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

Abstract

Provided are a resin composition, a molded article, and a composite having excellent electrical conductivity, toughness, processability, and long-term stability, and methods for producing the same. More specifically, the polyarylene sulfide resin composition is obtained by blending, as essential components, a polyarylene sulfide (hereinafter, PAS) resin (A) and a carbon-based material (B) other than carbon fibers, the melt viscosity (V6) of the PAS resin (A) being 200 Pa.s or less, the pH of the carbon-based material (B) other than carbon fibers being 6 or more, and the blending amount of the carbon-based material (B) other than carbon fibers being 5-80 parts by mass per 100 parts by mass of the PAS resin (A). Also provided are: a PAS resin composition having a flexural modulus of 18 GPa or less; a molded article; and a composite; and methods for producing the same.

Description

TECHNICAL FIELD

[0001] The present application relates to a polyarylene sulfide resin composition, a polyarylene sulfide resin molded article and a resin metal composite, and a method for producing the same. BACKGROUND

[0002] In recent years, with the electrification of vehicles and the popularization of renewable energy, the demand for secondary batteries typified by lithium ion batteries (LiB) has increased. As electrode members for LiB, moderate electrical conductivity and small variation in electrical conductivity, toughness, and reliability (long-term stability) during long-term use are required.

[0003] On the other hand, polyarylene sulfide (hereinafter sometimes referred to as "PAS") resins typified by polyphenylene sulfide (hereinafter sometimes referred to as "PPS") resins are excellent in mechanical strength, heat resistance, chemical resistance, moldability, dimensional stability, flame retardancy, and the like, and are therefore widely used as electrical / electronic device members, automobile member materials, and the like.

[0004] Since PAS resins are insulating materials, in order to be applied to safety members for anodes of LiB, electrical conductivity needs to be imparted, and a method of compounding a material having electrical conductivity such as carbon fiber or carbon black is generally used. In addition, since it is used in conjunction with metal members, it is required to have high toughness from the viewpoint of adhesion of the members.

[0005] As a conventional PAS resin composition for LiB, a PPS resin composition containing a PAS resin, graphite, carbon fiber, and a polyolefin wax is disclosed in Patent Document 1. A resin composition compounded with PPS, electrically conductive carbon black, carbon fiber, and graphite is disclosed in Patent Document 2.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT DOCUMENTS

[0008] Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 2006-19227

[0009] Patent Document 2: International Publication No. 2002 / 093670 SUMMARY

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] However, the current situation is that higher and higher characteristics are required, and there are cases where the conventional materials cannot sufficiently cope with them. In particular, small variation in electrical conductivity and suppression of degradation during long-term use are required, and it is difficult to balance these characteristics with high electrical conductivity and toughness.

[0012] Thus, the present application provides a PAS resin composition, a molded article, and a composite, each of which has excellent conductivity, toughness, processability, and long-term stability, and a method for producing the same.

[0013] Solution to the problem

[0014] The present inventors have conducted intensive studies in order to solve the above problem, and as a result, have found that a resin composition that solves the above problem can be obtained by compounding a specific amount of a carbon-based material other than carbon fibers having a specific pH in a PAS resin having a melt viscosity of 200 Pa·s or less, thereby completing the present application.

[0015] That is, the present disclosure relates to a PAS resin composition that is compounded by compounding a PAS resin (A) and a carbon-based material other than carbon fibers (B) as essential components,

[0016] The melt viscosity (V6) of the aforementioned PAS resin (A) is 200 Pa·s or less,

[0017] The aforementioned carbon-based material other than carbon fibers (B) has a pH of 6 or more,

[0018] The compounding amount of the aforementioned carbon-based material other than carbon fibers (B) is 5 to 80 parts by mass with respect to 100 parts by mass of the aforementioned PAS resin (A), and

[0019] The PAS resin composition has a flexural elastic modulus of 18 GPa or less.

[0020] In addition, the present disclosure relates to a PAS resin molded article that is molded from the aforementioned PAS resin composition.

[0021] In addition, the present disclosure relates to a composite member that is joined by the aforementioned molded article and a metal member.

[0022] In addition, the present disclosure relates to a method for producing a PAS resin composition, which has the following step: compounding a PAS resin (A) and a carbon-based material other than carbon fibers (B) as essential components, and melt-kneading at a temperature equal to or higher than the melting point of the PAS resin (A),

[0023] The melt viscosity (V6) of the aforementioned PAS resin (A) is 200 Pa·s or less,

[0024] The aforementioned carbon-based material other than carbon fibers (B) has a pH of 6 or more,

[0025] The compounding amount of the aforementioned carbon-based material other than carbon fibers (B) is 5 to 80 parts by mass with respect to 100 parts by mass of the aforementioned PAS resin (A), and

[0026] The PAS resin composition has a flexural modulus of 18 GPa or less.

[0027] Further, the present disclosure relates to a method for manufacturing a molded article, which has a step of manufacturing a PAS resin composition by the aforementioned manufacturing method, and a step of melt-molding the obtained PAS resin composition.

[0028] Further, the present disclosure relates to a method for manufacturing a composite, which has a step of manufacturing a molded article by the aforementioned manufacturing method, and a step of joining the obtained molded article to a metal member.

[0029] Effects of the Invention

[0030] According to the present invention, a resin composition, a molded article, and a composite each having excellent electrical conductivity, toughness, processability, and long-term stability, and a method for manufacturing the same can be provided. DETAILED DESCRIPTION

[0031] Hereinafter, an embodiment of the present invention will be described in detail, but the scope of the present invention is not limited to the one described here, and various modifications can be made without departing from the spirit of the present invention. In addition, with respect to a specific parameter, in the case where a plurality of upper limit values and lower limit values are described, any of the upper limit values and lower limit values can be combined to set an appropriate numerical range.

[0032] The PAS resin composition according to the present embodiment is characterized in that it is compounded by using a PAS resin (A) and a carbon-based material (B) other than carbon fibers as essential components,

[0033] The PAS resin (A) described above has a melt viscosity (V6) of 200 Pa s or less,

[0034] The carbon-based material (B) other than carbon fibers described above has a pH of 6 or more,

[0035] The compounding amount of the carbon-based material (B) other than carbon fibers described above is 5 to 80 parts by mass with respect to 100 parts by mass of the PAS resin (A), and

[0036] The PAS resin composition has a flexural modulus of 18 GPa or less. Hereinafter, it will be described.

[0037] <PAS resin (A)>

[0038] The PAS resin composition according to the present embodiment is compounded by using a PAS resin (A) as an essential component.

[0039] The PAS resin has a resin structure in which a structure in which an aromatic ring is bonded to a sulfur atom is a repeating unit, and specifically, is a resin in which the following structural site represented by General Formula (1) and, as needed, a trifunctional structural site represented by the following General Formula (2) are repeating units.

[0040]

[0041] (In the formula, R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having a carbon number in the range of 1 to 4, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group.)

[0042]

[0043] The trifunctional structural site represented by General Formula (2) is preferably in the range of 0.001 to 3 mol% and particularly preferably in the range of 0.01 to 1 mol% with respect to the total number of moles of other structural sites.

[0044] Here, the structural site represented by the aforementioned General Formula (1), and particularly R 1 and R 2 are preferably hydrogen atoms from the viewpoint of mechanical strength of the aforementioned PAS resin, in which case, a structure in which the bonding is at the para position represented by the following Formula (3) and a structure in which the bonding is at the meta position represented by the following Formula (4) can be cited.

[0045]

[0046] Among these, from the viewpoint of heat resistance of the aforementioned PAS resin, the bonding of the sulfur atom in the repeating unit to the aromatic ring is particularly preferably a structure in which the bonding is at the para position represented by the aforementioned General Formula (3).

