Polyarylene sulfide resin composition and metal member-polyarylene sulfide resin composition member composite

Abstract

To provide a polyarylene sulfide resin composition comprising a post consumer recycled polyamide resin which is excellent in cold-heat impact resistance and bonding properties with a metal without impairing the heat resistance, chemical resistance, flowability or the like inherent in a polyarylene sulfide resin and a composite comprising the same.SOLUTION: There is provided a polyarylene sulfide resin composition which comprises 10 to 90 pts.wt. of a post consumer recycled polyamide resin (B) based on 100 pts.wt. of a polyarylene sulfide resin (A) having a melt viscosity of 100 to 2000 poise as measured by a Koka type flow tester equipped with a die of 1 mm in diameter and 2 mm in length under a measuring temperature of 315°C and a load of 10 kg and comprises 10 to 110 pts.wt. of a glass fiber (C) and 1 to 40 pts.wt. of a thermoplastic elastomer (D) based on 100 pts.wt. of the total amount of the polyarylene sulfide resin (A) and the post-consumer recycled polyamide resin (B).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyarylene sulfide resin composition and a metal member-polyarylene sulfide resin composition member composite, and particularly relates to a polyarylene sulfide resin composition capable of providing a composite that, although containing a post-consumer recycled polyamide resin whose use is expected, is excellent in cold and heat shock resistance and exhibits excellent adhesiveness and airtightness even when formed into a composite with a metal member, and a metal member-polyarylene sulfide resin composition member composite comprising the composition.

Background Art

[0002] Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) typified by poly(p-phenylene sulfide) (hereinafter sometimes abbreviated as PPS) is a resin exhibiting excellent properties such as heat resistance, chemical resistance, and fluidity, and taking advantage of its excellent properties, it is widely used in electric and electronic device members, automotive members, OA device members, etc.

[0003] However, since PAS is inferior in cold and heat shock resistance compared to other engineering plastics, blending a modified ethylene-based copolymer with PAS has been proposed as a technique for improving the cold and heat shock resistance of PAS (see, for example, Patent Documents 1 and 2).

[0004] In addition, in order to reduce the weight of parts of transportation equipment such as automobiles and aircraft, methods of replacing a part of the metal with resin have been studied. As a method of composite integration of resin and metal, a method of directly integrating by inserting a metal member having a surface subjected to physical treatment and / or chemical treatment in a mold and injection molding the resin (hereinafter sometimes referred to as injection insert molding method) has attracted attention from the viewpoints of high mass productivity, few part numbers, low cost, high design freedom, and low environmental load, and has been proposed in the manufacturing process of portable electronic devices such as smartphones (see, for example, Patent Documents 3 to 5).

[0005] On the other hand, in recent years, there has been a growing demand, mainly in Europe and the United States, for the use of recycled resins in electrical and electronic equipment components, with the aim of reducing plastic waste, and this trend is spreading to automotive components and other areas.

[0006] Among these, used fishing nets and ropes are left in large quantities, becoming one of the main causes of marine pollution. In addition, many carpets and mats used in homes, automobiles, or for commercial purposes are also discarded, and attempts have begun to recycle the polyamide resin (sometimes referred to as nylon) used in many of these fishing nets, ropes, carpets, and mats. Recycled materials can be classified into post-consumer recycled materials (sometimes abbreviated as PCR) and post-industrial recycled materials (sometimes abbreviated as PIR). PCR refers to materials collected or recycled after products have been used and discarded by consumers, while PIR refers to materials collected or recycled from waste generated in the manufacturing process before products reach consumers. Compared to PIR, PCR is less stable in terms of degradation during use, and it is difficult to manufacture and obtain stable PCR suitable for use, resulting in higher costs. Therefore, its application is limited to certain areas such as PET bottles, and further dissemination and utilization of PCR are desired in the future.

[0007] Furthermore, as a resin composition containing recycled materials, a recycled resin composition for use as filament material for fused deposition modeling (FDM) 3D printers, comprising: (A) a recycled resin recycled from plastic packaging material, containing a polyolefin resin as the main component and unmelted material in which the proportion of particles with a maximum diameter of 200 μm or more is 15% or less; and (B) a resin having a melt flow rate of 5 g / 10 min or more as measured at a temperature of 230 °C and a load of 2.16 kg (see, for example, Patent Document 6), (A) recycled aromatic polycarbonate resin 40~ A polycarbonate resin composition has been proposed (see, for example, Patent Document 7) that contains (C) 10 to 60 parts by mass of un-nickel coated carbon fibers coated with a resin selected from polyamide, polyurethane, and epoxy resin, in a total of 100 parts by mass of (B) aromatic polycarbonate resin (80% by mass) and 20 to 60% by mass of (A), and does not contain nickel-coated carbon fibers.

[0008] Furthermore, a method for manufacturing molded articles containing recycled materials has been proposed, characterized by feeding 20 to 80% by weight of recycled pellets of fibrous filler-reinforced cross-linked polyphenylene sulfide composition and 80 to 20% by weight of non-recycled pellets of fibrous filler-reinforced cross-linked polyphenylene sulfide composition into an injection molding machine and performing injection molding (see, for example, Patent Document 8).

[0009] Furthermore, a method for recycling nylon has been proposed, which includes the steps of: providing nylon fiber waste, which is oil-resistant nylon 6 fiber waste or oil-resistant nylon 66 fiber waste; crushing the nylon fiber waste to form a plurality of nylon fiber fragments; washing the nylon fiber fragments to reduce the oil content of the nylon fiber fragments to 0.22 wt% or less; dehydration and extrusion to remove moisture from the nylon fiber fragments to form a plurality of nylon films with a moisture content of 4 wt% or less; melt granulation to form a plurality of recycled nylon particles by melt granulating the nylon films; and melt spinning to obtain recycled nylon fibers by melt spinning the recycled nylon particles (see, for example, Patent Document 9). [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Publication No. 2008-144003 [Patent Document 2] Japanese Patent Publication No. 2005-306926 [Patent Document 3] Patent No. 5701414 [Patent Document 4] Patent No. 5714193 [Patent Document 5] Patent No. 4020957 [Patent Document 6] Japanese Patent Publication No. 2021-115795 [Patent Document 7] Patent No. 6825890 [Patent Document 8] Patent No. 5386853 [Patent Document 9] Patent No. 6629943 [Overview of the project] [Problems that the invention aims to solve]

[0011] However, the resin compositions proposed in Patent Documents 1 and 2 do not mention any resin compositions containing recycled nylon. Furthermore, the method for producing composites described in Patent Document 3, the composite structures described in Patent Document 4, and the laser processing method described in Patent Document 5 also do not mention any resin compositions containing recycled nylon.

