Polyarylene sulfide resin composition

Abstract

To provide a polyarylene sulfide composition comprising a post-consumer recycled polyamide resin and a method for producing the same without impairing the heat resistance, chemical resistance, fluidity or the like inherent in a polyarylene sulfide resin.SOLUTION: There is provided a polyarylene sulfide resin composition which comprises 10 to 90 pts.wt. of a post-consumer recycled polyamide resin (B), 30 to 200 pts.wt. of a fibrous filler (C) and a non-fibrous filler (D) based on 100 pts.wt. of a polyarylene sulfide resin (A) having a melt viscosity of 100 to 3000 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, wherein the total amount of the fibrous filler (C) and the non-fibrous filler (D) is 30 to 220 pts.wt. 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 particularly relates to a polyarylene sulfide resin composition that does not impair the inherent heat resistance, chemical resistance, fluidity, etc. of the polyarylene sulfide resin, although it contains a post-consumer recycled polyamide resin whose utilization is expected.

Background Art

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

[0003] On the other hand, in recent years, for the purpose of reducing the discharge amount of plastics, etc., there has been an increasing demand to use recycled resins for electrical and electronic equipment members, mainly in Europe and the United States, and this trend is spreading to automotive members, etc.

[0004] Among these, used fishing nets and ropes are left in large quantities, becoming one of the main causes of marine pollution. In addition, carpets and mats used in homes, automobiles, or for commercial purposes are also largely discarded, and attempts have begun to recycle the polyamide resin (sometimes called nylon) used in many of these fishing nets, ropes, carpets, and mats. Generally, 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 deteriorates 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.

[0005] Furthermore, as a resin composition containing recycled materials, for example, a recycled resin composition used 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 1), (A) Recycled aromatic polycarbonate resin 4 A polycarbonate resin composition has been proposed (see, for example, Patent Document 2) 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 in the form of 0 to 80% by mass of (B) and 20 to 60% by mass of (C), (D) 10 to 20 parts by mass of a phosphate ester compound, (E) 0.01 to 1 part by mass of a fluorine compound, and (F) 0.5 to 10 parts by mass of a polyorganosiloxane-containing graft copolymer, and does not contain nickel-coated carbon fibers.

[0006] Furthermore, as a method for manufacturing molded articles containing recycled materials, for example, a method has been proposed in which 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 are subjected to injection molding in an injection molding machine (see, for example, Patent Document 3).

[0007] Furthermore, as a method for recycling nylon, a method for producing recycled nylon fibers has been proposed (see, for example, Patent Document 4), which includes the steps of: providing nylon fiber waste, such as oil-resistant nylon 6 fiber waste or oil-resistant nylon 66 fiber waste; crushing the nylon fiber waste to form multiple 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 multiple nylon films with a moisture content of 4 wt% or less; melt granulation to form multiple recycled nylon particles by melt granulating the nylon films; and melt spinning to obtain recycled nylon fibers by melt spinning the recycled nylon particles. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2021-115795 [Patent Document 2] Patent No. 6825890 [Patent Document 3] Patent No. 5386853 [Patent Document 4] Patent No. 6629943 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] However, the resin compositions proposed in Patent Documents 1 and 2 do not mention polyarylene sulfide resins at all. Furthermore, the method for manufacturing molded articles proposed in Patent Document 3 contains recycled fibrous filler-reinforced polyphenylene sulfide composition pellets, i.e., PIR, which are regenerated from sprues, runners, or unwanted parts of the molded article generated during injection molding, and does not propose any PCR, which is difficult to reuse. Moreover, the manufacturing method proposed in Patent Document 4 relates to a method for manufacturing recycled nylon fibers, and does not propose any resin compositions containing recycled nylon that can be reused as various molded articles.

[0010] Therefore, the present invention aims to provide a PAS resin composition containing PCR polyamide resin without impairing the inherent heat resistance, chemical resistance, fluidity, etc., of the PAS resin. [Means for solving the problem]

[0011] As a result of diligent research to solve the above problems, the inventors of the present invention have found that a specific PAS resin composition containing PCR polyamide resin can be made to have excellent heat resistance, dimensional accuracy, rigidity, heat and moisture resistance, and fluidity, and have completed the present invention.

[0012] In other words, the present invention relates to a PAS resin composition in which, per 100 parts by weight of PAS 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 with a diameter of 1 mm and a length of 2 mm is 100 to 3000 poise, the composition contains 10 to 90 parts by weight of PCR polyamide resin (B), 30 to 200 parts by weight of fibrous filler (C), and non-fibrous filler (D), wherein the total amount of fibrous filler (C) and non-fibrous filler (D) is 30 to 220 parts by weight per 100 parts by weight of the total amount of PAS resin (A) and PCR polyamide resin (B).

