flake graphite, "CNP15" manufactured by Ito Graphite Industries Co., Ltd., pH 8, average particle size 15μm B-5: Artificial graphite, "AGB-604" manufactured by Ito Graphite Industries Co., Ltd., pH 8, average particle size 55μm B-6: Expanded graphite, "EC500" manufactured by Ito Graphite Industries Co., Ltd., pH 8, average particle size 25μm

[0093] C-1: Carbon fiber, "HT C702" manufactured by Teijin Limited, average fiber length 6 mm. C-2: Glass fiber, "T-717H" manufactured by Nippon Electric Glass Co., Ltd., fiber length 3 mm, average diameter 10 μm.

[0094] D-1: Silane coupling agent, "XIAMETER (registered trademark) OFS-6040" manufactured by The Dow Chemical Company E-1: Thermoplastic elastomer (a copolymer of ethylene:methyl acrylate:glycidyl methacrylate = 64 mol %:30 mol %:6 mol %) F-1: Calcium carbonate, "Calcium Carbonate Grade 1" manufactured by Sankyo Flour Milling Co., Ltd.

[0095] Comparing the Examples and Comparative Examples in Tables 1 and 2, the molded articles melt-molded from the resin compositions of the Examples had excellent Charpy impact strength and low volume resistivity, and the composites of the Examples had small electrical resistance values ​​and variations, and also had excellent long-term stability. Compared to the Examples, Comparative Example 1 had poor long-term stability, Comparative Example 2 had high electrical resistance, Comparative Example 3 had poor toughness, Comparative Example 4 had poor processability, and Comparative Examples 5 and 6 had large variations in electrical resistance, and did not meet all the required performance requirements.

Claims

1. A polyarylene sulfide resin composition comprising a polyarylene sulfide resin (A) and a carbon-based material other than carbon fiber (B) as essential components, wherein the polyarylene sulfide resin (A) has a melt viscosity (V6) of 200 Pa·s or less, the carbon-based material other than carbon fiber (B) has a pH of 6 or more, the amount of the carbon-based material other than carbon fiber (B) is 5 to 80 parts by mass per 100 parts by mass of the polyarylene sulfide resin (A), and the flexural modulus is 18 GPa or less. (The melt viscosity (V6) represents the melt viscosity measured after holding the composition for 6 minutes using a flow tester at a temperature of 300°C, a load of 1.96 MPa, and an orifice having an orifice length to orifice diameter ratio of 10 / 1.) 2. The polyarylene sulfide resin composition according to claim 1, further comprising a fibrous filler (C).

3. The polyarylene sulfide resin composition according to claim 2, wherein the amount of the fibrous filler (C) is 20 to 80 parts by mass per 100 parts by mass of the polyarylene sulfide resin (A).

4. The carbon-based material (B) other than the carbon fiber contains furnace black, and the DBP absorption of the furnace black is 100 cm ３ 3. The polyarylene sulfide resin composition according to claim 1, wherein the polyarylene sulfide resin composition has a molecular weight of 1000 to 10000 g / mol and a primary particle size of 60 nm or less.

5. The polyarylene sulfide resin composition according to claim 1 or 2, wherein the carbon-based material (B) other than carbon fibers contains graphite having an average particle size of 5 to 400 μm.

6. The polyarylene sulfide resin composition according to claim 1 or 2, wherein the polyarylene sulfide resin (A) has a zeta potential of -70 mV or more at pH 7.8 to 8.2 as measured by a streaming potential method.

7. A molded article obtained by melt molding the polyarylene sulfide resin composition according to claim 1 or 2.

8. A composite member formed by joining the molded article according to claim 7 to a metal member.

9. A secondary battery member comprising the composite material according to claim 8.

10. A method for producing a polyarylene sulfide resin composition, comprising a step of blending a polyarylene sulfide resin (A) and a carbon-based material other than carbon fiber (B) as essential components, and melt-kneading the mixture at a temperature equal to or higher than the melting point of the polyarylene sulfide resin (A), wherein the melt viscosity (V6) of the polyarylene sulfide resin (A) is 200 Pa·s or less, the pH of the carbon-based material other than carbon fiber (B) is 6 or more, the blending amount of the carbon-based material other than carbon fiber (B) is 5 to 80 parts by mass per 100 parts by mass of the polyarylene sulfide resin (A), and the flexural modulus is 18 GPa or less. (Note that the melt viscosity (V6) represents the melt viscosity measured after holding the mixture for 6 minutes using a flow tester at a temperature of 300°C, a load of 1.96 MPa, and an orifice having an orifice length to orifice diameter ratio of 10 / 1.) 11. The polyarylene sulfide resin composition according to claim 10, further comprising a fibrous filler (C).

12. A method for producing a polyarylene sulfide resin composition according to claim 11, wherein the amount of the fibrous filler (C) is 20 to 80 parts by mass per 100 parts by mass of the polyarylene sulfide resin (A).

13. The carbon-based material (B) other than carbon fiber contains furnace black, and the DBP absorption of the furnace black is 100 cm ３ The method for producing a polyarylene sulfide resin composition according to claim 10 or 11, wherein the polyarylene sulfide resin composition has a mass per unit area of ​​100 g or more and a primary particle size of 60 nm or less.

14. The method for producing a polyarylene sulfide resin composition according to claim 10 or 11, wherein the carbon-based material (B) other than carbon fibers contains graphite having an average particle size of 5 to 400 μm.

15. The method for producing a polyarylene sulfide resin composition according to claim 10 or 11, wherein the polyarylene sulfide resin (A) has a zeta potential of -70 mV or more at pH 7.8 to 8.2 as measured by a streaming potential method.

16. A method for producing a molded article, comprising the steps of producing a polyarylene sulfide resin composition by the method according to claim 10 or 11, and melt-molding the polyarylene sulfide resin composition obtained.

17. A method for producing a composite, comprising the steps of producing a molded article by the method according to claim 16, and joining the obtained molded article to a metal member.

18. A method for using the composite according to claim 17 as a secondary battery member.

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