[0012] The resin compositions proposed in Patent Documents 6 and 7 do not mention polyarylene sulfide resins at all. Furthermore, the method for manufacturing molded articles proposed in Patent Document 8 contains recycled fibrous filler-reinforced polyphenylene sulfide composition pellets, i.e., PIR, which are regenerated from sprues, runners, or other waste materials of the molded articles generated during injection molding, and does not contain PCR, which is difficult to reuse. Moreover, the manufacturing method proposed in Patent Document 9 relates to a method for manufacturing recycled nylon fibers, and does not mention resin compositions containing recycled nylon at all.

[0013] Therefore, the present invention aims to provide a PAS resin composition containing PCR polyamide resin and a metal member-PAS resin composition composite member that does not impair the inherent heat resistance, chemical resistance, and fluidity of PAS resin, and exhibits excellent resistance to thermal shock and bonding to metals. [Means for solving the problem]

[0014] As a result of diligent research to solve the above problems, the present inventors have found that a specific PAS resin composition containing PCR polyamide resin can be made to have excellent heat resistance, mechanical strength, fluidity, thermal shock resistance, and bonding properties with metals, and have completed the present invention.

[0015] That is, the present invention relates to a polyarylene sulfide resin composition comprising 100 parts by weight of a PAS resin (A) having a melt viscosity of 100 to 2000 poise measured under the conditions of a measurement temperature of 315 ° C and a load of 10 kg using an aging type flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm, 10 to 90 parts by weight of a PCR polyamide resin (B), 10 to 110 parts by weight of glass fiber (C) and 1 to 40 parts by weight of a thermoplastic elastomer (D) based on 100 parts by weight of the total amount of the PAS resin (A) and the PCR polyamide resin (B).

[0016] The present invention will be described in detail below.

[0017] The PAS resin (A) constituting the PAS resin composition of the present invention may be any one belonging to the category generally referred to as a PAS resin. Examples of the PAS resin include homopolymers or copolymers composed of p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and biphenylene sulfide units. Specific examples of the PAS resin include PPS, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyphenylene sulfide ether, etc. Among them, PPS is preferable because it provides a PAS resin composition having particularly excellent heat resistance and strength characteristics.

[0018] The PAS resin (A) has a melt viscosity of 100 to 2000 poise measured under the conditions of a measurement temperature of 315 ° C and a load of 10 kg using an aging type flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. Here, if it is less than 100 poise, the resulting composition will be inferior in cold and heat shock resistance. On the other hand, if it exceeds 2000 poise, the fluidity and the bonding property with metal members will be inferior.

[0019] The PAS resin (A) can be produced by methods known for producing PAS resin, for example, by polymerizing an alkali metal sulfide salt and a polyhalogen aromatic compound in a polar solvent. Examples of polar organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, and dimethylacetamide. Examples of alkali metal sulfide salts include anhydrous or hydrated sodium sulfide, rubidium sulfide, and lithium sulfide. Alternatively, the alkali metal sulfide salt may be obtained by reacting an alkali metal hydrosulfide salt with an alkali metal hydroxide. Examples of polyhalogen aromatic compounds include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4'-dichlorodiphenylsulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, and 4,4'-dichlorodibiphenyl.

[0020] Furthermore, the PAS resin (A) may be linear, or it may be a PAS resin with some crosslinking or branching structures introduced by adding a small amount of polyhalogen compounds of trihalogen or higher during polymerization, or it may be a PAS resin in which part and / or the ends of the molecular chain are modified with functional groups such as carboxyl groups, carboxymetal salts, amino groups, alkyl groups, alkoxy groups, or nitro groups, or it may be a PAS resin that has been heat-treated in a non-oxidizing inert gas such as nitrogen, or it may be a mixture of these structures. In addition, the PAS resin (A) may be a PAS resin (A) that has had impurities such as sodium atoms, PAS resin oligomers, sodium chloride, and sodium salt of 4-(N-methyl-chlorophenylamino)butanoate reduced by deionization treatment (such as acid washing or hot water washing) or washing treatment with organic solvents such as acetone or methyl alcohol before or after heat curing. Furthermore, it may be a PAS resin (A) that has been heat-treated in an inert gas or oxidizing gas after the polymerization reaction is complete and cured.

[0021] As the PAS resin (A), not only the PAS resin called virgin resin obtained by the above production method, but also the PCR PAS resin collected or recycled after the product is used and discarded by consumers, and the recycled PAS resin which is the PIR PAS resin such as sprues, runners, unused products during molding, and defective molded products generated during the production process of the product. Among them, it is preferably the PIR PAS resin in which its deterioration is relatively suppressed.

[0022] The PCR polyamide resin (B) constituting the PAS resin composition of the present invention may be any polyamide resin collected or recycled after the product is used and discarded by consumers. Examples of the polyamide resin include polytetramethylene sebacamide (nylon 410), polypentamethylene sebacamide (nylon 510), polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene sebacamide (nylon 1010), polydodecaneamide (nylon 12), polyundecaneamide (nylon 11), polyhexamethylene terephthalamide (nylon 6T), polyxylylene adipamide (nylon XD6), polynonane methylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T) and other homopolyamide resins or copolyamides (nylon 6 / 66, nylon 6 / 10, nylon 6 / 66 / 610, 66 / 6T, 66 / 10T) which are copolymers of these. Furthermore, mixtures of these polyamide resins may also be used.

