Regenerated polyarylene sulfide resin composition and method for producing same

Abstract

Provided are: a regenerated fibrous filler-reinforced polyarylene sulfide resin composition containing a regenerated polyarylene sulfide resin composition without deteriorating the heat resistance, chemical resistance, flowability, and the like originally possessed by a polyarylene sulfide resin; and a method for producing the regenerated fibrous filler-reinforced polyarylene sulfide resin composition. A regenerated fibrous filler-reinforced polyarylene sulfide resin composition which is characterized by comprising a polyarylene sulfide resin (A), a regenerated polyarylene sulfide resin (B) and a fibrous filler (C), and wherein the amount of the regenerated polyarylene sulfide resin (B) blended is 10-250 parts by weight per 100 parts by weight of the polyarylene sulfide resin (A) having a melt viscosity of 100-3000 poise, and the amount of the fibrous filler (C) blended with the regenerated polyarylene sulfide resin (B) is 10-250 parts by weight per 100 parts by weight of the polyarylene sulfide resin (A) having a melt viscosity of 100-3000 poise. The amount of the fibrous filler (C) blended is 10-60 parts by weight per 100 parts by weight of the total of the polyarylene sulfide resin (A) and the regenerated polyarylene sulfide resin (B).

Description

Technical Field

[0001] The present invention relates to a regenerated fibrous filler-reinforced polyarylene sulfide resin composition containing a regenerated polyarylene sulfide resin. Further, the present invention relates to a regenerated fibrous filler-reinforced polyarylene sulfide resin composition which contains a polyarylene sulfide resin recovered from a polyarylene sulfide resin molded article or the like that has been discarded by incineration, landfilling, etc. after being put on the market, and a polyarylene sulfide resin obtained by collecting and regenerating polyarylene sulfide resins such as gates, runners, or unused parts of the molded article generated during the production of the polyarylene sulfide resin molded article, and which maintains excellent properties such as the mechanical properties and fluidity originally possessed by the polyarylene sulfide resin, and a method for producing the same. Background Art

[0002] Polyarylene sulfides (hereinafter sometimes simply referred to as PAS) represented by poly(phenylene sulfide) (hereinafter sometimes simply referred to as PPS) are resins that exhibit excellent properties such as heat resistance, chemical resistance, and fluidity, and are widely used in electrical / electronic device components, automotive components, and OA device components, etc. due to their excellent properties.

[0003] On the other hand, in recent years, for the purpose of reducing the discharge amount of plastics, etc., requirements for using recycled resins in electrical / electronic device components are increasing, mainly in Europe and the United States, and this trend has also spread to automotive components, etc.

[0004] Generally, recycled materials are roughly classified into post-consumer recycled materials (hereinafter sometimes simply referred to as PCR) and post-industrial recycled materials (hereinafter sometimes simply referred to as PIR). PCR refers to materials that are collected or recycled after being used and discarded by consumers, and PIR refers to materials that are collected or recycled from waste generated during the manufacturing process before the product is delivered to consumers. The recycled polyarylene sulfide resin obtained by recycling a molded article or the like discarded after being put on the market belongs to PCR, and the recycled polyarylene sulfide resin obtained by recycling industrial waste such as gates, runners, or unused parts of the molded article belongs to PIR.

[0005] Moreover, as a resin composition containing recycled materials, for example, there has been proposed: a recycled resin composition (for example, refer to Patent Document 1), which is a recycled resin composition for a filament material for a 3D printer using a thermal melting lamination method, and which contains a recycled resin (A) and a resin (B). The recycled resin (A) is recycled from a plastic packaging material and contains a polyolefin resin as a main component and unmelted matter with a proportion of 15% or less by number of particles having a maximum diameter of 200 μm or more. The resin (B) has a melt flow rate of 5 g / 10 minutes or more as measured at a temperature of 230°C and a load of 2.16 kg; and a polycarbonate resin composition (for example, refer to Patent Document 2), etc., which contains, based on a total of 100 parts by mass of 40 to 80% by mass of a recycled aromatic polycarbonate resin (A) and 20 to 60% by mass of an aromatic polycarbonate resin (B): (C) 10 to 60 parts by mass of carbon fibers covered with a resin selected from polyamides, polyurethanes, and epoxy resins and not coated with nickel, (D) 10 to 20 parts by mass of a phosphate compound, (E) 0.01 to 1 part by mass of a fluorine compound, (F) 0.5 to 10 parts by mass of a graft copolymer containing a polyorganosiloxane, and does not contain nickel-coated carbon fibers.

[0006] In addition, as a method for manufacturing a molded article containing recycled materials, for example, there has been proposed a method for manufacturing a molded article (for example, refer to Patent Document 3), etc., which supplies 20 to 80% by weight of recycled pellets of a fibrous filler-reinforced crosslinked polyphenylene sulfide composition and 80 to 20% by weight of non-recycled pellets of a fibrous filler-reinforced crosslinked polyphenylene sulfide composition to an injection molding machine for injection molding.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2021-115795

[0010] Patent Document 2: Japanese Patent No. 6825890

[0011] Patent Document 3: Japanese Patent No. 5386853 Summary of the Invention

[0012] Problems to be Solved by the Invention

[0013] However, in the resin compositions proposed in Patent Documents 1 and 2, no research or proposal has been made for those falling within the category of super engineering plastics, let alone polyphenylene sulfide resin with high operability and ease of use. In addition, in the manufacturing method of the molded body proposed in Patent Document 3, only a manufacturing method of a molded body in which a recycled fiber-like filler-reinforced crosslinked polyphenylene sulfide recycled pellet obtained by recycling waste products and the like and a non-recycled pellet of a fiber-like filler-reinforced crosslinked polyphenylene sulfide composition are supplied to an injection molding machine is proposed, and the application method of the recycled resin is limited.

[0014] Therefore, an object of the present invention is to provide a recycled fiber-like filler-reinforced PAS resin composition containing a recycled PAS resin and a manufacturing method thereof without impairing the mechanical properties, fluidity, etc. originally possessed by the PAS resin.

[0015] In addition, improving the recycling and efficiency of recycled polyphenylene sulfide resin contributes to the promotion of inclusive sustainable industrialization and is one of the technologies contributing to a sustainable society such as the SDGs (United Nations Sustainable Development Goals) called for in recent years.

[0016] Means for Solving the Problems

[0017] The inventors of the present invention conducted in-depth research to solve the above problems and found that the mechanical properties and fluidity of a specific recycled fiber-like filler-reinforced PAS resin composition containing a recycled PAS resin became excellent, and thus the present invention was completed.

[0018] That is, the present invention resides in the following [1] to [9].