[0013] The present invention will be described in detail below.

[0014] The PAS resin (A) constituting the PAS resin composition of the present invention may be any resin that generally falls within the category referred to as PAS resin. Examples of such PAS resins 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 such PAS resins include PPS, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, and polyphenylene sulfide ether. Among these, PPS is particularly preferred because it results in a PAS resin composition with excellent heat resistance and strength properties.

[0015] The PAS resin (A) has a melt viscosity of 100 to 3000 poises, measured using a high-efficiency flow tester 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. If the poise is less than 100 poises, the resulting composition will have inferior mechanical strength. On the other hand, if the poise exceeds 3000 poises, the fluidity will be inferior.

[0016] 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.

[0017] 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.

[0018] The PAS resin (A) may be a PAS resin called virgin resin obtained by the above manufacturing method, a PCRPAS resin collected or recycled after the product has been used and discarded by consumers, or a recycled PAS resin which is a PIRPAS resin consisting of sprues, runners, molding waste, and defective products generated during the manufacturing process of the product. Among these, a PIRPAS resin in which degradation is relatively suppressed is preferred.

[0019] 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 has been used and discarded by consumers. Examples of such polyamide resins include polytetramethylene sebaamide (nylon 410), polypentamethylene sebaamide (nylon 510), polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebaamide (nylon 610), polyhexamethylene dodecamide (nylon 612), and polydecamethylene sebaamide (nylon 1010). Examples include homopolyamide resins such as polydodecaneamide (nylon 12), polyundecaneamide (nylon 11), polyhexamethylene terephthalamide (nylon 6T), polyxylylene adipamide (nylon XD6), polynonanemethylene terephthalamide (nylon 9T), and polydecamethylene terephthalamide (nylon 10T), or copolymer polyamides such as nylon 6 / 66, nylon 6 / 10, nylon 6 / 66 / 610, 66 / 6T, and 66 / 10T, and mixtures of these polyamide resins are also acceptable.

[0020] Furthermore, as PCR polyamide resin (B), it is preferable to use PCR polyamide resin obtained from collected and / or recycled fishing nets, ropes, carpets, and mats, as large quantities of polyamide resin with the same structure, grade, and in some cases even from the same lot can be recycled from fishing nets, ropes, carpets, and mats, making it possible to obtain PCR polyamide resin with small variations in quality. As a result, it is possible to obtain a PAS resin composition with small variations in quality.

[0021] 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 150 parts by weight, the resulting composition will be inferior in terms of moisture and heat resistance, fluidity, heat resistance, chemical resistance, and color tone.

[0022] The fibrous filler (C) constituting the PAS resin composition of the present invention improves the mechanical strength of the PAS resin composition. Examples thereof include glass fibers; carbon fibers such as PAN-based carbon fibers and 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 rock wool, zirconia, alumina silica, barium titanate, silicon carbide, alumina, silica, blast furnace slag, etc.; organic fibers such as wholly aromatic polyamide fibers, phenol resin fibers, wholly aromatic polyester fibers, etc.; mineral fibers such as wollastonite, magnesiumoxysulfate, etc. Among them, glass fibers are preferred because they provide a PAS resin composition with particularly excellent mechanical strength and impact resistance. Any material generally referred to as glass fiber may be used as the glass fiber. Specific examples of the glass fiber include 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, milled fibers, rovings, etc.; silane fibers; aluminosilicate glass fibers; hollow glass fibers; non-holey glass fibers, etc. Among them, chopped strands with an average fiber diameter of 6 to 14 μm or chopped strands composed of flat glass fibers with an aspect ratio of the fiber cross-section of 2 to 4 are preferred because they provide a polyarylene sulfide resin composition with particularly excellent mechanical strength, impact resistance, and fluidity. These fibrous fillers can also be used in combination of two or more kinds, and if necessary, functional compounds or polymers such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, etc., which have been surface-treated in advance, may be used. The blending amount of the fibrous filler (C) is 30 to 200 parts by weight with respect to 100 parts by weight of the PAS resin, because it provides a PAS resin composition with an excellent balance between toughness, mechanical strength, and fluidity. Here, when the blending amount of the fibrous filler is less than 30 parts by weight, the resulting composition will be inferior in mechanical strength and impact resistance. On the other hand, when it exceeds 200 parts by weight, the fluidity will be inferior.