[0023] In addition, as the PCR polyamide resin (B), since a large amount of polyamide resin of the same structure, the same grade, and in some cases the same lot can be recycled from fishing nets, ropes, carpets, and mats, it is possible to obtain a PCR polyamide resin with little quality variation. As a result, it is possible to obtain a PAS resin composition with little quality variation. Therefore, it is preferably a PCR polyamide resin obtained by collecting and / or recycling fishing nets, ropes, carpets, and mats.

[0024] The amount of PCR polyamide resin (B) added is 10 to 90 parts by weight per 100 parts by weight of PAS resin (A). If the amount of PCR polyamide resin (B) is less than 10 parts by weight, the proportion of recycled material used is low, and the benefits of reuse are diminished. On the other hand, if it exceeds 90 parts by weight, the resulting composition will have inferior fluidity, adhesion to metals, and color.

[0025] The glass fibers (C) constituting the PAS resin composition of the present invention improve the mechanical strength of the PAS resin composition, and any type of glass fiber generally referred to as glass fiber may be used as the glass fiber (C). Specific examples of the glass fibers include chopped strands with an average fiber diameter of 6 to 14 μm, chopped strands made of flattened glass fibers with an aspect ratio of 2 to 4 in the fiber cross-section, milled fibers, roving, etc.; silane fibers; aluminosilicate glass fibers; hollow glass fibers; non-enamel glass fibers, etc. Among these, chopped strands with an average fiber diameter of 6 to 14 μm, or chopped strands made of flattened glass fibers with an aspect ratio of 2 to 4 in the fiber cross-section, are particularly preferred as they result in a PAS resin composition with excellent resistance to thermal shock, thin-wall fluidity, and mechanical strength. These glass fibers (C) can be used in combination of two or more types, and if necessary, they may be pre-treated with functional compounds or polymers such as epoxy compounds, isocyanate compounds, silane compounds, or titanate compounds.

[0026] The amount of glass fiber (C) to be added is 10 to 130 parts by weight per 100 parts by weight of the total amount of PAS resin (A) and PCR polyamide resin (B), in order to obtain a PAS resin composition with an excellent balance of toughness, mechanical strength, and fluidity. If the amount of glass fiber added is less than 10 parts by weight, the resulting composition will have poor mechanical strength and impact resistance. On the other hand, if it exceeds 130 parts by weight, it will have poor resistance to thermal shock, fluidity, and bonding to metals.

[0027] Furthermore, the thermoplastic elastomer (D) constituting the PAS resin composition of the present invention may be any thermoplastic elastomer that is generally referred to as such, and may be a thermoplastic elastomer having a reactive functional group, a thermoplastic elastomer not having a reactive functional group, or a mixture of a thermoplastic elastomer having a reactive functional group and a thermoplastic elastomer not having a reactive functional group. Examples of the reactive functional group include epoxy groups, maleic anhydride groups, carboxylic acid groups, amino groups, isocyanate groups, etc. Examples of thermoplastic elastomers having a reactive group include ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer, modified ethylene copolymers such as maleic anhydride graft-modified ethylene-α-olefin copolymer, hydrogenated styrene-butadiene-styrene block copolymer modified with maleic anhydride or a derivative thereof, etc. Examples include hydrogenated vinyl aromatic compound block copolymers such as hydrogenated ethylene-butadiene block copolymers modified with maleic anhydride or its derivatives, hydrogenated styrene-isoprene block copolymers modified with maleic anhydride or its derivatives, and hydrogenated styrene-isoprene-styrene block copolymers modified with maleic anhydride or its derivatives. In addition, polyurethane thermoplastic elastomers, polyester thermoplastic elastomers, polyamide thermoplastic elastomers, acrylonitrile-butadiene rubber thermoplastic elastomers, ethylene-propylene copolymers, and ethylene-propylene-diene copolymers can also be used, as long as they have functional groups that can react with PAS resin. Among these, modified ethylene copolymers are preferred because they result in polyarylene sulfide resin compositions with particularly excellent toughness.

[0028] On the other hand, thermoplastic elastomers that do not have reactive functional groups include those thermoplastic elastomers that do not have functional groups as described above, and among these, olefin-acrylic acid ester binary copolymers are preferred because they yield a PAS resin composition with an excellent balance of fluidity and toughness. Examples of olefins in this case include ethylene or α-olefins with 3 or more carbon atoms, and examples of acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, etc.

[0029] The amount of thermoplastic elastomer (D) added is 1 to 50 parts by weight per 100 parts by weight of the total amount of PAS resin (A) and PCR polyamide resin (B), in order to obtain a PAS resin composition with an excellent balance of toughness, adhesion to metals, and fluidity. If the amount of thermoplastic elastomer added is less than 1 part by weight, the resulting composition will have poor resistance to thermal shock and adhesion to metal components. On the other hand, if it exceeds 50 parts by weight, it will have poor fluidity and mechanical strength.

[0030] The PAS resin composition of the present invention exhibits particularly excellent mechanical strength and impact resistance, and may further contain a compatibilizer (E). The compatibilizer may be, for example, isocyanurate, epoxy resin, silane coupling agent, or a mixture of these compatibilizers.

[0031] Furthermore, any isocyanurate can be used, and among them, an aliphatic isocyanurate is particularly preferred because it results in a PAS resin composition with low mold contamination. Examples of aliphatic isocyanurates include 1,3,5-tris(6-isocyanatohexa-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(6-isocyanatotetra-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1,3,5-tris(6-isocyanatododeca-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and an aliphatic isocyanurate with a molecular weight of 500 or more is particularly preferred because it results in a PAS resin composition with low mold contamination. The aliphatic isocyanurate may be a polymer such as a dimer or trimer, or an isocyanurate containing a polymer such as a dimer or trimer in an aliphatic isocyanurate monomer. It is preferable that the aliphatic isocyanurate contains 20% or more isocyanate groups, as it exhibits excellent reactivity with PAS and PCR polyamide resins and results in a PAS resin composition with excellent impact resistance.