[0019] [1] A recycled fiber-like filler-reinforced polyphenylene sulfide resin composition, characterized in that it contains a polyphenylene sulfide resin (A), a recycled polyphenylene sulfide resin (B), and a fiber-like filler (C),

[0020] The molten viscosity of the polyphenylene sulfide resin (A) measured using a high-temperature rheometer equipped with a die having a diameter of 1 mm and a length of 2 mm under the conditions of a measurement temperature of 315 °C and a load of 10 kg is 100 to 3000 poise,

[0021] The compounding amount of the recycled polyphenylene sulfide resin (B) is 10 to 250 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin (A), and the compounding amount of the fiber-like filler (C) is 10 to 60 parts by weight with respect to 100 parts by weight of the total amount of the polyphenylene sulfide resin (A) and the recycled polyphenylene sulfide resin (B).

[0022] [2] The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to [1], wherein the regenerated polyarylene sulfide resin (B) is a post-consumer recycled polyarylene sulfide resin and / or a post-industrial recycled polyarylene sulfide resin.

[0023] [3] The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to [1] or [2], wherein the regenerated polyarylene sulfide resin (B) is a regenerated non-reinforced polyarylene sulfide resin.

[0024] [4] The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to any one of [1] to [3], wherein the regenerated polyarylene sulfide resin (B) is a regenerated non-reinforced polyarylene sulfide resin which is a regenerated product belonging to at least one selected from the group consisting of polyarylene sulfide resin fibers, polyarylene sulfide resin sheets, and polyarylene sulfide resin films.

[0025] [5] The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to any one of [1] to [4], wherein the fibrous filler (C) is a chopped strand having an average fiber diameter of 6 to 14 μm and / or a chopped strand composed of flat glass fibers having a fiber cross-sectional aspect ratio of 2 to 4.

[0026] [6] The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to any one of [1] to [5], wherein it further comprises a non-fibrous filler (D).

[0027] [7] The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to any one of [1] to [6], wherein it further comprises a thermoplastic elastomer (E), a compatibilizer (F), and / or a mold release agent (G).

[0028] [8] A pellet, characterized in that it is a pellet formed from the regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to any one of [1] to [7], and the pellet has a cylindrical shape with a diameter of 0.5 to 2.5 mm and a length of 1.5 to 4 mm or a spherical shape with a diameter of 1 to 3 mm.

[0029] [9]A method for manufacturing a regenerated fibrous filler-reinforced polyarylene sulfide resin composition, characterized in that a twin-screw extruder having a screw with a ratio (L1 / D1) of screw length (L1) to screw diameter (D1) of 30 or more and two or more kneading zones is used, and the polyarylene sulfide resin (A), regenerated polyarylene sulfide resin (B), and fibrous filler (C) are melt-kneaded and extruded under kneading conditions where the barrel temperature in the kneading zone is 280 to 330 °C, the circumferential speed of the screw is 50 to 400 mm / second, and the residence time is 30 to 100 seconds. The polyarylene sulfide resin (A) has a melt viscosity of 100 to 3000 poise as measured using a Koka-type rheometer equipped with a die having a diameter of 1 mm and a length of 2 mm under the conditions of a measurement temperature of 315 °C and a load of 10 kg.

[0030] Effects of the Invention

[0031] According to the present invention, there can be provided a regenerated fibrous filler-reinforced PAS resin composition containing a regenerated PAS resin, which has excellent impact resistance and fluidity, and is particularly useful in applications such as electrical / electronic components, automotive components, or water-using spaces, and has extremely high industrial value. Detailed Embodiments

[0032] Hereinafter, the present invention will be described in detail.

[0033] As the PAS resin (A) constituting the regenerated fibrous filler-reinforced PAS resin composition of the present invention, it suffices if it belongs to the category generally called PAS resin. Examples of such PAS resin include homopolymers or copolymers formed from p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenyl sulfone sulfide units, phenyl ketone sulfide units, phenyl ether sulfide units, and biphenyl sulfide units. Specific examples of such PAS resin include PPS, polyphenylene sulfone, polyphenylene ketone, and polyphenylene ether. Among them, from the aspect of forming a regenerated fibrous filler-reinforced PAS resin composition having excellent heat resistance and strength characteristics, PPS is particularly preferred.

[0034] Moreover, the melt viscosity of the PAS resin (A) as measured using a Koka-type rheometer equipped with a die having a diameter of 1 mm and a length of 2 mm under the conditions of a measurement temperature of 315 °C and a load of 10 kg is 100 to 3000 poise. Here, when it is less than 100 poise, the impact resistance of the obtained composition deteriorates. On the other hand, when it exceeds 3000 poise, the fluidity of the obtained composition deteriorates.

[0035] As a method for manufacturing the PAS resin (A), it can be manufactured by a method known as a method for manufacturing PAS. For example, it can be obtained by polymerizing an alkali metal sulfide salt and a polyhalogen aromatic compound in a polar organic solvent. Examples of the polar organic solvent at this time include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, dimethylacetamide, etc. Examples of the alkali metal sulfide salt include anhydrous or hydrated sodium sulfide, rubidium sulfide, and lithium sulfide. In addition, as the alkali metal sulfide salt, it can be one formed by reacting an alkali metal hydrosulfide salt with an alkali metal hydroxide. Examples of the polyhalogen aromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, 4,4'-dichlorobiphenyl, etc.

[0036] In addition, as the PAS resin (A), it can be linear, it can be one in which a small amount of a polyhalogen compound having three or more halogens is added during polymerization to introduce some crosslinked or branched structures, it can be one in which a part and / or the end of the molecular chain of the PAS resin is modified with functional groups such as carboxyl groups, carboxyl metal salts, amino groups, alkyl groups, alkoxy groups, nitro groups, etc., it can be one in which heat treatment is carried out in a non-oxidizing inert gas such as nitrogen, and furthermore, it can be a mixture of these structures. In addition, for the PAS resin (A), before or after heat curing, by performing deionization treatment (acid cleaning, hot water cleaning, etc.) or cleaning treatment based on organic solvents such as acetone and methanol, impurities such as sodium atoms, oligomers of the PAS resin, table salt, and sodium salts of 4-(N-methyl-chlorophenylamino) butyrate are reduced. Furthermore, after the polymerization reaction is completed, heat treatment can be carried out in an inert gas or an oxidizing gas for curing.

[0037] The recycled PAS resin (B) constituting the recycled fibrous filler-reinforced PAS resin composition of the present invention only needs to be a PAS resin recycled from industrial wastes such as molded bodies discarded after being on the market, and gates, runners generated during injection molding, or unused parts of the molded body. Moreover, the recycled PAS resin (B) recycled from the molded body discarded after being on the market belongs to PCR, and from the viewpoint of reducing resource consumption, etc., it has excellent sustainability and its application is expected. The recycled PAS resin (B) recycled from the gate, runner, or unused part of the molded body belongs to PIR. Since it is recycled from PAS resins of the same structure, the same grade, and in some cases the same batch, it becomes a recycled PAS resin with small quality fluctuations. Therefore, a recycled fibrous filler-reinforced PAS resin composition with small quality fluctuations can be obtained.