[0023] The non-fibrous filler (D) constituting the PAS resin composition of the present invention imparts dimensional accuracy and rigidity to the PAS resin composition. Examples thereof 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 balloon, glass flake, etc. Particularly, since it becomes a PAS resin composition excellent in dimensional accuracy and rigidity, it is preferably calcium carbonate or glass flake. Further, since it becomes a polyarylene sulfide resin composition particularly excellent in mechanical strength, impact resistance, and fluidity, it is preferably calcium carbonate or glass flake having an average particle size of 2 to 800 μm.

[0024] Also, the blending amount of the non-fibrous filler (D) is such that the total amount of the fibrous filler (C) and the non-fibrous filler (D) corresponds to 30 to 220 parts by weight with respect to 100 parts by weight of the total amount of the PAS resin (A) and the PCR amide resin (B). Here, when the total amount of the fibrous filler and the non-fibrous filler is less than 30 parts by weight, the resulting composition will be inferior in rigidity and dimensional accuracy. On the other hand, when it exceeds 220 parts by weight, it will be inferior in rigidity and fluidity.

[0025] Since the PAS resin composition of the present invention is particularly excellent in mechanical strength and impact resistance, it may further contain a compatibilizer (E). Examples of the compatibilizer include isocyanurate, epoxy resin, silane coupling agent, or a mixture of these compatibilizers may also be used.

[0026] The isocyanurate can be any isocyanurate, and among them, an aliphatic isocyanurate is particularly preferred because it results in a PAS resin composition with low mold contamination. Specific examples of the aliphatic isocyanurate 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 this results in a PAS resin composition with excellent reactivity with PAS resin and PCR polyamide resin and excellent impact resistance.

[0027] 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).

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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. The screw used in the twin-screw extruder in this case preferably has two or more kneading zones. Furthermore, to ensure sufficient compatibility between the PAS resin (A) and the PCR polyamide resin (B), and as a result, to obtain a PAS resin composition with excellent toughness such as impact resistance, a screw with a ratio of screw length (L) to screw diameter (D) (L / D) of 30 or more, and particularly 40 or more, is preferred.

[0034] 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 330°C, and particularly preferably to 290°C to 320°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.

[0035] 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. In particular, it is preferable to use cold cutting or hot cutting, 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 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, it is preferable that the pellets have a light brown or brown color, as this allows for the production of molded products with excellent appearance.

[0036] 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.

[0037] The PAS resin composition of the present invention contains PCR polyamide resin without impairing the heat resistance, chemical resistance, and fluidity inherent in PAS resin, and is suitable for use in electrical and electronic components, automotive parts, and other applications. [Effects of the Invention]

[0038] According to the present invention, a PAS resin composition containing PCR polyamide resin can be provided. This PAS resin composition has excellent heat resistance, dimensional accuracy, rigidity, moisture and heat resistance, and fluidity, and is particularly useful for applications such as electrical and electronic components and automotive parts, and has extremely high industrial value. [Examples]

[0039] The present invention will be described in detail below with reference to examples, but the present invention is not limited in any way thereto.

[0040] The polyarylene sulfide (A), post-consumer recycled polyamide resin (B), fibrous filler (C), non-fibrous filler (D), compatibilizer (E), and release agent (F) used in the examples and comparative examples are shown below.

[0041] <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 3220 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-5)): Melt viscosity 80 poise.

[0042] <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.

[0043] <Polyamide resin (B')> Polyamide 6 resin (B'); manufactured by Ube Industries, Ltd., (product name) 1013B.

[0044] <Fibrous filler (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.

[0045] <Non-fibrous filler (D)> Calcium carbonate (D-1); manufactured by Shiraishi Kogyo Co., Ltd., (product name) Whiteon P-30; average particle size 6 μm. Glass flakes (D-2); manufactured by Nippon Sheet Glass Co., Ltd., (product name) REFG-301; average particle size 160 μm.

[0046] <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.

[0047] <Release agent (F)> Release agent (F-1); manufactured by Kyoeisha Chemical Co., Ltd., (product name) Light Amid WH-255.

[0048] 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).

[0049] 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.

[0050] 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).

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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-4)). The melt viscosity of PPS(A-4) was 3220 poise.

[0056] 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).

[0057] 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.

[0058] The evaluation and measurement methods for the obtained PAS resin and PAS resin composition are shown below.

[0059] ~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.

[0060] ~Measurement of the flexural modulus of PAS resin composition~ Test specimens were prepared using an injection molding machine (Sumitomo Heavy Industries, Ltd., product name SE-75S), and measurements were performed in accordance with ISO 178. The flexural modulus was 15 kJ / m². 2 The above materials were deemed to have superior rigidity.