[0032] Furthermore, the aliphatic isocyanurate may be one in which a portion of the aliphatic isocyanate has been modified with an alcohol such as 1,3-butanediol or 2,2,4-trimethyl-1,3-pentadiol. Among the aliphatic isocyanurates, 1,3,5-tris(6-isocyanatohexa-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is particularly preferred because it has excellent resistance to cold and heat and is readily available. Specific examples of 1,3,5-tris(6-isocyanatohexa-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione include (trade name) Coronate HXR (manufactured by Tosoh Corporation) and (trade name) Duranate TPA-100 (manufactured by Asahi Kasei Corporation).

[0033] Furthermore, any epoxy resin belonging to the category of epoxy resins may be used. Specific examples include 2,2-bis(4'-hydroxyphenyl)propane (bisphenol A), bis(2-hydroxyphenyl)methane (bisphenol F), 4,4'-dihydroxydiphenylsulfone (bisphenol S), 4,4'-dihydroxybiphenyl, resorcinol, saligenin, trihydroxydiphenyldimethylmethane, tetraphenyloleethane, halogen-substituted and alkyl-substituted compounds thereof, butanediol, ethylene glycol, erythritol, novolac, glycerin, polyoxyalkylene, and other compounds containing two or more hydroxyl groups in their molecule, synthesized from epichlorohydrin, etc. Examples of epoxy resins containing glycidyl groups include glycidyl ether-based epoxy resins; glycidyl ester-based epoxy resins synthesized from compounds containing two or more hydroxyl groups in the molecule and glycidyl phthalate esters, etc.; glycidylamine-based epoxy resins synthesized from primary or secondary amines such as aniline, diaminodiphenylmethane, metaxylenediamine, 1,3-bisaminomethylcyclohexane and epichlorohydrin, etc.; and epoxy resins that do not contain glycidyl groups, such as epoxidized soybean oil, epoxidized polyolefins, vinylcyclohexene dioxide, dicyclopentadiene dioxide, etc. Among these, bisphenol-type epoxy resins such as glycidyl ether-based epoxy resins and glycidyl ester-based epoxy resins of bisphenols such as bisphenol A, bisphenol F, and bisphenol S are preferred because the resulting PAS resin composition exhibits particularly excellent impact resistance. A bisphenol A-type epoxy resin is even more preferred.

[0034] Furthermore, any silane coupling agent belonging to the category of silane coupling agents may be used, but among them, a silane coupling agent comprising a trialkoxysilane coupling agent having a glycidyl group and / or a trialkoxysilane coupling agent having an amino group is preferred because it results in a PAS resin composition with excellent impact resistance and mechanical strength. The silane capryling agent used in this process is not particularly limited as long as it is a trialkoxysilane coupling agent having a glycidyl group or an amino group. Specific examples of agents belonging to this category include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane.

[0035] Furthermore, the amount of the compatibilizer (E) is preferably 0.1 to 15 parts by weight per 100 parts by weight of PAS resin, in order to obtain a PAS resin composition that has excellent impact resistance, mechanical strength, and low mold contamination.

[0036] Furthermore, the PAS resin composition of the present invention may contain a release agent (F) to improve mold release properties and appearance when forming molded articles. Suitable release agents (F) include, for example, polyethylene wax, polypropylene wax, and fatty acid amide wax. Commonly available commercially available polyethylene wax and polypropylene wax can be used. The fatty acid amide wax is a polycondensate composed of a higher aliphatic monocarboxylic acid, a polybasic acid, and a diamine; any product belonging to this category can be used. For example, a polycondensate composed of stearic acid, sebacic acid, and ethylenediamine, such as (trade name) Light Amid WH-255 (manufactured by Kyoeisha Chemical Co., Ltd.), can be cited.

[0037] Furthermore, since the PAS resin composition of the present invention has particularly excellent dimensional accuracy, it may also contain a non-fibrous filler (G). Examples of the non-fibrous filler include calcium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, mica, silica, talc, clay, calcium sulfate, kaolin, wollastonite, zeolite, silicon oxide, magnesium oxide, zirconium oxide, tin oxide, magnesium silicate, calcium silicate, calcium phosphate, magnesium phosphate, hydrotalcite, glass powder, glass balloons, glass flakes, etc. Calcium carbonate or glass flakes are preferred, as they result in a PAS resin composition with particularly excellent dimensional accuracy and mechanical strength.

[0038] The PAS resin composition of the present invention may be used in combination with various additives without departing from the objectives of the present invention. For example, it may contain one or more conventional additives such as plasticizers, antioxidants, heat stabilizers, UV inhibitors, foaming agents, and pigments such as carbon black, which are conventionally known; polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organophosphorus compounds; antioxidants; heat stabilizers; UV inhibitors; foaming agents; and pigments such as carbon black. Furthermore, it may be composed of a mixture of one or more thermoplastic resins such as various thermosetting resins, cyanate ester resins, phenolic resins, polyimides, silicone resins, polyesters, polyphenylene oxide, polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, polyamideimide, and polyalkylene oxide.

[0039] As a method for producing the PAS resin composition of the present invention, conventionally used heat-melt kneading methods can be used. For example, heat-melt kneading methods using a single-screw or twin-screw extruder, kneader, mill, brabender, etc. are used, and a heat-melt kneading method using a twin-screw extruder, which has excellent kneading capacity, is particularly preferred. In this case, it is preferable that the screw used in the twin-screw extruder has two or more kneading zones. Furthermore, in order to ensure sufficient compatibility between the PAS resin (A) and the PCR polyamide resin (B), and as a result obtain a PAS resin composition with excellent toughness such as impact resistance, it is preferable that the screw has a screw length (L) to screw diameter (D) ratio (L / D) of 30 or more, and particularly 40 or more.