[0047] In addition, the aforementioned PAS resin not only includes the structural sites represented by the aforementioned General Formulas (1) and (2), but can include structural sites represented by the following Structural Formulas (5) to (8) in a total of 30 mol% or less of the structural sites represented by General Formulas (1) and (2).

[0048]

[0049] In the present disclosure, from the viewpoint of heat resistance and mechanical strength of the PAS, it is particularly preferable that the structural sites represented by the aforementioned General Formulas (5) to (8) be 10 mol% or less. In the case where the aforementioned General Formulas (5) to (8) are included in the aforementioned PAS resin, as the bonding mode thereof, any of a random copolymer and a block copolymer can be used.

[0050] In addition, the aforementioned PAS resin can have a naphthyl sulfide bond or the like in the molecular structure thereof, and the content thereof is preferably 3 mol% or less, and particularly preferably 1 mol% or less, relative to the total number of moles of other structural sites.

[0051] In addition, the physical properties of the PAS resin (A) are not particularly limited as long as the effects of the present application are not impaired, and are as described below.

[0052] (Melt viscosity)

[0053] The melt viscosity of the PAS resin (A) used in the present embodiment is in the range of 200 Pa s or less at 300°C, from the viewpoint of a good balance between processability and toughness. In addition, it is preferably in the range of 2 Pa s or more, and more preferably in the range of 30 Pa s or more. Furthermore, it is preferably in the range of 180 Pa s or less, and more preferably in the range of 160 Pa s or less. Note that the measurement of the melt viscosity (V6) is performed using a flow tester, CFT-500D, manufactured by Shimadzu Corporation, on the PAS resin at 300°C, under a load of 1.96 x 10 6 Pa, L / D = 10 (mm) / 1 (mm) for 6 minutes.

[0054] (Non-Newtonian index)

[0055] The non-Newtonian index of the PAS resin (A) used in the present embodiment is not particularly limited, and 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 in the range of 0.95 or more, and preferably in the range of 1.50 or less, and more preferably in the range of 1.20 or less. Such a PAS resin is excellent in mechanical strength and flowability. Note that in the present disclosure, the non-Newtonian index (N value) is a value calculated using Capilograph under the conditions of a temperature of the melt point + 20°C, a ratio L / D of the orifice length (L) to the orifice diameter (D) = 40, and using the following equation, from the measured shear rate (SR) and shear stress (SS). The closer the non-Newtonian index (N value) is to 1, the closer the structure is to a linear structure, and the higher the non-Newtonian index (N value), the higher the degree of branching of the structure.

[0056] [Mathematical equation 1]

[0057]

[0058] [wherein SR represents a shear rate (sec -1 ), SS represents a shear stress (dyn / cm 2 ), and K represents a constant.]

[0059] (Carboxyl content)

[0060] The carboxyl group content of the PAS resin (A) used in the present embodiment is preferably in the range of 10 μmol / g or more and 200 μmol / g or less, and more preferably in the range of 20 μmol / g or more and 180 μmol / g or less. In this range, a molded article having good processability and excellent long-term stability can be obtained. Note that, in the present disclosure, the carboxyl group content is a value determined using the method described in the Examples.

[0061] (zeta potential)

[0062] The zeta potential of the PAS resin (A) used in the present embodiment, as determined using the flow potential method under conditions of pH 7.8 to 8.2, is preferably -70 mV or more, and more preferably -50 mV or more. The zeta potential of the PAS resin is a value determined using SurPASS3 (Anton Paar) with a film containing the PAS resin as a test piece, in an electrolyte: 1 mmol / L aqueous KCl solution, at a measurement temperature of 22 to 26°C. It refers to the average value when the zeta potential of the surface of the test piece is measured three times.

[0063] (manufacturing method)

[0064] As the production method of the aforementioned PAS resin, there are no particular limitations, and for example, the following methods can be given: (Production Method 1) a method in which a dihalogenated aromatic compound is added in the presence of sulfur and sodium carbonate, a polyhalogenated aromatic compound and / or other copolymerization components are added as necessary, and polymerization is performed; (Production Method 2) a method in which a dihalogenated aromatic compound is added in the presence of a sulfurizing agent or the like in a polar solvent, a polyhalogenated aromatic compound and / or other copolymerization components are added as necessary, and polymerization is performed; (Production Method 3) a method in which p-chlorothiophenol (other copolymerization components are added as necessary) is subjected to self-condensation; (Production Method 4) a method in which a diiodo aromatic compound and elemental sulfur are subjected to melt polymerization in the presence of a polymerization inhibitor that can have a functional group such as a carboxyl group or an amino group, while reducing the pressure, and the like. Among these methods, the method of (Production Method 2) is general, and is thus preferred. At the time of the reaction, in order to adjust the degree of polymerization, an alkali metal salt of a carboxylic acid, a sulfonic acid, an alkali (earth) metal hydroxide can be added. In the aforementioned (Production Method 2) method, a substance obtained by the following method is particularly preferred: a method in which, in a mixture containing a heated organic polar solvent and a dihalogenated aromatic compound, an aqueous sulfurizing agent is introduced at a rate at which water can be removed from the reaction mixture, a dihalogenated aromatic compound and a sulfurizing agent are added in an organic polar solvent, a polyhalogenated aromatic compound is added as necessary, a reaction is performed, and the amount of water in the reaction system is controlled to be in the range of 0.02 to 0.5 moles per 1 mole of the organic polar solvent, thereby producing a PAS resin (see Japanese Patent Application Publication No. 07-228699); a method in which a dihalogenated aromatic compound and a polyhalogenated aromatic compound and / or other copolymerization components as necessary are added in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, a reaction is performed while controlling the alkali metal hydrosulfide and the organic acid alkali metal salt to be in the range of 0.01 to 0.9 moles of the organic acid alkali metal salt per 1 mole of the sulfur source, and the amount of water in the reaction system is controlled to be 0.02 moles or less per 1 mole of the aprotic polar organic solvent (see WO2010 / 058713).As specific examples of the dihalogenated aromatic compound, there can be mentioned p-dihalogenated benzene, m-dihalogenated benzene, o-dihalogenated benzene, 2,5-dihalogenated toluene, 1,4-dihalogenated naphthalene, 1-methoxy-2,5-dihalogenated benzene, 4,4'-dihalogenated diphenyl, 3,5-dihalogenated benzoic acid, 2,4-dihalogenated benzoic acid, 2,5-dihalogenated nitrobenzene, 2,4-dihalogenated nitrobenzene, 2,4-dihalogenated anisole, p,p'-dihalogenated diphenyl ether, 4,4'-dihalogenated benzophenone, 4,4'-dihalogenated diphenyl sulfone, 4,4'-dihalogenated diphenyl sulfoxide, 4,4'-dihalogenated diphenyl sulfide, and a compound having an alkyl group having a carbon number of 1 to 18 on the aromatic ring of each of the above compounds, and as the polyhalogenated aromatic compound, there can be mentioned 1,2,3-trihalogenated benzene, 1,2,4-trihalogenated benzene, 1,3,5-trihalogenated benzene, 1,2,3,5-tetrahalogenated benzene, 1,2,4,5-tetrahalogenated benzene, 1,4,6-trihalogenated naphthalene, and the like. In addition, the halogen atom contained in each of the above compounds is preferably a chlorine atom or a bromine atom.

