CN118119669A - Polyarylene sulfide composition and method for producing same - Google Patents

Abstract

Provided are a polyarylene sulfide composition containing a post-consumer recycled polyamide and a fibrous filler without impairing the heat resistance, chemical resistance, flowability, etc. inherent in polyarylene sulfide, and a method for producing the same. A polyarylene sulfide composition comprising 10 to 90 parts by weight of a post-consumer recycled polyamide (B) per 100 parts by weight of a polyarylene sulfide (A), and 20 to 110 parts by weight of a fibrous filler (C) per 100 parts by weight of the total amount of the polyarylene sulfide (A) and the post-consumer recycled polyamide (B), wherein the polyarylene sulfide (A) has a melt viscosity of 100 to 3000 poise measured by a high-pressure rheometer equipped with a die having a diameter of 1mm and a length of 2mm and under a load of 10kg at a measurement temperature of 315 ℃.

Description

Polyarylene sulfide composition and method for producing same

Technical Field

The present invention relates to a polyarylene sulfide composition, and more particularly, to a polyarylene sulfide composition which does not impair heat resistance, chemical resistance, fluidity, and the like inherent in a polyarylene sulfide even though it contains a post-consumer recycled polyamide which is expected to be used, and a method for producing the same; in particular, the present invention relates to a polyarylene sulfide composition which can provide a composite body excellent in thermal shock resistance and excellent in adhesion and air tightness even when the polyarylene sulfide composition is formed into a composite body with a metal member.

Background

Polyarylene sulfide (hereinafter, abbreviated as "PPS") represented by poly (p-phenylene sulfide) (hereinafter, abbreviated as "PPS") is a resin exhibiting excellent properties such as heat resistance, chemical resistance, and fluidity, and is widely used for electric/electronic equipment members, automobile members, OA equipment members, and the like, by utilizing the excellent properties.

On the other hand, in recent years, for the purpose of reducing the amount of plastic discharged, the demand for use of a recycled resin in electric/electronic equipment members has been increasing, and the trend has been spreading to automobile members and the like.

Among them, the used fishing net and rope are put aside in large quantity, which becomes one of the main causes of marine pollution. In addition, carpets and mats used for home use, automobile use, or business use are often discarded. Attempts have been made to regenerate the polyamide (sometimes also referred to as nylon) used in large quantities for such nets, ropes, carpets, mats. In general, the regenerated materials are roughly classified into post-consumer regenerated materials (hereinafter, also simply referred to as PCR), which is a material obtained by collecting or recycling products after they are used and discarded by consumers, and post-industrial regenerated materials (hereinafter, also simply referred to as PIR), which is a material obtained by collecting or recycling waste generated in a manufacturing process before the products are delivered to consumers. Moreover, PCR is unstable with respect to PIR due to deterioration during use, and it is difficult to manufacture and obtain stable PCR suitable for use, and therefore, the cost is high, and the field of use is limited to a part of PET bottles and the like, and further popularization and use of PCR are expected in the future.

As a resin composition containing a recycled material, for example, there has been proposed: a recycled resin composition (see, for example, patent document 1) for a filament material for a 3D printer of a hot melt lamination system, which comprises a recycled resin (a) and a resin (B), wherein the recycled resin (a) is recycled from a plastic packaging material and contains a polyolefin resin as a main component and an unmelted product having a particle ratio of 200 μm or more in a maximum diameter of 15% or less, and the resin (B) has a melt flow rate of 5g/10 minutes or more measured at a temperature of 230 ℃ under a load of 2.16 kg; a polycarbonate resin composition (see, for example, patent document 2) which comprises, based on 100 parts by mass of the total of (A) 40 to 80% by mass of a recycled aromatic polycarbonate resin and (B) 20 to 60% by mass of an aromatic polycarbonate resin, 10 to 60 parts by mass of (C) nickel-uncoated carbon fibers covered with a resin selected from the group consisting of polyamides, polyurethanes and epoxy resins, (D) 10 to 20 parts by mass of a phosphate 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 which does not contain nickel-coated carbon fibers.

As a method for producing a molded article containing a recycled material, for example, a method for producing a molded article has been proposed (for example, see patent document 3) in which 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 are fed to an injection molding machine and injection molded.