[0040] Furthermore, to ensure sufficient compatibility between the PAS resin (A) and the PCR polyamide resin (B), and to facilitate the suppression of thermal decomposition of the PCR polyamide resin (B), it is preferable to set the cylinder temperature of the kneading zone of the extruder to 285°C to 320°C, and particularly preferably to 290°C to 310°C. In addition, to ensure good dispersibility and distribution of the PCR polyamide resin in the PAS resin phase of the PAS resin composition, and as a result, to obtain a PAS resin composition with excellent toughness such as impact resistance, the peripheral speed of the screw is preferably 50 to 400 mm / second, and particularly preferably 150 to 300 mm / second. Furthermore, as the residence time of the molten resin in the extruder, it is preferable to have a sufficient melt-kneading time between the PAS resin (A) and the PCR polyamide resin (B), and to facilitate the suppression of thermal decomposition of the PCR polyamide resin (B), and therefore preferably 30 to 100 seconds, and particularly preferably 30 to 80 seconds.

[0041] The melt-mixed PAS resin composition can be formed into pellets by methods such as hot cutting or mist cutting of the extruded melt-mixed composition, or by methods such as cold cutting of the strands. Cold cutting is preferred, in which the melt-mixed composition is cooled by methods such as water cooling or air cooling to form strands, and then the strands are cut to form pellets, as this allows for the stable and efficient production of pellets with particularly excellent quality and color. The pellets in this case are preferably cylindrical pellets with a diameter of 0.5 to 2.5 mm and a length of 1.5 to 4 mm, or spherical pellets with a diameter of 1 to 3 mm, as these have excellent processability when injection molding various molded products. In particular, pellets with a light brown or brown color are preferred, as this allows for the production of molded products with excellent appearance.

[0042] The PAS resin composition of the present invention is suitable for use as an insert molded article and a metal member-PAS resin composition composite because it has excellent resistance to thermal shock and bonding with metals. The metal member-PAS resin composition composite can be obtained by injection insert molding the PAS resin composition onto a metal member. As for the injection insert molding, a method is preferred in which a surface-roughened metal member is placed in a mold, a molten polyarylene sulfide resin composition is filled into the metal member to form a polyarylene sulfide resin member, and the metal member and the PAS resin composition member are directly integrated, as this method has excellent bonding and productivity.

[0043] The melting temperature of the PAS resin composition in this case can be 280 to 340°C, and as the molding machine for insert molding, it is preferable to use an injection molding machine for injection insert molding because it is particularly efficient in terms of productivity. Furthermore, the mold temperature when performing insert molding is preferably 130°C or higher, and particularly preferably 140 to 160°C, as it is possible to efficiently manufacture metal member-PAS resin composition member composites that have excellent bonding properties. In addition, the mold holding pressure is preferably 1 MPa or higher, and particularly preferably 30 MPa to 100 MPa.

[0044] Methods for roughening the surface of the metal component include physical and / or chemical treatment of the surface. Examples of physical treatments include contacting or impacting the surface with fine solid particles, and irradiating it with high-energy electromagnetic rays. More specifically, examples include sandblasting, liquid honing, and laser processing. Furthermore, examples of abrasives used in sandblasting and liquid honing include sand, steel grit, steel shot, cut wire, alumina, silicon carbide, metal slag, glass beads, and plastic beads. Examples of laser processing include the methods proposed in WO2007 / 072603 and Japanese Patent Publication No. 2015-142960.

[0045] Furthermore, examples of chemical treatments include anodic oxidation and chemical treatment with an aqueous solution of acid or alkali. As for anodic oxidation, for example, a method in which an electrolytic reaction is carried out in an electrolyte with a metal component as the anode to form an oxide film on its surface may be used, and methods that are generally known as anodic oxidation methods in fields such as plating can be used. More specifically, examples include 1) DC electrolysis, in which electrolysis is carried out by applying a constant DC voltage, and 2) bipolar electrolysis, in which electrolysis is carried out by applying a voltage in which an AC component is superimposed on a DC component. Specific examples of anodic oxidation methods include the method proposed in WO2004 / 055248, etc. Furthermore, as a method of chemical treatment with an aqueous solution of acid or alkali, for example, a method of chemically treating the surface of a metal component by immersing it in an aqueous solution of acid or alkali, in which case the aqueous solution of acid or alkali may be, for example, phosphoric acid compounds such as phosphoric acid; chromic acid compounds such as chromic acid; hydrofluoric acid compounds such as hydrofluoric acid; nitric acid compounds such as nitric acid; hydrochloric acid compounds such as hydrochloric acid; sulfuric acid compounds such as sulfuric acid; alkaline aqueous solutions such as sodium hydroxide and ammonia aqueous solution; triazine thiol aqueous solution, triazine thiol derivative aqueous solution Methods such as chemical treatment with a solution can be cited, and more specifically, methods proposed in Japanese Patent Publication No. 2017-132243, Japanese Patent Publication No. 2019-188651, WO2008 / 133296, Japanese Patent No. 5622785, Japanese Patent Publication No. 10-096088, Japanese Patent Publication No. 10-056263, Japanese Patent Publication No. 04-032585, Japanese Patent Publication No. 04-032583, Japanese Patent Publication No. 02-298284, WO2009 / 151099, WO2011 / 104944, etc.

[0046] Furthermore, the metal member may be made of any material that falls within the category of metal members, and among these, aluminum members, aluminum alloy members, copper members, copper alloy members, magnesium members, magnesium alloy members, iron members, titanium members, titanium alloy members, and stainless steel members are preferred because they can be adapted to various applications when combined with PAS resin composition members. In particular, aluminum members, aluminum alloy members, magnesium members, magnesium alloy members, titanium members, and titanium alloy members are preferred because they are excellent in terms of weight reduction, and aluminum members and aluminum alloy members are more preferred. In addition, the metal member may be a wrought material represented by a plate, a cast material represented by die casting, or a forged material.

[0047] Furthermore, the PAS resin composition of the present invention can be molded into any shape using an injection molding machine, extrusion molding machine, transfer molding machine, compression molding machine, blow molding machine, etc.