[0065] As the method for post-treating the reaction mixture containing the PAS resin obtained by the polymerization step, there is no particular limitation, and for example, there can be mentioned a method in which, after the polymerization reaction is completed, the reaction mixture is first kept in this state or after an acid or a base is added, the solvent is distilled off under reduced pressure or under normal pressure, and then the solid substance after the distillation of the solvent is washed once or two or more times with water, a reaction solvent (or an organic solvent having the same solubility for a low-molecular polymer), acetone, methyl ethyl ketone, an alcohol, or the like, and further neutralized, washed with water, filtered, and dried (post-treatment 1); or a method in which, after the polymerization reaction is completed, a solvent (a solvent which is soluble in the polymerization solvent used and which is at least a poor solvent for PAS) such as water, acetone, methyl ethyl ketone, an alcohol, an ether, a halogenated hydrocarbon, an aromatic hydrocarbon, an aliphatic hydrocarbon, or the like is added to the reaction mixture as a precipitant, and a solid product such as PAS or an inorganic salt is precipitated, and they are filtered, washed, and dried (post-treatment 2); or a method in which, after the polymerization reaction is completed, a reaction solvent (or an organic solvent having the same solubility for a low-molecular polymer) is added to the reaction mixture and stirred, and then a low-molecular weight polymer is removed by filtration, and then the resultant is washed once or two or more times with water, acetone, methyl ethyl ketone, an alcohol, or the like, and then neutralized, washed with water, filtered, and dried (post-treatment 3); a method in which, after the polymerization reaction is completed, water is added to the reaction mixture, and washed with water, filtered, and dried as needed with acid treatment at the time of the water washing (post-treatment 4); a method in which, after the polymerization reaction is completed, the reaction mixture is filtered, and as needed, washed once or two or more times with a reaction solvent, and further washed with water, filtered, and dried (post-treatment 5); and the like. Among these methods, the method of the post-treatment 4 can obtain a PAS resin in which the molecular terminal of the PAS resin has a carboxyl group, and thus is preferred.

[0066] Note that in the post-treatment methods exemplified above (post-treatment 1) to (post-treatment 5), drying of the PAS resin can be performed in a vacuum, or in air or in a non-reactive gas atmosphere such as nitrogen.

[0067] In the PAS resin composition of the present embodiment, the compounding amount of the PAS resin (A) is preferably in a range of 30 parts by mass or more, more preferably 40 parts by mass or more, and preferably in a range of 80 parts by mass or less, more preferably 70 parts by mass or less, relative to 100 parts by mass of the resin composition. In this range, the resin composition has good processability, and the molded article is excellent in chemical resistance, toughness, and the like, and is thus preferred.

[0068] In addition, the PAS resin (A) used in the present embodiment can also use a PAS resin newly polymerized by the above method, or a recycled PAS resin. For example, a PAS resin recovered from a PAS resin composition or a PAS resin molded article can be used, and 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 contained PAS and performing the above post-treatment on the obtained solution can be cited. In addition, a substance obtained by mechanically pulverizing a PAS resin composition or a PAS resin molded article can be used as a PAS resin, and specifically, a substance obtained by pulverizing a sprue or a runner generated at the time of molding a molded article, a substance recovered from a molded article that is out of standard, a molded article that has been used as a product, and the like can be cited. At this time, the pulverized product of a PAS resin composition or a PAS resin molded article containing components other than the PAS resin, and from the viewpoint of mechanical strength, the PAS resin content is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, and further preferably 98 parts by mass or more.

[0069] <Carbon-based material other than carbon fibers (B)>

[0070] The PAS resin composition according to the present embodiment is a composition in which a carbon-based material other than carbon fibers (B) is compounded as a necessary component. Note that in the present disclosure, carbon fibers are included in the fibrous filler (C) and are not included in the carbon-based material (B).

[0071] As the carbon-based material (B) other than carbon fibers which can be applied to the present embodiment, there is no particular limitation as long as it is a carbon-based material other than carbon fibers, and a publicly known material can be used. For example, carbon blacks such as furnace black, thermal black, channel black, ketjen black, gas black, oil black, and acetylene black; graphites such as earthy graphite, spheroidal graphite, flaky graphite, scaly graphite, expanded graphite, and exfoliated graphite; carbon nanotubes such as single-walled nanotubes and multi-walled nanotubes; and fullerenes can be exemplified. As the graphite, either of natural graphite and artificial graphite can be used, and the shape is not limited. In addition, the carbon nanotubes can be generally produced by a laser ablation method, an arc discharge CVD method, a plasma CVD method, a vapor phase method, a combustion method, and the like, and the carbon nanotubes produced by any of these methods can be used in the present disclosure. In addition, the surface and the end of the carbon nanotubes can be modified with a functional group in order to increase the affinity with the resin, and for example, the functional group can be implemented with a hydroxyl group, a carboxyl group, and an amino group by using an acid and a base. Furthermore, the carbon nanotubes can be used after being pretreated with a coupling agent, and as the coupling agent, isocyanate-based compounds, organosilane-based compounds, organotitanate-based compounds, and epoxy compounds can be exemplified. Among them, from the viewpoint of stability of the electrical conductivity, carbon black is preferable, and particularly, furnace black is preferably used.

[0072] In addition, the pH of the carbon-based material (B) other than carbon fibers which can be applied to the present embodiment is preferably 6 or more, and more preferably more than 6. In this range, the resin composition and the molded article are less likely to be corroded by a contact object (excellent in corrosion resistance), and thus are preferable. The upper limit of the pH is not particularly limited, and is preferably 12 or less, and more preferably 10 or less. Note that the pH of the carbon-based material (B) other than carbon fibers is a value obtained by measuring the pH of a mixed solution of the carbon-based material (B) other than carbon fibers and distilled water using a glass electrode pH meter in accordance with JIS K 6221.

[0073] As a commercially available product of such a carbon-based material (B) other than carbon fibers, for example, "CNP15" manufactured by Ito Graphite Co., Ltd., "DENKA BLACK" manufactured by Denka Company Limited., "3400B" manufactured by Mitsubishi Chemical Corporation, and "Ketjenblack" manufactured by Lion Specialty Chemicals Co., Ltd. can be exemplified.

[0074] In the case where furnace black is used as the aforementioned carbon-based material (B) other than carbon fibers, the DBP absorption amount is preferably 100 cm 3 / 100 g or more, and more preferably 110 cm 3 / 100 or more. In this range, the balance between the electrical conductivity and the flowability is excellent, and thus is preferred. Note that the DBP absorption amount of the furnace black is a value measured according to the method described in JIS K6221.

[0075] In addition, in the case where the furnace black is used as the carbon-based material (B) other than the carbon fiber, the primary particle diameter is preferably 60 nm or less, and more preferably 50 nm or less. In this range, the balance between the electrical conductivity and the flowability is excellent, and thus is preferred. Note that the primary particle diameter is measured by observation using a transmission electron microscope, and the average value of at least 5 or more samples is measured.

[0076] In the case where the graphite is used as the carbon-based material (B) other than the carbon fiber, the average particle diameter thereof is preferably 5 to 400 μm. In this range, the resin composition can exhibit excellent dispersibility. From the same viewpoint, the average particle diameter is more preferably 10 μm or more, and further preferably 15 μm or more, and in addition, the average particle diameter is more preferably 350 μm or less, and further preferably 300 μm or less. Note that the average particle diameter is an average particle diameter (D50) calculated from the particle size distribution measured according to a conventional method using a laser diffraction scattering type particle size distribution measuring machine (Microtrac MT3300EXII) based on the particle size distribution. 50

[0077] In the PAS resin composition of the present embodiment, the compounding amount of the carbon-based material (B) other than the carbon fiber is preferably in the range of 5 parts by mass or more, and more preferably 10 parts by mass or more, with respect to 100 parts by mass of the PAS resin (A), and is preferably in the range of 80 parts by mass or less, and more preferably 60 parts by mass or less. In this range, the resin composition has good processability, and the electrical conductivity, the mechanical strength, and the dimensional stability of the molded article are excellent, and thus is preferred.