[0038] As the recycled PAS resin (B) at this time, recycled non-reinforced PAS resin, a fibrous filler-reinforced PAS resin composition containing a fibrous filler, etc. can be cited. From the aspect of being able to efficiently form the recycled fibrous filler-reinforced PAS resin composition of the present invention, a fibrous filler-reinforced PAS resin composition is particularly preferred.

[0039] Herein, the recycled non-reinforced PAS resin refers to a resin in which no inorganic filler or the like is compounded in the recycled PAS resin.

[0040] Moreover, as the recycled PAS resin (B), those obtained by recycling commercially available PAS resins can be cited. As the commercially available PAS resins, for example, (registered trademark) SUSTEEL (manufactured by Tosoh Corporation), (registered trademark) Torelina (manufactured by Toray Industries, Inc.), (trade name) FZ-1140 (manufactured by DIC Corporation), (registered trademark) Durafide (manufactured by Polyplastics Co., Ltd.), etc. can be cited. Incidentally, as the fibrous filler when the recycled PAS resin (B) is a fibrous filler-reinforced product, for example, the following can be cited: glass fiber; carbon fibers such as PAN-based carbon fiber and pitch-based carbon fiber; graphitized fiber; whiskers such as silicon nitride whisker, basic magnesium sulfate whisker, barium titanate whisker, potassium titanate whisker, silicon carbide whisker, boron whisker, zinc oxide whisker; metal fibers such as stainless steel fiber; inorganic fibers such as asbestos, zirconia, alumina silica, barium titanate, silicon carbide, alumina, silica, blast furnace slag; organic fibers such as wholly aromatic polyamide fiber, phenolic resin fiber, wholly aromatic polyester fiber; mineral fibers such as wollastonite, basic magnesium sulfate.

[0041] In addition, when the recycled PAS resin (B) is a recycled non-reinforced PAS resin, not only is it possible to suppress excessive breakage of fillers and the like during recycling, but also it is possible to suppress resin deterioration caused by exotherm during compounding of fillers and the like, and the mechanical properties become excellent. Moreover, as the recycled non-reinforced PAS resin, those obtained by recycling commercially available PAS resin fibers, PAS resin sheets, PAS resin films, and further products using these can be cited. They can be used alone or in combination of two or more.

[0042] As the compounding amount of the recycled PAS resin (B), from the aspect that even if the use ratio of the recycled material is increased, the reduction in mechanical properties such as impact resistance is small, it is 10 to 250 parts by weight with respect to 100 parts by weight of the PAS resin (A). Herein, when the recycled PAS resin (B) is less than 10 parts by weight, the use ratio of the recycled material is low and the significance of recycling becomes low. On the other hand, when it exceeds 250 parts by weight, the impact resistance of the obtained composition becomes poor.

[0043] Regarding the compounding amount of the recycled PAS resin (B) relative to 100 parts by weight of the PAS resin (A), from the aspect that the balance between impact strength and fluidity becomes excellent, it is preferably 15 to 245 parts by weight, and among them, from the aspect that it becomes in line with the meaning of recycling, it is particularly preferably 60 to 245 parts by weight.

[0044] As the fibrous filler (C) constituting the recycled fibrous filler-reinforced PAS resin composition of the present invention, as long as it belongs to the category of fibrous fillers, for example, it can be cited: glass fiber; carbon fibers such as PAN-based carbon fibers or pitch-based carbon fibers; graphitized fibers; whiskers such as silicon nitride whiskers, basic magnesium sulfate whiskers, barium titanate whiskers, potassium titanate whiskers, silicon carbide whiskers, boron whiskers, zinc oxide whiskers, etc.; metal fibers such as stainless steel fibers; inorganic fibers such as asbestos, zirconia, alumina-silica, barium titanate, silicon carbide, alumina, silica, blast furnace slag, etc.; organic fibers such as wholly aromatic polyamide fibers, phenolic resin fibers, wholly aromatic polyester fibers, etc.; mineral fibers such as wollastonite, basic magnesium sulfate, etc. From the aspect of making the recycled fibrous filler-reinforced PAS resin composition excellent in mechanical strength and impact resistance, glass fiber is particularly preferred. As this glass fiber, any substance can be used as long as it is generally called glass fiber. As specific examples of this glass fiber, it can be cited chopped strands with an average fiber diameter of 6 to 14 μm, chopped strands composed of flat glass fibers with an aspect ratio of the fiber cross-section of 2 to 4, ground fibers, rovings, etc.; silane fibers; aluminosilicate glass fibers; hollow glass fibers; enamel-free glass fibers, etc. Among them, from the aspect of making the recycled fibrous filler-reinforced PAS resin composition excellent in mechanical strength, impact resistance, and fluidity, chopped strands with an average fiber diameter of 6 to 14 μm and / or chopped strands composed of flat glass fibers with an aspect ratio of the fiber cross-section of 2 to 4 are particularly preferred. Two or more of these fibrous fillers can also be used in combination, and those surface-treated in advance with functional compounds or polymers such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, etc. according to need can also be used. Regarding the compounding amount of the fibrous filler (C), from the aspect of making the recycled fibrous filler-reinforced PAS resin composition excellent in the balance between toughness, mechanical strength, and fluidity, relative to 100 parts by weight of the total amount of the PAS resin (A) and the recycled PAS resin (B), the fibrous filler (C) is 10 to 60 parts by weight. Here, when the fibrous filler is less than 10 parts by weight, the impact resistance of the obtained composition deteriorates. On the other hand, when it exceeds 60 parts by weight, the fluidity deteriorates.

[0045] Regarding the compounding amount of the fibrous filler (C) with respect to 100 parts by weight in total of the PAS resin (A) and the recycled PAS resin (B), from the aspect of having excellent properties as a composition, it is preferably 15 to 55 parts by weight, and among them, from the aspect of excellent balance between impact strength and fluidity, it is more preferably 20 to 50 parts by weight.