[0048] The PAS resin composition of the present invention does not impair the heat resistance, chemical resistance, and fluidity inherent in PAS resin, and exhibits excellent thermal shock resistance and bonding properties with metals. It contains PCR polyamide resin and is suitable for use in electrical and electronic components, automotive parts, and other applications. [Effects of the Invention]

[0049] According to the present invention, a PAS resin composition containing PCR polyamide resin can be provided, which has excellent heat resistance, thermal shock resistance, bonding properties with metals, heat and humidity resistance, and fluidity, and is particularly useful for applications such as electrical and electronic components and automotive parts, and has extremely high industrial value. [Brief explanation of the drawing]

[0050] [Figure 1] Schematic diagram of the insert test specimen used in the example. [Examples]

[0051] The present invention will be described in detail below with reference to examples, but the present invention is not limited in any way thereto.

[0052] The polyarylene sulfide (A), post-consumer recycled polyamide resin (B), glass fiber (C), thermoplastic elastomer (D), compatibilizer (E), and mold release agent (F) used in the examples and comparative examples are shown below.

[0053] <Polyarylene sulfide (A)> Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-1)): Melt viscosity 470 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-2)): Melt viscosity 820 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-3)): Melt viscosity 1580 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-4)): Melt viscosity 2500 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-5)): Melt viscosity 80 poise.

[0054] <Post-consumer recycled polyamide resin (B)> PCR polyamide resin (hereinafter referred to as PCR(B-1)); manufactured by Refineverse Co., Ltd., (product name) RA6G00, recycled fishing net polyamide 6 resin. PCR polyamide resin (hereinafter referred to as PCR(B-2)); manufactured by Refineverse Co., Ltd., (product name) RA6R00, recycled fishing net polyamide 6 resin.

[0055] <Polyamide resin (B')> Polyamide 6 resin (B'); manufactured by Ube Industries, Ltd., (product name) 1013B.

[0056] <Glass fiber (C)> Glass fiber (C-1); manufactured by Nippon Electric Glass Co., Ltd., (product name) T-760H; fiber diameter 10 μm, fiber length 3 mm. Glass fiber (C-2); chopped strand manufactured by Nitto Boseki Co., Ltd., (product name) CSG-3PA 830, fiber cross-sectional aspect ratio 4.

[0057] <Thermoplastic elastomer (D)> Ethylene-α,β-unsaturated carboxylate alkyl ester-maleic anhydride copolymer (D-1) (hereinafter simply referred to as thermoplastic elastomer (D-1)): Manufactured by SK global chemical, (product name) Bondine AX8390, ethylene residue units: α,β-unsaturated carboxylate alkyl ester residue units: maleic anhydride residue units (weight ratio) = 69.7:29:1.3. Ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer (D-2) (hereinafter simply referred to as thermoplastic elastomer (D-2)): Manufactured by SK global chemical, (product name) LOTADER AX8700, ethylene residue units: α,β-unsaturated carboxylic acid glycidyl ester residue units: α,β-unsaturated carboxylic acid alkyl ester residue units (weight ratio) = 67:8:25.

[0058] <Compatibilizer (E)> Trialkoxysilane coupling agent containing a glycidyl group (E-1); manufactured by Shin-Etsu Chemical Co., Ltd., (product name) KBM-403; 3-glycidoxypropyltrimethoxysilane. Isocyanurate (E-2); manufactured by Tosoh Corporation, (product name) Coronate HXR (isocyanate content 21.8%, molecular weight 504). Epoxy resin (E-3); manufactured by Mitsubishi Chemical Corporation, (product name) 1004.

[0059] <Release agent (F)> Release agent (F-1); manufactured by Kyoeisha Chemical Co., Ltd., (product name) Light Amid WH-255.

[0060] Synthesis Example 1 In a 50-liter autoclave equipped with a stirrer, 6214 g of Na2S·2,9H2O and 17000 g of N-methyl-2-pyrrolidone were charged. The mixture was gradually heated to 205°C while stirring under a nitrogen stream, and 1355 g of water was removed by distillation. After cooling the system to 140°C, 7168 g of p-dichlorobenzene, 12 g of 3,5-dichloroaniline, and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225°C over 2 hours, polymerized at 225°C for 2 hours, then heated to 250°C over 30 minutes, and polymerized further at 250°C for 3 hours. After polymerization was complete, the mixture was cooled to room temperature, and the solids were isolated by centrifugation. The solid was washed with hot water at 180°C and dried at 100°C overnight to obtain poly(p-phenylene sulfide).

[0061] The obtained poly(p-phenylene sulfide) was dried in a vacuum dryer under reduced pressure at 240°C for 4 hours to obtain linear amino group-containing poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-1)). The melt viscosity of PPS(A-1) was 470 poise.

[0062] Synthesis Example 2 In a 50-liter autoclave equipped with a stirrer, 6214 g of Na2S·2,9H2O and 17000 g of N-methyl-2-pyrrolidone were charged. The mixture was gradually heated to 205°C while stirring under a nitrogen stream, and 1355 g of water was removed by distillation. After cooling the system to 140°C, 7180 g of p-dichlorobenzene, 6 g of 3,5-dichloroaniline, and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225°C over 2 hours, polymerized at 225°C for 2 hours, then heated to 250°C over 30 minutes, and polymerized further at 250°C for 3 hours. After polymerization was complete, the system was cooled to room temperature, and the solid was isolated by centrifugation. The solid was washed with 180°C hot water and dried at 100°C overnight to obtain poly(p-phenylene sulfide).

[0063] The obtained poly(p-phenylene sulfide) was dried in a vacuum dryer under reduced pressure at 240°C for 6 hours to obtain linear amino group-containing poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-2)). The melt viscosity of PPS(A-2) was 820 poise.

[0064] Synthesis Example 3 Poly(p-phenylene sulfide) was obtained by the same polymerization method as in Synthesis Example 1, except that 3,5-dichloroaniline was not used.

[0065] The obtained poly(p-phenylene sulfide) was cured at 250°C for 3 hours in an air atmosphere to obtain branched poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-3)). The melt viscosity of PPS(A-3) was 1580 poise.