As a method for regenerating nylon, for example, a method for producing regenerated nylon fiber (for example, see patent document 4) has been proposed, which includes: providing nylon fiber waste, wherein the nylon fiber waste is oil-resistant nylon 6 fiber waste or oil-resistant nylon 66 fiber waste; a pulverizing step of pulverizing the nylon fiber waste to form a plurality of pieces of nylon fibers; a cleaning step of cleaning the chips of the nylon fibers to reduce the oil content of the chips of the nylon fibers to 0.22wt% or less; a dehydration extrusion step of removing moisture from the fragments of the nylon fibers to form a plurality of nylon films having a moisture content of 4wt% or less; a melt granulation step of melt granulating the nylon film to form a plurality of regenerated nylon particles; and a melt spinning step of melt spinning the regenerated nylon particles to obtain regenerated nylon fibers.

Further, as a technique for improving the thermal shock resistance of PAS, a technique of blending a modified ethylene copolymer into PAS has been proposed (for example, see patent documents 5 and 6) because the thermal shock resistance of PAS is inferior to that of other engineering plastics.

In order to reduce the weight of components of transportation equipment such as automobiles and airplanes, a method of replacing a part of metal with a resin has been studied. As a method for compounding and integrating a resin and a metal, a method in which a metal member having a surface subjected to physical treatment and/or chemical treatment is inserted into a mold and the resin is injection molded to be directly integrated (hereinafter, sometimes referred to as an injection insert molding method) has been attracting attention from the viewpoints of good mass productivity, a small number of parts, low cost, high design freedom, and low environmental load, and has been proposed in a manufacturing process of a portable electronic device such as a smart phone (for example, refer to patent documents 7 to 9).

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2021-115795

Patent document 2: japanese patent No. 6825890

Patent document 3: japanese patent No. 5386853

Patent document 4: japanese patent No. 6629943

Patent document 5: japanese patent application laid-open No. 2008-144003

Patent document 6: japanese patent laid-open No. 2005-306926

Patent document 7: japanese patent No. 5701414

Patent document 8: japanese patent No. 5714193

Patent document 9: japanese patent No. 4020957

Disclosure of Invention

Problems to be solved by the invention

However, in the resin compositions proposed in patent documents 1 and 2, there is no mention at all of super engineering plastics, needless to say, of polyarylene sulfide resins which are difficult to handle and use. The method for producing a molded article proposed in patent document 3 contains PIR, which is a pellet of a polyphenylene sulfide composition reinforced by a recycled fibrous filler such as sprue (sprue), runner (runner) or a unnecessary product of the molded article, which is produced by injection molding, and does not suggest PCR which is difficult to reuse. The production method proposed in patent document 4 relates to a production method of recycled nylon fibers, and there is no proposed any resin composition containing recycled nylon which can be reused as various molded articles.

In addition, the resin compositions proposed in patent documents 5 and 6 are not mentioned at all as resin compositions containing recycled nylon. The method for producing the composite described in patent document 7, the composite structure described in patent document 8, and the laser processing method described in patent document 9 are not mentioned at all as a resin composition containing recycled nylon.

Accordingly, an object of the present invention is to provide a PAS composition containing a PCR polyamide without impairing the heat resistance, chemical resistance, fluidity and the like inherent in PAS, and a method for producing the same; also provided is a PAS composition which can provide a composite body excellent in thermal shock resistance and excellent in adhesion and air tightness even when formed into a composite body with a metal member.

Solution for solving the problem

The present inventors have made intensive studies to solve the above problems, and as a result, have found that a specific PAS composition containing a PCR polyamide is excellent in heat resistance, chemical resistance and flowability, and further, by blending a thermoplastic elastomer, a composite body which is excellent in thermal shock resistance and exhibits excellent adhesion and air tightness even when formed into a composite body with a metal member can be produced, and have completed the present invention.

That is, the present invention resides in the following [1] to [10].

[1] A polyarylene sulfide composition comprising 10 to 90 parts by weight of a post-consumer recycled polyamide (B) per 100 parts by weight of a polyarylene sulfide (A) and 20 to 110 parts by weight of a fibrous filler (C) per 100 parts by weight of the total amount of the polyarylene sulfide (A) and the post-consumer recycled polyamide (B), wherein the polyarylene sulfide (A) has a melt viscosity of 100 to 3000 poise measured by a high-pressure rheometer equipped with a die having a diameter of 1mm and a length of 2mm and under conditions of a measurement temperature of 315 ℃ and a load of 10 kg.

[2] The polyarylene sulfide composition according to [1], wherein the polyarylene sulfide (A) is a regenerated polyarylene sulfide.