[0046] For the recycled fibrous filler-reinforced PAS resin composition of the present invention, from the aspect of excellent dimensional accuracy and rigidity, it preferably contains a non-fibrous filler (D). Examples of such non-fibrous fillers include calcium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, mica, silica, talc, clay, calcium sulfate, kaolin, wollastonite, zeolite, silica, magnesium oxide, zirconium oxide, tin oxide, magnesium silicate, calcium silicate, calcium phosphate, magnesium phosphate, hydrotalcite, glass powder, glass beads, glass flakes, etc. From the aspect of forming a recycled fibrous filler-reinforced PAS resin composition with excellent dimensional accuracy and rigidity, calcium carbonate or glass flakes are particularly preferred. In addition, from the aspect of forming a recycled fibrous filler-reinforced PAS resin composition with excellent mechanical strength, impact resistance, and fluidity, calcium carbonate or glass flakes with an average particle size of 2 to 800 μm are particularly preferred. Here, the average particle size refers to the particle size (D50) at which the cumulative mass percentage is equivalent to 50% in the particle size distribution measured based on the laser diffraction scattering method. In addition, regarding the compounding amount of this non-fibrous filler (D), from the aspect of excellent balance between rigidity, dimensional accuracy, and fluidity, with respect to 100 parts by weight in total of the PAS resin (A) and the recycled PAS resin (B), it is preferably an amount such that the total amount of the fibrous filler (C) and the non-fibrous filler (D) is equivalent to 20 to 80 parts by weight.

[0047] For the recycled fibrous filler-reinforced PAS resin composition of the present invention, from the aspect of excellent toughness, it particularly preferably contains a thermoplastic elastomer (E). As the thermoplastic elastomer (E), any one can be used as long as it is generally called a thermoplastic elastomer. It can be a thermoplastic elastomer having reactive functional groups, a thermoplastic elastomer not having reactive functional groups, or a mixture of the thermoplastic elastomer having reactive functional groups and the thermoplastic elastomer not having reactive functional groups.

[0048] As such reactive functional groups, epoxy groups, maleic anhydride groups, carboxylic acid groups, amino groups, isocyanate groups, etc. can be cited, for example. As the thermoplastic elastomers having such reactive groups, for example, modified ethylene-based copolymers such as ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymers, ethylene-α,β-unsaturated glycidyl carboxylate copolymers, ethylene-α,β-unsaturated glycidyl carboxylate-vinyl acetate copolymers, ethylene-α,β-unsaturated glycidyl carboxylate-α,β-unsaturated carboxylic acid alkyl ester copolymers, maleic anhydride graft-modified ethylene-α-olefin copolymers, etc.; those obtained by modifying the hydrogenated product of a styrene-butadiene-styrene block copolymer with maleic anhydride or its derivative, those obtained by modifying the hydrogenated product of a styrene-butadiene block copolymer with maleic anhydride or its derivative, those obtained by modifying the hydrogenated product of a styrene-isoprene block copolymer with maleic anhydride or its derivative, those obtained by modifying the hydrogenated product of a styrene-isoprene-styrene block copolymer with maleic anhydride or its derivative, etc., hydrogenated products of vinyl aromatic compound-based block copolymers, etc. In addition, as long as it has a functional group capable of reacting with the PAS resin, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, acrylonitrile-butadiene rubber-based thermoplastic elastomers, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, etc. can also be used. Among them, from the aspect of becoming a regenerated fibrous filler-reinforced PAS resin composition with excellent toughness, modified ethylene-based copolymers are particularly preferred.

[0049] On the other hand, as the thermoplastic elastomers not having reactive functional groups, those not having functional groups among the above-mentioned thermoplastic elastomers can be cited. Among them, from the aspect of obtaining a regenerated fibrous filler-reinforced PAS resin composition with excellent balance between fluidity and toughness, an olefin-acrylate binary copolymer is particularly preferred. Moreover, as the olefin at this time, ethylene or an α-olefin having 3 or more carbon atoms can be cited, and as the acrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, etc. can be cited.

[0050] As the compounding amount of the thermoplastic elastomer (E), from the aspect of becoming a regenerated fibrous filler-reinforced PAS resin composition with excellent balance between toughness and fluidity, it is preferably 1 to 20 parts by weight relative to 100 parts by weight of the total amount of the PAS resin (A) and the regenerated PAS resin (B).

[0051] For the regenerated fibrous filler-reinforced PAS resin composition of the present invention, from the aspect of excellent mechanical strength and impact resistance, it is particularly preferred to further contain a compatibilizer (F). As the compatibilizer at this time, for example, isocyanurate, epoxy resin, silane coupling agent, and mixtures thereof can be cited.

[0052] Moreover, as the isocyanurate, any compound known as isocyanurate may be used. From the perspective of obtaining a regenerated fibrous filler-reinforced PAS resin composition with low mold contamination, aliphatic isocyanurates are particularly preferred. Specific examples of such aliphatic isocyanurates include 1,3,5-tris(6-isocyanatohexan-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(6-isocyanatobutan-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(6-isocyanatododecan-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, etc. From the perspective of obtaining a regenerated fibrous filler-reinforced PAS resin composition with low mold contamination, aliphatic isocyanurates with a molecular weight of 500 or more are particularly preferred. The aliphatic isocyanurate may be a dimer, trimer or other polymer, or an isocyanurate containing a dimer, trimer or other polymer in an aliphatic isocyanurate monomer. From the perspective of excellent reactivity with PAS resin (A), regenerated PAS resin (B), and thermoplastic elastomer (E) as appropriate, and obtaining a regenerated fibrous filler-reinforced PAS resin composition with excellent impact resistance, aliphatic isocyanurates containing 20% or more isocyanate groups are preferred.

[0053] In addition, the aliphatic isocyanurate may be one obtained by modifying a part of the aliphatic isocyanate with an alcohol such as 1,3-butanediol or 2,2,4-trimethyl-1,3-pentanediol. Among these aliphatic isocyanurates, 1,3,5-tris(6-isocyanatohexan-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is particularly preferred from the perspectives of excellent heat and cold resistance and easy availability. Specific examples of 1,3,5-tris(6-isocyanatohexan-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione include (trade name) CORONATE HXR (manufactured by Tosoh Corporation), (trade name) Duranate TPA-100 (manufactured by Asahi Kasei Corporation), etc.

[0054] In addition, as the epoxy resin, any one can be used as long as it belongs to the category of what is called epoxy resin. Specific examples thereof include glycidyl ether type epoxy resins synthesized from compounds having two or more hydroxyl groups in the molecule such as 2,2-bis(4'-hydroxyphenyl)propane (bisphenol A), bis(2-hydroxyphenyl)methane (bisphenol F), 4,4'-dihydroxydiphenyl sulfone (bisphenol S), 4,4'-dihydroxybiphenyl, resorcinol, salicyl alcohol, trihydroxydiphenyldimethylmethane, tetrahydroxyphenylethane, their halogenated substituents and alkyl substituents, butanediol, ethylene glycol, erythritol, novolac, glycerol, polyalkylene oxide and epichlorohydrin; glycidyl ester type epoxy resins synthesized from the compounds having two or more hydroxyl groups in the molecule and phthalic acid glycidyl ester; glycidylamine type epoxy resins containing glycidyl groups synthesized from primary amines or secondary amines such as aniline, diaminodiphenylmethane, m-xylenediamine, 1,3-bis(aminomethyl)cyclohexane and epichlorohydrin; epoxy resins without glycidyl groups such as epoxidized soybean oil, epoxidized polyolefin, vinylcyclohexene dioxide, dicyclopentadiene dioxide. Among them, from the aspect that the impact resistance of the obtained regenerated fibrous filler-reinforced PAS resin composition becomes particularly excellent, glycidyl ether type epoxy resins and glycidyl ester type epoxy resins of bisphenols such as bisphenol A, bisphenol F and bisphenol S are preferred. As a more preferred one, bisphenol A type epoxy resin is used.