[0078] <Filler (C)>

[0079] The PAS resin composition of the present embodiment can further compounding a fibrous filler (C) as an arbitrary component in order to improve the mechanical strength and improve the processability at the time of molding. As the fibrous filler (C) that can be applied to the present embodiment, there is no particular limitation, and a publicly known substance can be used. For example, a fibrous filler such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, and natural fiber can be used.

[0080] ​The fibrous filler (C) used in the present application can also use, as necessary, a substance processed with a surface treatment agent, a bundling agent. By this, the adhesion to the PAS resin (A) can be improved, and the mechanical strength of the obtained resin composition, molded article can be improved, and thus is preferred. As the aforementioned surface treatment agent or bundling agent, for example, at least one polymer selected from the group consisting of silane compounds having a functional group such as an amino group, an epoxy group, an isocyanate group, a vinyl group, titanate compounds, acrylic resins, urethane resins, polyether resins, and epoxy resins, and the like can be exemplified, and particularly in the case of using glass fibers, from the viewpoint of suppressing excessive defibration during processing, a urethane resin is preferred. In the case where the aforementioned surface treatment agent or bundling agent contains a urethane resin, the content thereof is not particularly limited, and from the viewpoint of moisture resistance and the like, a range of 35% by mass or less is preferred, and a range of 20% by mass or less is more preferred.

[0081] In the case where the fibrous filler (C) is compounded in the PAS resin composition of the present embodiment, the compounding amount thereof is not particularly limited, and a range of 20 parts by mass or more, more preferably a range of 35 parts by mass or more, relative to 100 parts by mass of the PAS resin (A) is preferred, and a range of 80 parts by mass or less, more preferably a range of 60 parts by mass or less is preferred. In this range, the resin composition has good processability, and the mechanical strength of the molded article is excellent, and thus is preferred.

[0082] <silane coupling agent (D)>

[0083] The PAS resin composition of the present embodiment can further compound a silane coupling agent (D) as an arbitrary component in order to improve the mechanical strength and reduce burrs during molding.

[0084] As the silane coupling agent (D) which can be applied to the present embodiment, there is no particular limitation as long as the effect of the present application is not impaired, and as a preferable silane coupling agent, a silane coupling agent having a functional group which reacts with a carboxyl group, such as a silane coupling agent having an epoxy group, an isocyanate group, an amino group, or a hydroxyl group can be cited. As such a silane coupling agent, for example, an epoxy group-containing alkoxysilane compound such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, an isocyanate group-containing alkoxysilane compound such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, and the like, an amino group-containing alkoxysilane compound such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and the like, a hydroxyl group-containing alkoxysilane compound such as γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyltriethoxysilane, and the like can be cited.

[0085] In the present embodiment, the silane coupling agent (D) is not an essential component, but in the case of compounding, the compounding amount thereof is not particularly limited as long as the effect of the present application is not impaired. For example, it is preferable that the amount be in the range of 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the PAS resin (A), and be 10 parts by mass or less, more preferably 5 parts by mass or less. In this range, the resin composition has good moldability, particularly, mold release property, and the molded product exhibits excellent adhesion to an epoxy resin, and the mechanical strength is further improved, and thus it is preferable.

[0086] <Thermoplastic Elastomer (E)>

[0087] The PAS resin composition of the present embodiment can further compound a thermoplastic elastomer (E) as an arbitrary component in order to improve the mechanical strength.

[0088] As the thermoplastic elastomer (E) which can be applied to the present embodiment, a polyolefin-based elastomer, a fluorine-based elastomer, or a silicone-based elastomer can be cited, and among them, a polyolefin-based elastomer can be cited as a preferable substance. In the case of adding these elastomers, the compounding amount thereof is not particularly limited as long as the effect of the present application is not impaired, and it is preferable that the amount be in the range of 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the PAS resin (A), and be 10 parts by mass or less, more preferably 5 parts by mass or less. In this range, the obtained PAS resin composition has improved impact resistance, and thus it is preferable.

[0089] For example, the aforementioned polyolefin-based elastomer can include a homopolymer of an α-olefin, or a copolymer of two or more α-olefins, or a copolymer of one or two or more α-olefins and a vinyl polymerizable compound having a functional group. In this case, as the aforementioned α-olefin, an α-olefin having a carbon number of 2 or more to 8 or less, such as ethylene, propylene, 1-butene, or the like, can be mentioned. In addition, as the aforementioned functional group, a carboxyl group, an anhydride group (-C(=0)OC(=0)-), an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, an oxazoline group, or the like can be mentioned. Then, as the aforementioned vinyl polymerizable compound having a functional group, one or two or more of vinyl acetate; an α,β-unsaturated carboxylic acid such as (meth)acrylic acid; an alkyl ester of an α,β-unsaturated carboxylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, or the like; a metal salt (alkali metal such as sodium, alkaline earth metal such as calcium, zinc, or the like) of an α,β-unsaturated carboxylic acid such as an ionomer; a glycidyl ester of an α,β-unsaturated carboxylic acid such as glycidyl methacrylate, or the like; an α,β-unsaturated dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid, or the like; a derivative (monoester, diester, anhydride) of the aforementioned α,β-unsaturated dicarboxylic acid, or the like can be mentioned. The aforementioned thermoplastic elastomer can be used alone or in combination with two or more.

[0090] The PAS resin composition of the present embodiment can, within a range that does not impair the effects of the present application, incorporate, as an arbitrary component, a filler other than the aforementioned carbon-based material (B) and fibrous filler (C) (hereinafter referred to as other filler). For example, fillers of various shapes such as plate-shaped, powder-particle-shaped, or the like can be mentioned. Specifically, glass flake, clay, pyrophyllite, bentonite, sericite, mica, attapulgite, ferrite, calcium silicate, zeolite, boehmite, silicon dioxide, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, diatomite, metal oxides such as iron oxide, titanium oxide, zinc oxide, aluminum oxide, metal carbonates such as calcium carbonate, magnesium carbonate, metal sulfates such as calcium sulfate, barium sulfate, fumed silica, other silicon carbide, silicon nitride, boron nitride, various metal powders, plant-derived fillers such as cocoa bean meal, or the like can be mentioned.

[0091] In the present embodiment, the other filler is not an essential component, but when incorporated, the amount thereof is not particularly limited as long as the effects of the present application are not impaired. As the amount of the other filler to be incorporated, for example, 1 part by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the PAS resin (A), and 600 parts by mass or less, more preferably 200 parts by mass or less, are preferable. Within this range, the resin composition exhibits good moldability, and the molded product is excellent in mechanical strength, and thus is preferable.

[0092] Further, in the PAS resin composition of the present embodiment, in addition to the above-mentioned components, the following resins can be appropriately blended as an arbitrary component according to the purpose: polyester resins, polyamide resins, polyimide resins, polyetherimide resins, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyethersulfone resins, polyether ether ketone resins, polyether ketone resins, polyarylate resins, polyethylene resins, polypropylene resins, polytetrafluoroethylene resins, polyvinylidene fluoride resins, polystyrene resins, ABS resins, epoxy resins, phenol resins, urethane resins, liquid crystal polymers, and the like synthetic resins (hereinafter, simply referred to as synthetic resins). In particular, if a fluorine-based resin is blended, the sliding properties are further improved, and thus it is preferable. In the present application, the above-mentioned synthetic resins are not essential components, but when blended, the blending ratio thereof is not particularly limited as long as the effects of the present application are not impaired, and furthermore, it cannot be generally prescribed according to the respective purposes, and as the blending ratio of the synthetic resins in the resin composition of the present embodiment, for example, a range of 5 parts by mass or more and a range of 15 parts by mass or less with respect to 100 parts by mass of the PAS resin (A) can be exemplified. In other words, the ratio of the PAS resin with respect to the total of the PAS resin (A) and the synthetic resins is preferably in a range of (100 / 115) or more, and more preferably in a range of (100 / 105) or more on a mass basis.