[3] The polyarylene sulfide composition according to [1] or [2], wherein the post-consumer recycled polyamide (B) is a post-consumer recycled polyamide obtained by collecting and/or recycling at least 1 or more selected from the group consisting of fishing nets, ropes, carpets, mats.

[4] The polyarylene sulfide composition according to any one of [1] to [3], further comprising a compatibilizer (D) selected from at least 1 or more of isocyanurate, epoxy resin, and silane coupling agent, and/or a release agent (E) selected from at least 1 or more of polyethylene wax, polypropylene wax, and fatty acid amide-based wax.

[5] The polyarylene sulfide composition according to any one of [1] to [4], further comprising a non-fibrous filler (F).

[6] The polyarylene sulfide composition according to any one of [1] to [5], wherein the polyarylene sulfide (A) is a polyarylene sulfide having a melt viscosity of 100 to 2000 poise, the fibrous filler (C) is a glass fiber, and the polyarylene sulfide composition further comprises a thermoplastic elastomer (G).

[7] The process for producing a polyarylene sulfide composition according to any one of [1] to [6], wherein at least the polyarylene sulfide (A), the post-consumer recycled polyamide (B) and the fibrous filler (C) are melt kneaded and extruded under kneading conditions in which the barrel temperature in the kneading zone is 280 to 330 ℃, the peripheral speed of the screw is 50 to 400 mm/sec, and the residence time is 30 to 100 seconds, by using a twin-screw extruder having a screw with a screw length (L) to screw diameter (D) ratio (L/D) of 30 or more and a kneading zone of 2 or more.

[8] A pellet comprising the polyarylene sulfide composition according to any one of [1] to [6], wherein the pellet has a cylindrical shape having a diameter of 0.5 to 2.5mm and a length of 1.5 to 4mm or a spherical shape having a diameter of 1 to 3 mm.

[9] The pellet according to [8], characterized by having a light brown or brown hue.

[10] The pellet according to [8] or [9], characterized in that it is a cold-cut pellet.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a PAS composition containing a PCR polyamide, which is excellent in impact resistance, mechanical strength, heat resistance, chemical resistance, moisture resistance, fluidity, thermal shock resistance and adhesion to metals, and which is particularly useful for applications such as electric/electronic parts, automobile parts or building pipes, and which has extremely high industrial value.

Drawings

FIG. 1 is a schematic view of an embedded test piece used in the examples.

Detailed Description

The present invention will be described in detail below.

The PAS (a) constituting the PAS composition of the present invention may be any PAS falling within the category commonly referred to as PAS, and examples thereof include: a homopolymer or copolymer comprising 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, and as a specific example of the PAS, there may be mentioned: among them, PPS is preferable from the viewpoint of forming a PAS composition excellent in heat resistance and strength characteristics.

The PAS (A) has a melt viscosity of 100 to 3000 poise measured at a measurement temperature of 315℃under a load of 10kg by using a high-pressure rheometer equipped with a die having a diameter of 1mm and a length of 2 mm. In this case, the mechanical strength of the resulting composition is poor at less than 100 poise. On the other hand, in the case of exceeding 3000 poise, the fluidity of the resulting composition is poor.

The PAS (A) can be produced by a known method for producing PAS, for example, by polymerizing an alkali metal sulfide or a polyhaloaromatic compound in a polar solvent. Examples of the polar organic solvent include: examples of the alkali metal sulfide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, dimethylacetamide, and the like: anhydrous or hydrated forms of sodium sulfide, rubidium sulfide, and lithium sulfide. The alkali metal sulfide may be an alkali metal sulfide obtained by reacting an alkali metal hydrosulfide with an alkali metal hydroxide. Examples of the polyhaloaromatic compound include: p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4 '-dichlorodiphenyl sulfone, 4' -dichlorobenzophenone, 4 '-dichlorodiphenyl ether, 4' -dichlorobenzene, and the like.

The PAS (a) may be a linear PAS (a), a PAS (a) in which a trihalo compound is added in a small amount during polymerization to introduce a plurality of crosslinking or branching structures, a PAS (a) in which a part and/or a terminal of the molecular chain of the PAS resin is modified with a functional group such as a carboxyl group, a carboxyl metal salt, an amino group, an alkyl group, an alkoxy group, or a nitro group, or the like, or a PAS (a) in which a heat treatment is performed in a non-oxidizing inert gas such as nitrogen, or a mixture of these structures. The PAS (A) may be subjected to a deionization treatment (acid washing, hot water washing, etc.) before or after the heat curing, or a washing treatment with an organic solvent such as acetone or methanol to obtain PAS (A) having reduced impurities such as sodium atoms, oligomers of PAS, salt, sodium salt of 4- (N-methyl-chlorophenylamino) butyrate, etc. The PAS (A) may be obtained by heating and curing in an inert gas or an oxidizing gas after completion of the polymerization reaction.