[0061] ~Measurement of molding shrinkage rate of PAS resin composition~ Using an injection molding machine (Sumitomo Heavy Industries, Ltd., product name SE-75S), injection molding was performed at a cylinder temperature of 310°C and a mold temperature of 135°C to produce test specimens with a thickness of 2 mm, a width of 70 mm, and a length of 70 mm. Next, the molded test specimens were left to stand for 24 hours in a constant temperature chamber adjusted to 23°C × 50% Rh, and then the dimensions in the MD and TD directions were measured. The molding shrinkage rate was then calculated as (mold dimensions - measured values ​​of the test specimen) / mold dimensions (percentage). A molding shrinkage rate of less than 0.8% was judged to indicate excellent dimensional accuracy.

[0062] ~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.

[0063] ~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 70 mm was judged to have excellent fluidity.

[0064] ~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.

[0065] Example 1 To 100 parts by weight of PPS(A-1) obtained in Synthesis Example 1, 35 parts by weight of PCR(B-1) and 130 parts by weight of calcium carbonate(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 100 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 320°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 obtain cylindrical, light brown pellets with a diameter of 1.7 mm and a length of 2.0 mm, thereby producing a PAS resin composition.

[0066] 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. Furthermore, the flexural modulus, dimensional change rate, color tone, and heat and humidity resistance were evaluated using the injection-molded test pieces. The results of each measurement and evaluation are shown in Table 1.

[0067] Examples 2-11 Pellet-shaped PAS resin compositions were prepared using the same method as in Example 1, with the blending ratios of PPS resin (A), PCR polyamide resin (B), fibrous filler (C), non-fibrous filler (D), compatibilizer (E), and mold release agent (F) as shown in Table 1. These compositions were then evaluated using the same method as in Example 1. The evaluation results are shown in Table 1.

[0068] All of the obtained PAS resin compositions exhibited excellent rigidity, dimensional accuracy, heat and humidity resistance, fluidity, and color tone.

[0069] [Table 1]

[0070] Comparative Examples 1-9, Reference Example 1 Pellet-shaped resin compositions were prepared using the same method as in Example 1, with the blending ratios of PPS resin (A), PCR polyamide resin (B), polyamide resin (B'), fibrous filler (C), and non-fibrous filler (D) as shown in Table 2. These compositions were then evaluated using the same method as in Example 1. The evaluation results are shown in Table 2.

[0071] The resin compositions obtained from Comparative Examples 3, 4, 5, 6, 7, 8, and 9 had inferior rigidity. The resin compositions obtained from Comparative Examples 2, 5, and 9 had inferior dimensional accuracy. The resin composition obtained from Comparative Example 1 had inferior resistance to moisture and heat, and the resin compositions obtained from Comparative Examples 1, 2, 3, 6, and 7 had inferior fluidity. The resin composition and test specimen obtained from Comparative Example 1, and the test specimens obtained from Comparative Examples 5 and 7, had inferior color tone.

[0072] [Table 2] [Industrial applicability]

[0073] The PAS resin composition of the present invention contains PCR polyamide resin without impairing the heat resistance, chemical resistance, and fluidity inherent in PAS resin, and is particularly useful for applications such as electrical and electronic components, automotive parts, and plumbing and fittings.

Claims

1. A polyarylene sulfide resin composition comprising 100 parts by weight of a polyarylene sulfide resin (A) having a melt viscosity of 100 to 3000 poise as measured at a 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, 10 to 90 parts by weight of a post-consumer recycled polyamide resin (B), 43 to 170 parts by weight of a fibrous filler (C), and a non-fibrous filler (D), wherein the total amount of fibrous filler (C) and non-fibrous filler (D) is 67 to 170 parts by weight relative to the total amount of polyarylene sulfide resin (A) and post-consumer recycled polyamide resin (B) of 100 parts by weight.

2. The polyarylene sulfide resin composition according to claim 1, characterized in that the polyarylene sulfide resin (A) is a recycled polyarylene sulfide resin.

3. The polyarylene sulfide resin composition according to claim 1 or 2, 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.

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), a fibrous filler (C), and a non-fibrous filler (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 pellet comprising 100 parts by weight of polyarylene sulfide resin (A), the melt viscosity measured at a 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 3000 poise, 10 to 90 parts by weight of post-consumer recycled polyamide resin (B), 43 to 170 parts by weight of fibrous filler (C), and non-fibrous filler (D), wherein the total amount of fibrous filler (C) and non-fibrous filler (D) is 67 to 170 parts by weight for every 100 parts by weight of the total amount of polyarylene sulfide resin (A) and post-consumer recycled polyamide resin (B), and having 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, and having a light brown or brown color.

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