[0093] Further, in the PAS resin composition of the present embodiment, a coloring agent, an antistatic agent, an antioxidant, a heat-resistant stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, a flame retardant aid, a rust preventive, and a mold release agent (including metal salts, esters, polyethylene and the like polyolefin-based waxes of a fatty acid having a carbon number of 18 to 30 such as stearic acid and montanic acid), an antibacterial agent, an antiviral agent, and the like generally known additives can be appropriately blended as an arbitrary component as needed. These additives are not essential components, and for example, with respect to 100 parts by mass of the PAS resin (A), it is preferable to be in a range of 0.01 parts by mass or more, and furthermore, it is preferable to be in a range of 1000 parts by mass or less, more preferably in a range of 100 parts by mass or less, and further preferably in a range of 10 parts by mass or less, and the use thereof can be appropriately adjusted according to the purpose and the use in a manner that does not impair the effects of the present application.

[0094] In addition, the PAS resin composition of the present disclosure is characterized in that the flexural modulus is 18 GPa or less. Further, it is preferably 16 GPa or less, and more preferably 15 GPa or less. In this range, the adhesion when the PAS resin molded product is combined with a metal member is excellent, and thus the electrical conductivity of the composite member is excellent. In order to make the flexural modulus in this range, for example, a method of adjusting the melt viscosity (V6) of the PAS resin in the range of 50 to 2000 Pa-s can be exemplified depending on the content rate of the PAS resin in the resin composition. For example, in the case of compounding a large amount of components other than the PAS resin, there is a tendency that the crystallization rate increases due to the increase in the thermal conductivity of the resin composition, and thus the melt viscosity of the PAS resin can be increased to adjust the crystallization behavior. Note that the adjustment method of the weld strength is not limited to the above method. In addition, the flexural modulus in the present disclosure is a value measured according to the measurement method of ISO 178 using a dumbbell-shaped injection molded product according to Type A test piece prescribed in ISO 20753 as a test piece, and can be measured by the method described in the examples.

[0095] <Method for producing PAS resin composition>

[0096] The method for producing the PAS resin composition according to the present embodiment is characterized by having a step of compounding a PAS resin (A) and a carbon-based material other than carbon fibers (B) as essential components, and melt-kneading at a temperature equal to or higher than the melting point of the PAS resin (A),

[0097] The melt viscosity (V6) of the aforementioned PAS resin (A) is 200 Pa-s or less,

[0098] The aforementioned carbon-based material other than carbon fibers (B) has a pH of 6 or more,

[0099] The compounding amount of the aforementioned carbon-based material other than carbon fibers (B) is 5 to 80 parts by mass with respect to 100 parts by mass of the aforementioned PAS resin (A), and

[0100] The PAS resin composition has a flexural modulus of 18 GPa or less. Details are described below.

[0101] The production method of the PAS resin composition of the present embodiment has a step of compounding the aforementioned necessary components and melt-kneading in a temperature range of the melting point of the PAS resin (A) or higher. More specifically, the PAS resin composition of the present embodiment is compounded of each of the necessary components and other arbitrary components as needed. As the method of producing the resin composition used in the present application, there is no particular limitation, and the following methods can be exemplified: a method of compounding the necessary components and other arbitrary components as needed and melt-kneading, more specifically, uniformly dry-mixing as needed with a tumbler mixer or a Henschel mixer or the like, and then feeding into a twin-screw extruder to melt-knead.

[0102] The melt-kneading can be performed with heating to a temperature range in which the resin temperature is a temperature of the melting point of the PAS resin (A) or higher, preferably a temperature of the melting point + 10°C or higher, more preferably a temperature of the melting point + 10°C or higher, further preferably a temperature of the melting point + 20°C or higher, preferably a temperature of the melting point + 100°C or lower, more preferably a temperature of the melting point + 50°C or lower.

[0103] As the aforementioned melt-kneading machine, from the viewpoints of dispersibility and productivity, a twin-screw kneading extruder is preferred, and, for example, melt-kneading is preferably performed while appropriately adjusting the discharge amount of the resin components to a range of 5 to 500 (kg / hr) and the screw rotation speed to a range of 50 to 500 (rpm), and further preferably melt-kneading is performed under conditions in which the ratio (discharge amount / screw rotation speed) thereof is in a range of 0.02 to 5 (kg / hr / rpm). In addition, the addition and mixing of each component into the melt-kneading machine can be performed simultaneously or in divided portions. For example, when adding other fibrous fillers as needed, from the viewpoint of dispersibility, it is preferred to feed into the extruder from a side feeder of the aforementioned twin-screw kneading extruder. With respect to the position of the side feeder, the ratio of the distance from the resin feeding portion (top feeder) of the extruder to the side feeder with respect to the full length of the screw of the aforementioned twin-screw kneading extruder is preferably 0.1 or higher, more preferably 0.3 or higher. In addition, the ratio is preferably 0.9 or lower, more preferably 0.7 or lower.

[0104] The PAS resin composition of the present embodiment obtained by such melt-kneading is a melt-mixture containing the aforementioned necessary components, other arbitrary components added as needed, and components derived therefrom. Therefore, the PAS resin composition of the present embodiment has a morphology in which the PAS resin (A) forms a continuous phase in which the other necessary components and arbitrary components are dispersed.

[0105] The PAS resin composition of the present embodiment is preferably, after the melt kneading, pre-dried as needed in a temperature range of 100 to 150°C by a publicly known method, for example, after extrusion molding of the resin composition in a molten state into a thread-like shape, processing into a pellet, a chip, a granule, a powder, or the like, and the like.

[0106] <PAS resin molded article, method for producing PAS resin molded article>

[0107] The molded article of the present embodiment is obtained by melt molding the PAS resin composition. Further, the method for producing the molded article of the present embodiment has a step of melt molding the aforementioned PAS resin composition. Therefore, the molded article of the present embodiment has a morphology in which the PAS resin (A) forms a continuous phase, and other essential components, optional components are dispersed. By having the PAS resin composition in this morphology, a molded article excellent in thermal conductivity and mechanical strength can be obtained.

[0108] The PAS resin composition of the present embodiment can be used for various molding such as injection molding, compression molding, extrusion molding of a composite material, a sheet, a tube, and the like, pultrusion molding, blow molding, transfer molding, and the like, and is particularly excellent in mold releasability, and thus is suitable for injection molding applications. In the case of molding by injection molding, various molding conditions are not particularly limited, and molding can be performed by a usual method. For example, in an injection molding machine, after a step of melting the aforementioned PAS resin composition at a temperature range of the melting point of the PAS resin (A) or higher, preferably a temperature range of the melting point + 10°C or higher, more preferably a temperature range of the melting point + 10°C to the melting point + 100°C, further preferably a temperature range of the melting point + 20°C to the melting point + 50°C, the molding can be performed by injecting the resin from a resin discharge port into a mold. At this time, the mold temperature can also be set to a publicly known temperature range, for example, room temperature (23°C) to 300°C, and is preferably set to 130 to 190°C.

[0109] The method for manufacturing the molded article according to this embodiment may include a step of annealing the aforementioned molded article. The annealing treatment is performed under conditions most suitable for the intended use or shape of the molded article. The annealing temperature is within a range above the glass transition temperature of the PAS resin (A), preferably within a range of 10°C or more above that glass transition temperature, and more preferably within a range of 30°C or more above that glass transition temperature. Alternatively, a range of 260°C or less is preferred, and a range of 240°C or less is more preferred. The annealing time is not particularly limited, but is preferably 0.5 hours or more, and more preferably 1 hour or more. Alternatively, a range of 10 hours or less is preferred, and a range of 8 hours or less is more preferred. Within this range, the strain of the resulting molded article is reduced, and not only is the crystallinity of the resin improved, but the thermal conductivity and mechanical strength are also further improved, which is therefore preferable. The annealing treatment can be performed in air, but is preferably performed in an inert gas such as nitrogen.