As the PAS (a), the PAS called a virgin resin obtained by the above-mentioned production method may be PCRPAS obtained by collecting or recycling the product after the use and discarding thereof by a consumer, PIRPAS which is a recycled PAS which is a sprue, runner, non-product during molding and defective product during molding, and is produced by the production process of the product, and PIRPAS in which deterioration is suppressed is preferable.

The PCR polyamide (B) constituting the PAS composition of the present invention may be any polyamide as long as it is a polyamide obtained by collecting or recycling a product after being discarded by a consumer, and examples thereof include: polybutylene sebacamide (nylon 410), polybutylene sebacamide (nylon 510), polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecanoamide (nylon 612), polyhexamethylene sebacamide (nylon 1010), polylaurolactam (nylon 12), polyundecamide (nylon 11), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene adipamide (nylon XD 6), polyhexamethylene terephthalamide (nylon 9T), and polyamide copolymers (nylon 6/66, nylon 6/10, nylon 6/66/610, 66/6T, 66/10T) and the like, and also can be a mixture of these polyamides.

In addition, as the PCR polyamide (B), since a large amount of polyamides having the same structure, the same grade, and even the same lot can be regenerated from the fishing net, the rope, the carpet, and the mat, a PCR polyamide having small quality deviation can be obtained, and as a result, a PAS composition having small quality deviation can be obtained, and from this point of view, a PCR polyamide obtained by collecting and/or regenerating the fishing net, the rope, the carpet, and the mat is preferable.

The amount of the PCR polyamide (B) to be blended is 10 to 90 parts by weight based on 100 parts by weight of PAS (A). When the amount of the PCR polyamide (B) is less than 10 parts by weight, the use ratio of the recycled material is low, and the meaning of recycling is reduced. On the other hand, when the amount exceeds 90 parts by weight, the resulting composition is poor in wet heat resistance, fluidity, heat resistance, chemical resistance and color tone.

The fibrous filler (C) constituting the PAS composition of the present invention may improve the mechanical strength of the PAS composition, and examples thereof include: glass fibers; carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers; graphitized fibers; silicon nitride whisker, basic magnesium sulfate whisker, barium titanate whisker, potassium titanate whisker, silicon carbide whisker, boron whisker, zinc oxide whisker and other whiskers; metal fibers such as stainless steel fibers; mineral wool, zirconia, alumina silica, barium titanate, silicon carbide, alumina, silica, blast furnace slag, and other inorganic fibers; organic fibers such as wholly aromatic polyamide fibers, phenolic resin fibers, and wholly aromatic polyester fibers; mineral fibers such as wollastonite and basic magnesium sulfate are particularly preferably glass fibers from the viewpoint of forming a PAS composition excellent in mechanical strength and impact resistance. Any glass fiber can be used as the glass fiber as long as it is a material generally called glass fiber. Specific examples of the glass fiber include: chopped strands having an average fiber diameter of 6 to 14 μm, chopped strands composed of flat glass fibers having an aspect ratio of2 to 4 in fiber cross section, glass fibers such as milled fibers and rovings; silane fibers; aluminosilicate glass fibers; hollow glass fibers; among them, chopped strands having an average fiber diameter of 6 to 14 μm or chopped strands composed of flat glass fibers having a fiber cross-section aspect ratio of2 to 4 are preferable from the viewpoint of forming a PAS composition excellent in mechanical strength, impact resistance and flowability. These fibrous fillers may be used in combination of2 or more kinds, and may be surface-treated with functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, and the like, or polymers, as necessary. The amount of the fibrous filler (C) is 20 to 110 parts by weight based on 100 parts by weight of the total amount of PAS (A) and PCR polyamide (B) from the viewpoint of forming a PAS composition excellent in balance between toughness, mechanical strength and fluidity. Here, when the fibrous filler is less than 20 parts by weight, the impact resistance of the resulting composition is poor. On the other hand, when it exceeds 110 parts by weight, fluidity is poor.