[0055] Furthermore, as the silane coupling agent, any one can be used as long as it belongs to the category of what is called silane coupling agent. Among them, from the aspect of forming a regenerated fibrous filler-reinforced PAS resin composition excellent in impact resistance and mechanical strength, a silane coupling agent composed of a trialkoxysilane coupling agent having a glycidyl group and / or a trialkoxysilane coupling agent having an amino group is particularly preferred. As the silane coupling agent at this time, there is no particular limitation as long as it is a trialkoxysilane coupling agent having a glycidyl group or an amino group. Specific examples 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, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and the like.

[0056] In addition, the amount of the compatibilizer (F) is preferably 0.1 to 15 parts by weight relative to 100 parts by weight of the total amount of the PAS resin (A) and the recycled PAS resin (B) from the perspective of obtaining a recycled fibrous filler reinforced PAS resin composition having excellent impact resistance and mechanical strength and low mold contamination.

[0057] Furthermore, in order to improve the mold release and appearance when forming the molded product, the regenerated fibrous filler reinforced PAS resin composition of the present invention may also contain a release agent (G). As the release agent (G), for example, polyethylene wax, polypropylene wax, and fatty amide wax are suitable. As the polyethylene wax and polypropylene wax, conventional commercial products can be used. In addition, the fatty amide wax is a polycondensate formed by a higher aliphatic monocarboxylic acid, a polyacid, and a diamine. As long as it falls within this category, any substance can also be used, for example, Light Amide WH-255 (Kyoeisha Chemical Co., Ltd.), which is a polycondensate formed by stearic acid, sebacic acid, and ethylenediamine, etc. can be cited.

[0058] The regenerated fibrous filler reinforced PAS resin composition of the present invention can be mixed with various additives and used within the scope not departing from the purpose of the present invention. For example, one or more of conventional additives such as plasticizers such as conventionally known polyalkylene oxide oligomer compounds, sulfide compounds, ester compounds, and organic phosphorus compounds; antioxidants; heat stabilizers; ultraviolet light blocking agents; foaming agents; and pigments such as carbon black can be added. Furthermore, various thermosetting resins; one or more of thermoplastic resins such as cyanate resins, phenolic resins, polyimides, silicone resins, polyesters, polyphenylene ethers, polycarbonates, polysulfones, polyetherimides, polyethersulfones, polyetherketones, polyetheretherketones, polyamideimides, and polyalkylene oxides can also be mixed and used.

[0059] As a method for manufacturing a regenerated fibrous filler reinforced PAS resin composition of the present invention, a heating melt kneading method used in the past can be utilized. For example, it can be cited: a heating melt kneading method based on a single-screw extruder or a twin-screw extruder, a kneader, a grinder, a Brabender machine, etc., and a melt kneading method based on a twin-screw extruder with excellent kneading ability is particularly preferred. The screw used in the twin-screw extruder at this time preferably has more than two kneading zones. Furthermore, from the perspective of fully mixing the PAS resin (A) and the regenerated PAS resin (B), the result is a regenerated fibrous filler reinforced PAS resin composition with excellent toughness such as impact resistance, the ratio (L1 / D1) of the screw length (L1) to the screw diameter (D1) is preferably 30 or more, and a screw of 40 or more is particularly preferred.

[0060] Moreover, from the aspect of making the kneading of the PAS resin (A) and the recycled PAS resin (B) sufficient and making it easy to suppress the thermal decomposition of the recycled PAS resin (B), the barrel temperature in the kneading zone of the extruder is preferably set to 280 to 330°C, particularly preferably 290 to 320°C. In addition, from the aspect of making the kneading / uniformity of the PAS resin phase and the recycled PAS resin phase of the recycled fibrous filler-reinforced PAS resin composition good, and as a result, obtaining a recycled fibrous filler-reinforced PAS resin composition excellent in toughness such as impact resistance, the circumferential speed of the screw is preferably 50 to 400 mm / second, particularly preferably 150 to 300 mm / second. In addition, as the residence time of the molten resin in the extruder, from the aspect of making the melt-kneading time of the PAS resin (A) and the recycled PAS resin (B) sufficient and making it easy to suppress the thermal decomposition of the recycled PAS resin (B), it is preferably 30 to 100 seconds, particularly preferably 30 to 80 seconds.

[0061] Moreover, for the recycled fibrous filler-reinforced PAS resin composition after melt-kneading, the extruded melt-kneaded product can be formed into pellets by methods such as hot cutting, spray cutting, etc. or the wire material can be formed into pellets by methods such as cold cutting, etc. Particularly, from the aspect of stably and efficiently obtaining pellets with excellent quality and hue, it is preferable to cool the melt-kneaded product by methods such as water cooling, air cooling, etc. to form a wire material, and then cut the wire material to form pellets by cold cutting or hot cutting. As the pellets at this time, from the aspect of excellent processability when injection-molded into various molded products, it is preferable to use pellets having a cylindrical shape with an average diameter of 0.5 to 2.5 mm and an average length of 1.5 to 4 mm or spherical pellets with an average diameter of 1 to 3 mm. From the aspect of obtaining a molded body with excellent product appearance, it is particularly preferable to use pellets having a light brown or brown hue.

[0062] In addition, the recycled fibrous filler-reinforced PAS resin composition of the present invention can be formed into a molded body with an arbitrary shape using an injection molding machine, an extrusion molding machine, a transfer molding machine, a compression molding machine, a blow molding machine, etc.

[0063] The recycled fibrous filler-reinforced PAS resin composition of the present invention contains a recycled PAS resin without impairing the heat resistance, chemical resistance, fluidity, etc. originally possessed by the PAS resin, and is suitable for uses such as electrical / electronic components, automotive components, etc. or uses in water spaces such as piping / fittings.

[0064] Examples

[0065] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by any of these.

[0066] The following shows the PAS resin (A), recycled PAS resin (B), fibrous filler (C), non-fibrous filler (D), thermoplastic elastomer (E), compatibilizer (F), and mold release agent (G) used in the examples and comparative examples.