[0110] The molded articles of this embodiment include remolded articles, which are obtained by reusing molded articles formed by melt molding the aforementioned PAS resin composition. Specifically, these include, for example, articles obtained by washing and crushing main runner or branch runner waste generated during the manufacturing of molded articles, molded articles recycled as non-standard molded articles, and molded articles previously used as products, and then melting and molding them again at a temperature above the melting point of PAS resin. When reusing, from the viewpoint of mechanical strength, it is preferable to mix the crushed molded article with the aforementioned PAS resin composition. The size of the crushed molded article is not particularly limited, but from the viewpoint of mixability and processability, it is preferable to have a size similar to that of the mixed PAS resin composition. Furthermore, regarding the mixing ratio, relative to 100 parts by weight of the PAS resin composition, the crushed molded article is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and even more preferably 20 parts by weight or less. Within this range, recyclability can be improved without impairing the effects exhibited by the PAS resin composition of this disclosure.

[0111] <Compounds, Manufacturing Methods of Composites>

[0112] The composite of this embodiment is formed by joining the molded article described above with a metal component. Furthermore, the manufacturing method of the composite of this embodiment includes a step of manufacturing the molded article using the method described above, and a step of joining the obtained molded article with a metal component.

[0113] The metal member that can be applied to the present embodiment is not particularly limited as long as the effect of the present application is not impaired, and a publicly known metal member can be used. For example, aluminum, copper, stainless steel, magnesium, iron, titanium, or an alloy containing them can be listed. More specifically, an alloy in which iron is a main component and further contains carbon, silicon, manganese, chromium, tungsten, molybdenum, phosphorus, titanium, vanadium, nickel, zirconium, boron, or the like (hereinafter referred to as an iron alloy), an alloy in which aluminum is a main component and further contains copper, manganese, silicon, magnesium, zinc, nickel (hereinafter referred to as an aluminum alloy), an alloy in which magnesium is a main component and further contains zinc, aluminum, zirconium, or the like (hereinafter referred to as a magnesium alloy), an alloy in which copper is a main component and further contains zinc, tin, phosphorus, nickel, magnesium, silicon, chromium (hereinafter referred to as a copper alloy), and an alloy in which titanium is a main component and further contains copper, manganese, silicon, magnesium, zinc, nickel (hereinafter referred to as a titanium alloy) can be listed. Among them, iron, the iron alloy, the aluminum alloy, the magnesium alloy, the copper alloy, and the titanium alloy are more preferably listed, and the iron alloy, the aluminum alloy, and the magnesium alloy are further preferably listed. The shape of the metal member is not particularly limited, and a flat plate shape, a curved plate shape, a bar shape, a cylindrical shape, a block shape, or the like processed by plastic working, blanking working, cutting, grinding, discharge working, or the like can be listed. In addition, a thin film-like object such as a metal foil can also be used.

[0114] In addition, the aforementioned metal member can also be subjected to surface roughening treatment. As a method of surface roughening, a publicly known method can be used, and for example, (1) an immersion method using an aggressive aqueous solution or an aggressive suspension, (2) an anodizing method, and (3) mechanical cutting based on sandblasting processing, laser processing can be listed. Among them, as a method of surface roughening of the metal member, (1) the immersion method using the aggressive aqueous solution or the aggressive suspension or (2) the anodizing method is particularly preferable. In the case where the aforementioned metal member is subjected to surface treatment, it is preferable to process the aforementioned metal member into a predetermined shape by plastic working, blanking working, cutting, grinding, discharge working, or the like before forming the aforementioned fine concave-convex surface.

[0115] Note that a primer layer can also be formed on the surface of the metal member on which the surface treatment of the metal has been performed. The material constituting the primer layer is not particularly limited, and is typically formed from a primer resin material containing a resin component. The primer resin material is not particularly limited, and a publicly known material can be used. Specifically, publicly known polyolefin-based primers, epoxy-based primers, urethane-based primers, and the like can be cited. The method of forming the primer layer is not particularly limited, and, for example, a solution of the primer resin material described above, an emulsion of the primer resin material described above can be applied to the metal member on which the surface treatment described above has been performed to form. As the solvent used when the solution is prepared, toluene, methyl ethyl ketone (MEK), dimethylformamide (DMF), and the like can be cited. As the medium for the emulsion, aliphatic hydrocarbon media, water, and the like can be cited.

[0116] The method of joining the resin molded article of the present disclosure to the metal member is not particularly limited as long as the effects of the present application are not impaired, and a publicly known method and / or device can be used. For example, a method of joining by melt molding the resin composition of the present disclosure to the metal member, a method of fusion bonding the molded article of the present disclosure to the metal member, a method of riveting the molded article of the present disclosure to the metal member, a method of mechanically joining the molded article of the present disclosure to the metal member, and the like can be cited.

[0117] As the method of joining by melt molding the resin composition of the present disclosure to the metal member, a so-called insert molding method, in which the metal member is inserted into a mold of an injection molding machine, and then injection molding of the metal member is performed using the resin composition of the present disclosure, can be cited. The device and manufacturing method in the insert molding method are not particularly limited, and a commercially available device can be used, or a conventional method can be performed.

[0118] As the method of fusion bonding the molded article of the present disclosure to the metal member, the molded article of the present disclosure is brought into contact with the metal member, and then joined by heating, or brought into contact after heating, and then joined, and then cooled. Specifically, a hot plate bonding method, a vibration bonding method, an infrared bonding method, an infrared vibration bonding method, an ultrasonic bonding method, a high frequency bonding method, an induction heating bonding method, a spin bonding method, a laser bonding method, a hot press method, a hot stamping method, a friction stir joining method, and the like can be cited, and the device and manufacturing method used in these joining methods can use a commercially available device, or a conventional method can be performed.

[0119] As a method of riveting the molded article of the present disclosure to a metal member, a method in which a rivet is passed through a hole of the molded article of the present disclosure and a hole of the metal member, and the rivet is deformed to be fixed can be exemplified. Specifically, a press-riveting method, a spin-riveting method, a heat-riveting method, and the like can be exemplified, and the devices and manufacturing methods used in these joining methods can be used as commercially available devices or can be performed according to conventional methods. As a method of mechanically joining the molded article of the present disclosure to a metal member, a method of mechanical fastening using a screw, a pin, a shaft, a bolt, a nut, a clamp, and the like, fixation using a fitting structure, and the like can be exemplified.