[0066] Synthesis Example 4 Poly(p-phenylene sulfide) was obtained by the same polymerization method as in Synthesis Example 2, except that 3,5-dichloroaniline was not used.

[0067] The obtained poly(p-phenylene sulfide) was cured at 250°C for 5 hours in an air atmosphere to obtain branched poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-4)). The melt viscosity of PPS(A-4) was 2500 poise.

[0068] Synthesis Example 5 In a 15-liter autoclave equipped with a stirrer, 1814 g of Na2S·2.9H2O, 8.7 g of granular caustic soda (100% NaOH: Wako Pure Chemical Industries special grade), and 3232 g of N-methyl-2-pyrrolidone were charged. The mixture was gradually heated to 200°C while stirring under a nitrogen stream, and 339 g of water was distilled off. After cooling the system to 190°C, 2085 g of p-dichlorobenzene and 1783 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225°C over 2 hours, polymerized at 225°C for 1 hour, then heated to 250°C over 25 minutes, and polymerized at 250°C for another 2 hours. After polymerization was complete, the mixture was cooled to room temperature, and the solids were isolated by centrifugation. The solid was washed with hot water at 180°C and dried at 105°C overnight to obtain poly(p-phenylene sulfide).

[0069] The obtained poly(p-phenylene sulfide) was dried in a vacuum dryer under reduced pressure at 240°C for 6 hours to obtain linear poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-5)). The melt viscosity of PPS(A-5) was 80 poise.

[0070] The evaluation and measurement methods for the obtained polyarylene sulfide resin composition and the metal member-polyarylene sulfide resin composition composite are shown below.

[0071] ~Measuring the melt viscosity of PAS resin~ The melt viscosity was measured using a high-efficiency flow tester (manufactured by Shimadzu Corporation, product name CFT-500) equipped with a die with a diameter of 1 mm and a length of 2 mm, under conditions of a measurement temperature of 315°C and a load of 10 kg.

[0072] ~Measurement of thermal shock resistance~ Ten test pieces for evaluating thermal shock resistance were prepared by insert molding using an injection molding machine (Sumitomo Heavy Industries, Ltd., product name SE-75S), inserting a 30mm x 20mm x 10mm rectangular steel material (carbon steel) as shown in Figure 1, at a cylinder temperature of 310°C and a mold temperature of 140°C. Ten test pieces for evaluating thermal shock resistance were then coated with a 1mm thick PAS resin composition. The ten test pieces were subjected to a refrigeration cycle, where each cycle consisted of holding them at 150°C for 30 minutes, cooling them to -40°C for 30 minutes, and then heating them again to 150°C. This cycle was continued until cracks were visually observed. The number of refrigeration cycles until cracks were visually observed in 6 of the 10 test pieces was evaluated as thermal shock resistance. Test pieces that exceeded 100 refrigeration cycles were judged to have excellent thermal shock resistance.

[0073] ~Evaluation of bonding properties between resin and metal components~ A metal plate with a surface treatment is placed inside the injection molding machine die, and the PAS resin composition is fed into the hopper of the injection molding machine (Sumitomo Heavy Industries, product name SE75S), and injection insert molding is performed, resulting in a bonding area of ​​50 mm². 2 Shear tensile test specimens were obtained. Next, in accordance with ISO 19095, the joint strength of the joint surface was measured using these shear tensile test specimens and evaluated based on the shear tensile strength. Joints with a joint strength of 30 MPa or higher were judged to have excellent joint properties.

[0074] ~Evaluation of the heat and humidity resistance of PAS resin compositions~ Tensile test specimens were prepared using an injection molding machine (Sumitomo Heavy Industries, Ltd., product name SE-75S), and their tensile strength was measured in accordance with ISO 527-1,2. The tensile test specimens obtained were then placed in a constant temperature and humidity chamber (Hitachi Global Life Solutions, Ltd., product name EC46-HHP) maintained at 85°C and 85% humidity for 2000 hours. After 2000 hours, the specimens were removed, and their tensile strength was measured again in accordance with ISO 527-1,2. Specimens with a tensile strength of 75% or higher compared to the tensile strength measured without the chamber were considered to have excellent heat and humidity resistance.

[0075] ~Measurement of the fluidity of PAS resin composition~ A mold with a spiral groove measuring 1 mm thick and 10 mm wide was mounted on an injection molding machine (Sumitomo Heavy Industries, Ltd., product name SE-75S). Then, the PAS resin composition was introduced into the hopper of the injection molding machine, which was set to a cylinder temperature of 310°C, an injection pressure of 190 MPa, a maximum injection speed, an injection time of 1.5 seconds, and a mold temperature of 135°C, and injected. The length of the melted spiral groove inside the mold was measured as the molding fluidity. A molding fluidity exceeding 120 mm was judged to have excellent fluidity.

[0076] ~Evaluation of the color tone of PAS resin compositions~ Flat plates measuring 70 mm wide x 70 mm long x 1 mm thick were manufactured using an injection molding machine (Sumitomo Heavy Industries, Ltd., product name SE-75S), and their appearance was observed visually. Plates with a light brown or brown color were considered to have a superior color, while those that were black or dark green were considered to have a inferior color.

[0077] Example 1 An aluminum alloy (A5052) sheet (50mm x 10mm x 1mm thick) was immersed for 5 minutes in a degreasing tank containing a 7.5% aqueous solution of aluminum degreasing agent (at 60°C), and then rinsed with deionized water. Next, it was immersed for 1 minute in a tank containing a 1.5% aqueous solution of caustic soda (at 40°C), rinsed with deionized water, and then immersed for 1 minute in a tank containing a 3% nitric acid aqueous solution (at 40°C), and rinsed with deionized water. Next, it was immersed for 1 minute in a tank containing a 3.5% aqueous solution of hydrated hydrazine (at 60°C), rinsed with deionized water, and then immersed for 3 minutes in a tank containing a 0.5% aqueous solution of hydrated hydrazine (at 33°C), rinsed with deionized water, and finally dried in a hot air dryer to obtain a surface-roughened aluminum alloy (A5052) sheet.