[0067] <PAS resin (A)>

[0068] Poly(phenylene sulfide) (hereinafter referred to as PPS (A-1).): melt viscosity of 2500 poise.

[0069] Poly(phenylene sulfide) (hereinafter referred to as PPS (A-2).): melt viscosity of 350 poise.

[0070] Poly(phenylene sulfide) (hereinafter referred to as PPS (A-3).): melt viscosity of 3220 poise.

[0071] Poly(phenylene sulfide) (hereinafter referred to as PPS (A-4).): melt viscosity of 80 poise.

[0072] Amino-substituted poly(phenylene sulfide) (hereinafter referred to as PPS (A-5).); amino content of 0.1 mol%, melt viscosity of 1200 poise.

[0073] <Recycled PAS resin (B)>

[0074] Post-industrial recycled PPS resin (hereinafter referred to as PIRPPS resin (B-1).); the pulverized material of the gate and runner when injecting and molding (trade name) SUSTEEL GS-40 (manufactured by Tosoh Corporation; glass fiber reinforced product).

[0075] Post-consumer recycled non-reinforced PPS resin (hereinafter referred to as PCRPPS resin (B-2).); manufactured by Ningbo Topcentral New Material CO., Ltd., (trade name) rPPS-B103.

[0076] <Fibrous filler (C)>

[0077] Glass fiber (C-1); manufactured by Central Glass Co., Ltd., (trade name) ECS03-630; average fiber diameter of 9 μm, average fiber length of 3 mm.

[0078] Glass fiber (C-2); manufactured by Central Glass Co., Ltd., (trade name) ECS03-631K; average fiber diameter of 13 μm, average fiber length of 3 mm.

[0079] Glass fiber (C-3); manufactured by Nitto Boseki Co., Ltd., (trade name) CSG 3PL-830S; aspect ratio of 2.

[0080] Glass fiber (C-4); manufactured by Nippon Electric Glass Co., Ltd., (trade name) ECS03T-747-FGF; aspect ratio 4.

[0081] Glass fiber (C-5); manufactured by Nippon Electric Glass Co., Ltd., (trade name) T-760H; fiber diameter 10 μm, fiber length 3 mm.

[0082] <Non-fibrous filler (D)>

[0083] Glass flake (D-1); manufactured by Nippon Sheet Glass Co., Ltd., (trade name) REFG-312; average particle size 160 μm.

[0084] <Thermoplastic elastomer (E)>

[0085] Ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (E-1) (hereinafter, referred to as modified ethylene-based copolymer (E-1).): Manufactured by Arkema Inc., (trade name) BONDINE AX8390.

[0086] Ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer (E-2) (hereinafter, simply referred to as thermoplastic elastomer (E-2).); Manufactured by SK global chemical company, (trade name) LOTADER AX8700, ethylene residue unit: α,β-unsaturated carboxylic acid glycidyl ester residue unit: α,β-unsaturated carboxylic acid alkyl ester residue unit (weight ratio) = 67:8:25.

[0087] <Compatibilizer (F)>

[0088] Epoxy resin (F-1); manufactured by DIC Corporation, (trade name) EPICLON 3050PW.

[0089] Trialkoxysilane coupling agent with glycidyl group (F-2) (hereinafter, referred to as compatibilizer (F-2).); Manufactured by Shin-Etsu Chemical Co., Ltd., (trade name) KBM-403; 3-glycidoxypropyltrimethoxysilane.

[0090] <Release agent (G)>

[0091] Release agent (G-1); manufactured by NIKKO RICACORPORATION, (trade name) refined carnauba wax powder No. 1.

[0092] Release agent (G-2); manufactured by Kyoeisha Chemical Co., Ltd., (trade name) Light Amide WH-255.

[0093] Synthesis Example 1

[0094] Into a 50 L autoclave equipped with a stirrer, 6865 g of flaky sodium sulfide (Na2S·2.9H2O), 164 g of 30% caustic soda solution (30% NaOHaq), and 17000 g of N-methyl-2-pyrrolidone were charged. While stirring under a nitrogen gas stream, the temperature was slowly raised to 205 °C, and 1365 g of water was distilled off. After cooling to 190 °C, 7192 g of p-dichlorobenzene and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen gas 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 at 250 °C for 3 hours. After polymerization, N-methyl-2-pyrrolidone was recovered from the polymerization slurry by distillation under reduced pressure. The final temperature reached 170 °C and the pressure was 4.7 kPa. Hot water at 80 °C was added to the obtained filter cake to make the slurry concentration 20%, and it was washed. Again, hot water was added in the same way, the temperature was raised to 175 °C, and poly(p-phenylene sulfide) was washed. The obtained poly(p-phenylene sulfide) was dried at 105 °C for one day and night. Then, the dried polyphenylene sulfide was filled into a batch rotary kiln-type firing device, heated to 240 °C in an air atmosphere, and heat-treated with a 5-hour holding to obtain PPS (A-1) with a melt viscosity of 2500 poise.

[0095] Synthesis Example 2

[0096] Into a 15 L autoclave equipped with a stirrer, 1814 g of flaky sodium sulfide (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. While stirring under a nitrogen gas stream, the temperature was slowly raised to 200 °C, and 339 g of water was distilled off. After cooling to 190 °C, 2129 g of p-dichlorobenzene and 1783 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen gas 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 2 hours. Then, 509 g of distilled water was pressured into the system at 250 °C, the temperature was raised to 255 °C, and the polymerization reaction was further carried out for 2 hours. After polymerization, it was cooled to room temperature, and the polymerization slurry was subjected to solid-liquid separation with a centrifugal filter. The filter cake was washed repeatedly 3 times with N-methyl-2-pyrrolidone and acetone in turn under a nitrogen gas stream, and further washed with 0.2% hydrochloric acid and hot water in turn under a nitrogen gas stream. The obtained poly(p-phenylene sulfide) was dried at 105 °C for one day and night to obtain PPS (A-2) with a melt viscosity of 350 poise.

[0097] Synthesis Example 3

[0098] In a 50 L autoclave equipped with a stirrer, 6214 g of Na2S·2.9H2O and 17000 g of N-methyl-2-pyrrolidone were charged. While stirring under a nitrogen stream, the temperature was slowly raised to 205 °C, and 1355 g of water was distilled off. After cooling the system to 140 °C, 7180 g of p-dichlorobenzene 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 further polymerized at 250 °C for 3 hours. After the polymerization was completed, it was cooled to room temperature, and the solid component was separated using a centrifuge. The solid component was washed with hot water at 180 °C and dried at 100 °C for one day and night to obtain poly(p-phenylene sulfide).

[0099] The obtained poly(p-phenylene sulfide) was cured at 250 °C for 6 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 3220 poise.