[0120] <Use>

[0121] The PAS resin molded article of the present embodiment is excellent in toughness, and thus, when combined with a metal member or another resin member, the adhesion is high, the conduction loss of heat and electricity at the interface can be reduced, and furthermore, the long-term stability of the interface is excellent. Thus, it is suitable for use as a member that forms a composite with a metal member or a resin member. In addition, the composite of the present embodiment is characterized by being excellent in conductivity and long-term stability, and thus, is particularly suitable for conductive member applications and electromagnetic wave shielding member applications. Specifically, it can be suitably used for conductive members such as electrode peripheral members for lithium ion batteries, conveyance pallets, battery members, conductive reels, conductive pallets, electromagnetic wave shielding members such as electronic device housings, inverter housings, ECU housings, medical device housings, and the like. In addition, the molded article and the composite of the present embodiment can be used not only for conductive members and electromagnetic wave shielding members, but also for the following general uses.For example, electrical / electronic components such as electrical / electronic components represented by a box-shaped protection / support member for an electrical / electronic component integrated module, a plurality of individual semiconductors or modules, a sensor, an LED lamp, a connector, a socket, a resistor, a relay housing, a switch, a coil holder, a capacitor, a variable capacitor housing, an optical pickup, an oscillator, various terminal boards, a transformer, a plug, a printed board, a tuner, a speaker, a microphone, an earphone, a small motor, a magnetic head base, a power module, a terminal board, a semiconductor, a liquid crystal, an FDD bracket, an FDD chassis, a motor brush holder, a parabolic antenna, computer-related components, and the like; household and office electrical product components represented by VTR components, television components, an iron, a hair dryer, an electric rice cooker component, a microwave oven component, a sound equipment component, an audio / video equipment component such as an audio CD / DVD / Blu-ray disc, an illumination component, a refrigerator component, an air conditioner component, a typewriter component, a word processor component, or a water heater, a bath water amount, a temperature sensor, and the like; mechanical-related components represented by an office computer-related component, a telephone-related component, a facsimile-related component, a copier-related component, a cleaning jig, a motor component, a recorder, a typewriter, and the like; optical equipment and precision machinery-related components represented by a microscope, a binocular, a camera, a timepiece, and the like; various valves such as an alternator terminal, an alternator connector, a brush holder, a slip ring, an IC regulator, a potentiometer base for a dimmer, a relay module, a suppression switch, an exhaust gas valve, various pipes for a fuel-related / exhaust system / intake system, an intake nozzle communication pipe, an intake manifold, an engine cooling water joint, a carburetor main body, a carburetor partition, a waste gas sensor, a cooling water sensor, an oil temperature sensor, a brake pad wear sensor, a throttle position sensor, a crank position sensor, a temperature sensor, an air flow meter, a brake pad wear sensor, an air conditioning thermostat base, a heating hot air flow control valve, a radiator motor brush holder, a water pump impeller, a turbine blade, a wiper motor-related component, a dispenser, a starter switch, an ignition coil and a coil holder thereof, a motor insulator, a motor rotor, a motor core, a starting relay, a wire harness for a transmission, a windshield washer nozzle, an air conditioning panel switch base plate, a coil for a fuel-related solenoid valve, a connector for a fuse, a horn terminal, an electrical component insulating plate, a stepping motor rotor, a lamp base, a lamp reflector, a lamp cover, a brake piston, a solenoid coil holder, an engine oil filter, an ignition device housing, and the like; and automobile / vehicle-related components, and the like can be cited. The present application can also be applied to other various uses.

[0122] Embodiment

[0123] Hereinafter, the present application will be described using examples and comparative examples, but the present application is not limited to these examples. Note that, hereinafter, "%" and "parts" are based on mass unless otherwise specified.

[0124] <Examples 1 to 10 and Comparative Examples 1 to 6>

[0125] Each material was compounded according to the composition and compounding amount described in Table 1. Then, the compounded materials were fed into a twin-screw extruder "TEX-30α (product name) " manufactured by Nippon Steel & Sumikin Engineering Co., Ltd. with a vent, and melt-kneaded at a resin discharge amount 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. The glass fiber and the polyamide fiber were fed from a side feeder (S / T ratio 0.5), and the other materials were uniformly premixed in a banbury mixer and fed from a top feeder. After the obtained pellets of the resin composition were dried in a Geer oven at 140°C for 2 hours, injection molding was performed to produce various test pieces, and the following tests were performed.

[0126] <Assessment>

[0127] (1) Measurement of Charpy Impact Strength

[0128] The pellets obtained in each of the examples and comparative examples were supplied to a Sumitomo Heavy Industries, Ltd. injection molding machine (SE-75D-HP) set at a cylinder temperature of 310°C, and injection molding was performed using an ISO Type 1A dumbbell piece molding die adjusted to a mold temperature of 140°C to obtain ISO Type-A dumbbell pieces. Note that the injection molding was performed in such a manner that the resin was injected from one gate so as to become a test piece not including a weld. The central portion of the dumbbell-shaped test piece was cut into a bar shape having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm, and the test piece subjected to the notch processing was used as an impact resistance test piece, and a Charpy impact test was performed in accordance with ISO 179-1 / 1eA to measure the impact strength (kJ / mm 2 ).

[0129] (2) Measurement of Flexural Modulus

[0130] The same ISO Type-A dumbbell pieces as in (1) were used as test pieces, and the flexural modulus (GPa) was measured in accordance with ISO 178, respectively. The results are shown in Table 1 and Table 2.

[0131] (3) Measurement of Volume Resistivity

[0132] The volume resistivity was measured using "Loresta AX MCP-T370" (upper limit of measurement: 1016Ωcm) manufactured by Nittoseiko Analytech Co., Ltd. The results are shown in Table 1 and Table 2. 6The volume resistivity of each test piece was measured at room temperature 21°C, humidity 67RH% according to JIS K 7194 "Resistivity test method for electrically conductive plastics based on 4-probe method". The test pieces were formed by feeding the pellets obtained in each of the examples and comparative examples to a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) set at a cylinder temperature of 310°C, using a mold temperature-adjusted mold for sheet molding at a mold temperature of 140°C to perform injection molding, and molding into a sheet shape (80 mm x 50 mm x 2 mm t). The results are shown in Tables 1 and 2.

[0133] (4) Resistance value measurement of molded product

[0134] The pellets obtained in each of the examples and comparative examples were fed to a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) set at a cylinder temperature of 310°C, using a mold temperature-adjusted mold for molding at a mold temperature of 140°C to perform injection molding, and molded into a molded product having a length of 20 mm x width of 40 mm x thickness of 1 mm. The obtained molded product was pressed with two aluminum alloy (A1050) sheets of 30 mm x 50 mm x 1 mm overlapped in the thickness direction, in a state in which the entire molded product was in contact with the aluminum sheets at a pressure of 30 kPa. An electrode was attached to each of the aluminum alloy sheets in this state, and the resistance value (kΩ) when a current of 0.1 mA was applied was measured using a Sibata electric resistance meter RM3545. The resistance values were measured for 30 pieces, and the average value of the measured resistance values was taken as the resistance value (kΩ) of the molded product, and the value obtained by dividing the standard deviation by the average value was taken as the deviation. The results are shown in Tables 1 and 2.

[0135] (5) Long-term stability evaluation

[0136] The same molded product and aluminum sheet as in (4) were left to stand in a constant temperature and humidity chamber at 85°C / 95% RH for 6 months in a state in which they were pressed at 10 kPa. For the aluminum sheet after standing, the corrosion product was removed by the chemical corrosion product removal method of JIS Z 2371, the corrosion product was removed by a method using nitric acid, and observation was performed using a three-dimensional measuring machine (KEYENCE VR-6000), and the maximum value of the pitting depth of the surface in contact with the molded product was measured as the maximum pitting depth. The smaller the maximum pitting depth, the more excellent the long-term stability. The results are shown in Tables 1 and 2.

[0137] (6) Quantification of carboxyl group content of PAS resin

[0138] The PPS resin used in each of the examples and comparative examples was pressed at 350°C under a load of 10 MPa for 60 seconds, and then quenched to 25°C for 60 seconds, thereby producing a thin film showing amorphousness. The thin film showing amorphousness thus obtained was measured by a Fourier transform infrared spectrometer (hereinafter abbreviated as "FT-IR apparatus"). The relative intensity of the absorbance at 1705 cm -1 in the infrared absorption spectrum to the absorbance at 630.6 cm -1 was calculated, and the content of carboxyl groups in the measurement sample (hereinafter abbreviated as "total content of carboxyl groups") was calculated using a standard curve prepared by a method described later. The results are shown in Tables 1 and 2. Note that the content of carboxyl groups is expressed by the number of moles in 1 g of the resin mixture, and is expressed by [μmol / g]. The standard curve was prepared by the following method. First, a predetermined amount of 4-chlorophenylacetic acid was added to a PAS resin produced in such a manner that carboxylate groups are contained at the molecular terminal without acid treatment, and the mixture was sufficiently mixed, and then a thin film was produced in the same manner as described above, and measurement was performed by the FT-IR apparatus. The standard curve was prepared by plotting the relative intensity ratio of the absorbances at the above two wavelengths with respect to the content of carboxyl groups calculated from the added amount of 4-chlorophenylacetic acid.