[0078] To 100 parts by weight of the PPS resin (A-1) obtained in Synthesis Example 1, 30 parts by weight of PCR (B-1) and 15 parts by weight of thermoplastic elastomer (D-1) were uniformly mixed beforehand and fed into the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX-25αIII, L / D=55) having four kneading zones. Meanwhile, glass fiber (C-1) was fed from the side feeder hopper of the twin-screw extruder in an amount of 40 parts by weight per 100 parts by weight of PPS (A-1). The mixture was melt-kneaded at a raw material supply rate of 25 kg / hr and a screw rotation speed of 200 rpm (peripheral speed: 258 mm / sec) under conditions where the cylinder temperature of the kneading zone was heated to 310°C. After a residence time of 50 seconds, the molten composition flowing out of the die was cooled with water to form strands, which were then cut to produce cylindrical, light brown pellet-shaped PAS resin compositions with a diameter of 1.7 mm and a length of 2.3 mm.

[0079] The obtained PAS resin composition was then injected into an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name SE75S) heated to a cylinder temperature of 310°C and a mold temperature of 140°C, and the molding flow length of the PAS resin composition was measured. In addition, by insert molding of the PAS resin composition with a surface-roughened aluminum alloy plate material placed inside the mold, a bonding area of ​​50 mm² was measured. 2 A composite material consisting of an aluminum alloy member and a PAS resin composition member was obtained as a shear tensile test specimen. Furthermore, the cold and thermal shock resistance and humid heat resistance, as well as the joint strength, were evaluated using test specimens that had been injection-molded and injection-insert-molded. The color tone of the test specimens was also confirmed. The results of each measurement and evaluation are shown in Table 1.

[0080] Examples 2-10 A pelletized PAS resin composition was prepared using the same method as in Example 1, with the blending ratios of PPS resin (A), PCR polyamide resin (B), glass fiber (C), thermoplastic elastomer (D), compatibilizer (E), and mold release agent (F) as shown in Table 1. The obtained PAS resin composition had a light brown or brown color. Then, a metal member-PAS resin composition composite was prepared and evaluated using the same method as in Example 1. The evaluation results are shown in Table 1.

[0081] All of the obtained PAS resin compositions exhibited excellent resistance to thermal shock, bonding to metals, resistance to humid heat, fluidity, and color.

[0082] [Table 1]

[0083] Comparative Examples 1-7, Reference Example 1 A pelletized resin composition was prepared using the same method as in Example 1, with the blending ratios of PPS resin (A), PCR polyamide resin (B), polyamide resin (B'), glass fiber (C), and thermoplastic elastomer (D) as shown in Table 2. Then, a composite was created and evaluated using the same method as in Example 1. The evaluation results are shown in Table 2.

[0084] The resin compositions obtained from Comparative Examples 1 to 7 exhibited poor resistance to thermal shock and poor bonding to metals. The resin compositions obtained from Comparative Examples 3 and 7 exhibited poor resistance to humid heat. The resin compositions obtained from Comparative Examples 1, 3, and 5 exhibited poor fluidity. The resin compositions obtained from Comparative Examples 1 and 6 exhibited poor color tone.

[0085] [Table 2] [Industrial applicability]

[0086] The PAS resin composition of the present invention does not impair the heat resistance, chemical resistance, and fluidity inherent in PAS resin, and exhibits excellent thermal shock resistance and bonding properties with metals. It contains PCR polyamide resin and is particularly useful for applications such as electrical and electronic components and automotive parts. [Explanation of symbols]

[0087] 1; Gate position. 2; Through hole. 3; Insert block. 4; Weld formation position.

Claims

1. A polyarylene sulfide resin composition characterized by comprising 100 parts by weight of polyarylene sulfide resin (A), the melt viscosity measured at a measurement temperature of 315°C and a load of 10 kg using a high-efficiency flow tester equipped with a die of 1 mm in diameter and 2 mm in length, with a melt viscosity of 100 to 2000 poise, and 10 to 90 parts by weight of post-consumer recycled polyamide resin (B), and further comprising 10 to 110 parts by weight of glass fiber (C) and 1 to 40 parts by weight of thermoplastic elastomer (D) per 100 parts by weight of the total amount of polyarylene sulfide resin (A) and post-consumer recycled polyamide resin (B).

2. The polyarylene sulfide resin composition according to claim 1, characterized in that the post-consumer recycled polyamide resin (B) is a post-consumer recycled polyamide resin obtained by collecting at least one selected from fishing nets, ropes, carpets, and mats.

3. The polyarylene sulfide resin composition according to claim 1 or 2, characterized in that the thermoplastic elastomer (D) is a modified ethylene copolymer and / or an olefin-acrylic acid ester binary copolymer.

4. The polyarylene sulfide resin composition according to any one of claims 1 to 3, further characterized by comprising at least one compatibilizer (E) selected from isocyanurate, epoxy resin, and silane coupling agent, and / or at least one release agent (F) selected from the group consisting of polyethylene wax, polypropylene wax, and fatty acid amide wax.

5. A method for producing a polyarylene sulfide resin composition according to any one of 1 to 4, characterized in that at least a polyarylene sulfide resin (A), a post-consumer recycled polyamide resin (B), glass fiber (C), and a thermoplastic elastomer (D) are melt-kneaded and extruded in a twin-screw extruder having a screw with a screw length (L) to screw diameter (D) ratio (L / D) of 30 or more and two or more kneading zones, under kneading conditions of a cylinder temperature of 285°C to 330°C in the kneading zone, a peripheral screw speed of 50 mm / sec to 400 mm / sec, and a residence time of 30 seconds to 100 seconds.

6. A molded article characterized by being an insert molded article of the polyarylene sulfide resin composition described in any one of claims 1 to 4.

7. A metal member-polyarylene sulfide resin composition member composite characterized by being a joint of a metal member having a surface that has been chemically or physically treated and an insert molded member of the polyarylene sulfide resin composition according to any one of claims 1 to 4.

Images