[0100] Synthesis Example 4

[0101] In a 15 L autoclave equipped with a stirrer, 1814 g of Na2S·2.9H2O, 8.7 g of granular caustic soda (100% NaOH: Wako Pure Chemical Industries, Ltd., special grade), and 3232 g of N-methyl-2-pyrrolidone were charged. While stirring under a nitrogen stream, the temperature was slowly raised to 200 °C, 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 further polymerized at 250 °C for 2 hours. After the polymerization was completed, it was cooled to room temperature, and the solid component was separated using a centrifuge. The solid component was washed with hot water at 180 °C and dried at 105 °C for one day and night to obtain poly(p-phenylene sulfide).

[0102] The obtained poly(p-phenylene sulfide) was dried at 240 °C for 6 hours under reduced pressure using a vacuum dryer to obtain linear poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-4)). The melt viscosity of PPS(A-4) was 80 poise.

[0103] Synthesis Example 5

[0104] In a 50-liter autoclave equipped with a stirrer, 6214 g of flaky sodium sulfide (Na2S·2.9H2O) and 17000 g of N-methyl-2-pyrrolidone were charged. While stirring under a nitrogen gas stream, the temperature was slowly raised to 205 °C, and 1355 g of water was distilled off. After cooling the system to 140 °C, 7278 g of p-dichlorobenzene, 11.7 g of 3,5-dichloroaniline, and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen gas 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 further polymerized at 250 °C for 3 hours. After the polymerization was completed, it was cooled to room temperature, and the polymer was separated by a centrifugal separator. For this solid component, the polymer was repeatedly washed with hot water and dried at 100 °C for one day and night, thereby obtaining amino-substituted poly(phenylene sulfide) having a melt viscosity of 400 poises. Next, the dried amino-substituted poly(phenylene sulfide) was filled into a batch rotary kiln-type firing device and cured at 240 °C for 2 hours in an air atmosphere, thereby obtaining PPS (A-5) having a melt viscosity of 1200 poises and an amino content relative to phenyl of 0.1 mol%.

[0105] The following shows the evaluation / determination methods of the obtained PAS resin composition.

[0106] [Measurement of melt viscosity of PAS resin]

[0107] The melt viscosity was measured using a high-temperature rheometer (manufactured by Shimadzu Corporation, (trade name) CFT-500) equipped with a die having a diameter of 1 mm and a length of 2 mm under the conditions of a measurement temperature of 315 °C and a load of 10 kg.

[0108] [Measurement of Charpy impact strength (notched)]

[0109] Test pieces were produced using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE-75S) and measured according to ISO 179-1. Those with a Charpy impact strength of 6 kJ / m 2 or more were rated as having excellent impact resistance.

[0110] [Measurement of fluidity]

[0111] An injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name: SE-75S) was installed with a mold spirally grooved with a thickness of 1 mm and a width of 10 mm. Then, in the hopper of this injection molding machine with the barrel temperature set at 310 °C, the injection pressure set at 190 MPa, the injection speed set to maximum, the injection time set at 1.5 seconds, and the mold temperature set at 135 °C, a PAS resin composition was put in and injection was carried out. Then, the length of the spiral groove in the mold that melted and flowed was measured as the overflow length (hereinafter referred to as BFL), and the molding fluidity was evaluated. When the molding fluidity was 150 mm or more, it was judged that the fluidity was excellent.

[0112] Example 1

[0113] To 100 parts by weight of PPS (A-1) obtained in Synthesis Example 1, 18 parts by weight of PIRPPS resin (B-1) was uniformly premixed and put into the hopper of a twin-screw extruder (manufactured by Japan Steel Works, Ltd., trade name: TEX-25αIII, L1 / D1 = 55) having 4 kneading zones. On the other hand, from the hopper of the side feeder of this twin-screw extruder, glass fiber (C-1) was put in such a manner as to be 61 parts by weight (equivalent to 52 parts by weight based on the total of 100 parts by weight of PPS resin (A-1) and PIRPPS resin (B-1)), and a mold release agent (G-1) was put in such a manner as to be 2 parts by weight. Under the condition of heating the barrel temperature of the kneading zone to 300 °C, melt kneading was carried out at a raw material supply speed of 25 kg / hour and a screw rotation speed of 200 rpm (circumferential speed: 258 mm / second). The melt of the regenerated fibrous filler-reinforced PAS resin composition flowing out from the die head with a residence time of 50 seconds was water-cooled, formed into strands, and then cut to obtain pellets having a cylindrical shape with a diameter of 0.5 to 2.5 mm (average diameter 1.7 mm) and a length of 1.5 to 4 mm (average length 2.5 mm), thus obtaining a regenerated fibrous filler-reinforced PAS resin composition.

[0114] Then, the obtained regenerated fibrous filler-reinforced PAS resin composition was put into an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name: SE75S) with the barrel temperature heated to 300 °C and the mold temperature heated to 140 °C, and the molding flow length of this regenerated fibrous filler-reinforced PAS resin composition was measured. Furthermore, the Charpy impact strength was evaluated using the injection-molded test pieces. The results of each measurement and evaluation are shown in Table 1.

[0115] Examples 2 to 8

[0116] The compounding ratios of PAS resins (A-1, A-2), PIRPPS resin (B-1), glass fibers (C-1 to C-4), glass flakes (D-1), modified vinyl copolymers (E-1), epoxy resins (F-1), and mold release agents (G-1, G-2) are the conditions shown in Table 1. In addition, according to the same method as in Example 1, a granular regenerated fiber-filled reinforced PAS resin composition was obtained. Then, evaluation was carried out according to the same method as in Example 1. The evaluation results are shown in Table 1.

[0117] All of the obtained regenerated fiber-filled reinforced PAS resin compositions have excellent impact resistance and fluidity.

[0118] [Table 1]

[0119]

[0120] Comparative Examples 1 to 5

[0121] The compounding ratios of PPS (A-1, A-2, A-3, A-4), PIRPPS resin (B-1), glass fibers (C-1, C-2), glass flakes (D-1), modified vinyl copolymers (E-1), epoxy resins (F-1), and mold release agents (G-1, G-2) were set to the conditions shown in Table 2. In addition, according to the same method as in Example 1, a granular resin composition was obtained. Then, evaluation was carried out according to the same method as in Example 1. The evaluation results are shown in Table 2.

[0122] The resin compositions obtained in Comparative Examples 2, 3, and 5 have poor impact resistance. The resin compositions obtained in Comparative Examples 1 and 4 have poor fluidity.