[0139] [Table 1]

[0140]

[0141] [Table 2]

[0142]

[0143] Note that the compounding ratio of the compounding components in Tables 1 and 2 was used as follows.

[0144] • PPS resin

[0145] A-1: PPS resin (melt viscosity (V6) 10 Pa-s, zeta potential -58 mV, carboxyl group amount 30 μmol / g)

[0146] A-2: PPS resin (melt viscosity (V6) 50 Pa-s, zeta potential -64 mV, carboxyl group amount 30 μmol / g)

[0147] A-3: PPS resin (melt viscosity (V6) 200 Pa-s, zeta potential -63 mV, carboxyl group amount 30 μmol / g)

[0148] A-4: PPS resin (melt viscosity (V6) 400 Pa-s, zeta potential -60 mV, carboxyl group amount 20 μmol / g)

[0149] • Carbon-based material

[0150] B-1: Carbon black, "MA-100" manufactured by Mitsubishi Chemical Corporation, pH 3.5, DBP absorption 100 cm 3 / 100 g, average primary particle diameter 24 nm

[0151] B-2: Carbon black, "#4400" manufactured by Tokai Carbon Co Ltd, pH 6, DBP absorption 138 cm 3 / 100 g, average primary particle diameter 38 nm

[0152] B-3: Carbon black, "Ketjenblack" manufactured by Lion Specialty Chemicals Co., Ltd., pH 9, DBP absorption 360 cm 3 / 100 g, average primary particle diameter 40 nm

[0153] B-4: Flaky graphite, "CNP15" manufactured by Ito Graphite Co., Ltd., pH 8, average particle diameter 15 μm

[0154] B-5: Artificial graphite, "AGB-604" manufactured by Ito Graphite Co., Ltd., pH 8, average particle diameter 55 μm

[0155] B-6: Expanded graphite, "EC500" manufactured by Ito Graphite Co., Ltd., pH 8, average particle diameter 25 μm

[0156] C-1: Carbon fiber, "HT C702" manufactured by Teijin Limited, average fiber length 6 mm

[0157] C-2: Glass fiber, "T-717H" manufactured by Nippon Electric Glass Co., Ltd., fiber length 3 mm, average diameter 10 μm

[0158] D-1: Silane coupling agent, "XIAMETER (registered trademark) OFS-6040" manufactured by Dow Corning Toray Co., Ltd.

[0159] E-1: Thermoplastic elastomer (copolymer of ethylene:methyl acrylate:glycidyl methacrylate = 64 mol%:30 mol%:6 mol%)

[0160] F-1: Calcium carbonate, "Calcium carbonate 1st grade" manufactured by Shiseido Powder Co., Ltd.

[0161] Comparing the examples of Tables 1-2 with the comparative examples, the molded products molded from the resin compositions of the examples have excellent Charpy impact strength, and the volume resistivity shows a low value, and furthermore, the composite of the examples shows a small resistance value and deviation, and excellent long-term stability. In comparison with the examples, the long-term stability of Comparative Example 1 is poor, the resistance value of Comparative Example 2 is large, the toughness of Comparative Example 3 is poor, the processability of Comparative Example 4 is poor, the deviation of the resistance value of Comparative Examples 5 and 6 is large, and all of the required properties are not satisfied.

Claims

1. A polyarylene sulfide resin composition, wherein a polyarylene sulfide resin (A) and a carbon-based material (B) other than carbon fiber are compounded as essential components. The melt viscosity (V6) of the polyarylene sulfide resin (A) is below 200 Pa·s. The pH of the carbon-based material (B) other than carbon fiber is above 6. The amount of the carbon-based material (B) other than carbon fiber is 5 to 80 parts by weight relative to 100 parts by weight of the polyarylether sulfide resin (A), and, The flexural modulus of the polyarylene sulfide resin composition is below 18 GPa. in, Melt viscosity (V6) represents the melt viscosity after holding the material for 6 minutes using a flow tester at a temperature of 300°C, a load of 1.96 MPa, and an orifice with a length-to-diameter ratio of 10 / 1.

2. The polyarylene sulfide resin composition according to claim 1, further comprising a fibrous filler (C).

3. The polyaryl sulfide resin composition according to claim 2, wherein, The amount of fibrous filler (C) is 20 to 80 parts by weight relative to 100 parts by weight of the polyarylether sulfide resin (A).

4. The polyarylene sulfide resin composition according to claim 1 or 2, wherein, The carbon-based material (B) other than carbon fiber includes furnace black. The DBP absorption of the furnace black is 100 cm⁻¹. 3 / 100g or more, and the primary particle size is less than 60nm.

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

6. The polyarylene sulfide resin composition according to claim 1 or 2, wherein, The zeta potential of the polyarylene sulfide resin (A), as determined by the flow potential method, is above -70mV under pH conditions of 7.8 to 8.

2.

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

8. A composite component formed by joining the molded article of claim 7 with a metal component.

9. A secondary battery component comprising the composite component of claim 8.

10. A method for manufacturing a polyarylene sulfide resin composition, comprising the steps of: compounding a polyarylene sulfide resin (A) and a carbon-based material (B) other than carbon fiber as essential components, and performing melt mixing at a temperature above the melting point of the polyarylene sulfide resin (A). The melt viscosity (V6) of the polyarylene sulfide resin (A) is below 200 Pa·s. The pH of the carbon-based material (B) other than carbon fiber is above 6. The amount of the carbon-based material (B) other than carbon fiber is 5 to 80 parts by weight relative to 100 parts by weight of the polyarylether sulfide resin (A), and, The flexural modulus of the polyarylene sulfide resin composition is below 18 GPa. in, Melt viscosity (V6) represents the melt viscosity after holding the material for 6 minutes using a flow tester at a temperature of 300°C, a load of 1.96 MPa, and an orifice with a length-to-diameter ratio of 10 / 1.

11. The polyarylene sulfide resin composition according to claim 10, further compounded with a fibrous filler (C).

12. The method for manufacturing the polyarylene sulfide resin composition according to claim 11, wherein, The amount of fibrous filler (C) is 20 to 80 parts by weight relative to 100 parts by weight of the polyarylether sulfide resin (A).

13. The method for manufacturing the polyarylene sulfide resin composition according to claim 10 or 11, wherein, The carbon-based material (B) other than carbon fiber includes furnace black. The DBP absorption of the furnace black is 100 cm⁻¹. 3 / 100g or more, and the primary particle size is less than 60nm.

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

15. The method for manufacturing the polyarylene sulfide resin composition according to claim 10 or 11, wherein, The zeta potential of the polyarylene sulfide resin (A), as determined by the flow potential method, is above -70mV under pH conditions of 7.8 to 8.

2.

16. A method for manufacturing a molded article, comprising: a step of manufacturing a polyarylene sulfide resin composition using the method of claim 10 or 11, and a step of melt molding the obtained polyarylene sulfide resin composition.

17. A method for manufacturing a composite, comprising: a step of manufacturing a molded article using the method of claim 16, and a step of joining the obtained molded article with a metal component.

18. A method for using the composite of claim 17 in a secondary battery component.

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