[0123] [Table 2]

[0124]

[0125] Example 9

[0126] To 100 parts by weight of PPS (A-5) obtained in Synthesis Example 5, 19 parts by weight of PCRPPS resin (B-2) was uniformly premixed and charged into the hopper of a twin-screw extruder (manufactured by Japan Steel Works, Ltd., (trade name) TEX-25αIII, L1 / D1 = 55) having four kneading zones. On the other hand, from the hopper of the side feeder of this twin-screw extruder, glass fiber (C-5) was charged in such a manner as to be 56 parts by weight (equivalent to 47 parts by weight based on the total of 100 parts by weight of PPS resin (A-5) and PCRPPS resin (B-2)), thermoplastic elastomer (E-2) was charged in such a manner as to be 9 parts by weight, compatibilizer (F-2) was charged in such a manner as to be 0.3 parts by weight, and mold release agent (G-2) was charged in such a manner as to be 3 parts by weight. Under the condition that the barrel temperature of the kneading zone was heated to 300°C, melt-kneading was carried out at a raw material supply rate of 25 kg / h and a screw rotation speed of 200 rpm (circumferential speed; 258 mm / s). The melt of the regenerated fibrous filler-reinforced PAS resin composition flowing out from the die with a residence time of 50 seconds was water-cooled, formed into a strand, and then cut to form pellets having a cylindrical shape with an average diameter of 0.7 mm and an average length of 2.1 mm, thereby obtaining a regenerated fibrous filler-reinforced PAS resin composition.

[0127] Then, the obtained regenerated fibrous filler-reinforced PAS resin composition was charged into an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75S) with the barrel temperature heated to 300°C and the mold temperature heated to 140°C, and the molding flow length (BFL) of the regenerated fibrous filler-reinforced PAS resin composition was measured. Furthermore, the Charpy impact strength was evaluated using the injection-molded test piece. The results of each measurement and evaluation are shown in Table 3.

[0128] Examples 10 to 13

[0129] The compounding ratios of PAS resin (A-5), PCRPPS resin (B-2), glass fiber (C-3 to C-5), thermoplastic elastomer (E-2), compatibilizer (F-2), and mold release agent (G-2) were set to the conditions shown in Table 3. Except for this, pellet-shaped regenerated fibrous filler-reinforced PAS resin compositions were obtained according to the same method as in Example 9. Then, evaluation was carried out according to the same method as in Example 9. The evaluation results are shown in Table 3.

[0130] All of the obtained regenerated fibrous filler-reinforced PAS resin compositions had excellent impact resistance and fluidity.

[0131] [Table 3]

[0132]

[0133] Comparative Examples 6 - 9

[0134] The compounding ratios of PPS (A - 1, A - 3, A - 4), PCRPPS resin (B - 2), and glass fiber (C - 1) were set to the conditions shown in Table 4. Except for this, granular resin compositions were obtained according to the same method as in Example 9. Then, evaluation was carried out according to the same method as in Example 1. The evaluation results are shown in Table 4.

[0135] The resin compositions obtained from Comparative Examples 6 - 9 had poor fluidity.

[0136] [Table 4]

[0137]

[0138] It should be noted that the entire contents of the claims, the specification, and the abstract of Japanese Patent Application No. 2022 - 192698 filed on December 1, 2022 are incorporated herein by reference as the disclosure of the specification of the present invention.

[0139] Industrial Applicability

[0140] The recycled fibrous filler - reinforced PAS resin composition of the present invention contains recycled PAS resin without impairing the mechanical properties, fluidity, etc. originally possessed by the PAS resin, and is particularly useful in applications such as electrical / electronic components, automotive components, etc., or applications in water - using spaces such as pipes / fittings.

Claims

1. A regenerated fibrous filler-reinforced polyarylene sulfide resin composition, characterized in that, It contains a polyarylene sulfide resin (A), a recycled polyarylene sulfide resin (B), and a fibrous filler (C). The polyarylene sulfide resin (A) has a melt viscosity of 100 to 3000 poises as measured by a high-temperature rheometer equipped with a die having a diameter of 1 mm and a length of 2 mm under the conditions of a measurement temperature of 315°C and a load of 10 kg. The compounding amount of the recycled polyarylene sulfide resin (B) is 10 to 250 parts by weight relative to 100 parts by weight of the polyarylene sulfide resin (A). The compounding amount of the fibrous filler (C) is 10 to 60 parts by weight relative to 100 parts by weight of the total amount of the polyarylene sulfide resin (A) and the recycled polyarylene sulfide resin (B).

2. The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to claim 1, wherein The recycled polyarylene sulfide resin (B) is a post-consumer recycled polyarylene sulfide resin and / or a post-industrial recycled polyarylene sulfide resin.

3. The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to claim 1 or 2, wherein The recycled polyarylene sulfide resin (B) is a recycled non-reinforced polyarylene sulfide resin.

4. The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to any one of claims 1 to 3, characterized in that The recycled polyarylene sulfide resin (B) is a recycled non-reinforced polyarylene sulfide resin that is a recycled product belonging to at least one selected from the group consisting of polyarylene sulfide resin fibers, polyarylene sulfide resin sheets, and polyarylene sulfide resin films.

5. The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to any one of claims 1 to 4, characterized in that, The fibrous filler (C) is a chopped strand having an average fiber diameter of 6 to 14 μm and / or a chopped strand composed of flat glass fibers having an aspect ratio of the fiber cross-section of 2 to 4.

6. The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to any one of claims 1 to 5, characterized in that, It further contains a non-fibrous filler (D).

7. The regenerated fibrous filler-reinforced polyarylene sulfide resin composition according to any one of claims 1 to 6, characterized in that, It further contains a thermoplastic elastomer (E), a compatibilizer (F), and / or a mold release agent (G).

8. A pellet, characterized in that, It is a pellet formed from the recycled fibrous filler-reinforced polyarylene sulfide resin composition according to any one of claims 1 to 7, and the pellet has a cylindrical shape with a diameter of 0.5 to 2.5 mm and a length of 1.5 to 4 mm or a spherical shape with a diameter of 1 to 3 mm.

9. A method for manufacturing a regenerated fibrous filler-reinforced polyarylene sulfide resin composition, characterized in that, Using a twin-screw extruder having a screw with a ratio of screw length (L1) to screw diameter (D1) of 30 or more and two or more kneading zones, under the kneading conditions of a barrel temperature in the kneading zone of 280 to 330°C, a screw circumferential speed of 50 to 400 mm / second, and a residence time of 30 to 100 seconds, the polyarylene sulfide resin (A), the recycled polyarylene sulfide resin (B), and the fibrous filler (C) are melt-kneaded and extruded. The polyarylene sulfide resin (A) has a melt viscosity of 100 to 3000 poises as measured by a high-temperature rheometer equipped with a die having a diameter of 1 mm and a length of 2 mm under the conditions of a measurement temperature of 315°C and a load of 10 kg.

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