In particular, the PAS composition of the present invention preferably further contains a compatibilizer (D) from the viewpoint of excellent mechanical strength and impact resistance. Examples of the compatibilizing agent include: isocyanurate, epoxy, silane coupling agent, mixtures of these.

Further, the isocyanurate may be any one called isocyanurate, and among them, aliphatic isocyanurate is preferable from the viewpoint of forming a PAS composition having low mold fouling. Specific examples of the aliphatic isocyanurate include: 1,3, 5-three (6-isocyanatohexyl-1-base) -1,3, 5-three triazine-2, 4,6 (1H, 3H, 5H) -three ketone, 1,3, 5-three (6-isocyanatobutyl-1-base) -1,3, 5-three triazine-2, 4,6 (1H, 3H, 5H) -three ketone, 1,3, 5-three (6-isocyanatododecyl-1-base) -1,3, 5-three triazine-2, 4,6 (1H, 3H, 5H) -three ketone, especially from the view point of forming PAS composition with low mold pollution, preferably molecular weight of more than 500 aliphatic isocyanurate. The aliphatic isocyanurate may be a dimer, trimer or other polymer, or an isocyanurate containing a dimer, trimer or other polymer in the aliphatic isocyanurate monomer, and from the viewpoint of having excellent reactivity with PAS and PCR polyamide and being a PAS composition having excellent impact resistance, an aliphatic isocyanurate containing 20% or more of isocyanate groups is preferable.

The aliphatic isocyanurate may be obtained by modifying a part of the aliphatic isocyanate with an alcohol such as 1, 3-butanediol or 2, 4-trimethyl-1, 3-pentanediol. Among these aliphatic isocyanurates, 1,3, 5-tris (6-isocyanatohexyl-1-yl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione is preferable, in particular, from the viewpoint of excellent heat resistance and availability. Specific examples of 1,3, 5-tris (6-isocyanatohexyl-1-yl) -1,3, 5-triazine-2, 4,6 (1 h,3h,5 h) -trione include: (trade name) coronate HXR (manufactured by Tosoh corporation) and (trade name) duranate TPA-100 (manufactured by Asahi chemical Co., ltd.).

Any epoxy resin may be used as long as it is in the category called epoxy resins. Specific examples thereof include: glycidyl ether-based epoxy resins synthesized from 2, 2-bis (4 ' -hydroxyphenyl) propane (bisphenol a), bis (2-hydroxyphenyl) methane (bisphenol F), 4' -dihydroxydiphenyl sulfone (bisphenol S), 4' -dihydroxybiphenyl, resorcinol, salicyl alcohol, trihydroxydiphenyldimethylmethane, tetrahydroxyphenylethane, halogen substituents thereof, alkyl substituents, butanediol, ethylene glycol, erythritol, novolak, glycerol, a compound containing 2 or more hydroxyl groups in the molecule of polyoxyalkylene, and epichlorohydrin; a glycidyl ester-based epoxy resin synthesized from a compound having 2 or more hydroxyl groups in the molecule, such as glycidyl phthalate; glycidyl group-containing epoxy resins such as glycidyl amine-based epoxy resins synthesized from primary or secondary amines such as aniline, diaminodiphenylmethane, m-xylylenediamine, 1, 3-diaminomethylcyclohexane, and epichlorohydrin; glycidyl-free epoxy resins such as epoxidized soybean oil, epoxidized polyolefin, vinylcyclohexene dioxide, dicyclopentadiene dioxide and the like. Among them, bisphenol epoxy resins such as glycidyl ether epoxy resins and glycidyl ester epoxy resins of bisphenol compounds such as bisphenol a, bisphenol F and bisphenol S are preferable from the viewpoint of particularly excellent impact resistance of the obtained PAS composition. Further preferred are bisphenol a type epoxy resins.

Further, as the silane coupling agent, any silane coupling agent may be used as long as it falls within the category called silane coupling agents, and among them, 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 preferable from the viewpoint of forming a PAS composition excellent in impact resistance and mechanical strength. The silane coupling agent in this case is not particularly limited as long as it is a trialkoxysilane coupling agent having a glycidyl group or an amino group, and specific examples belonging to this category include: 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane, 3-glycidoxypropyl triethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane, N-2- (aminoethyl) -3-aminopropyl methyl dimethoxy silane, N-2- (aminoethyl) -3-aminopropyl trimethoxy silane, and the like.

The blending amount of the compatibilizer (D) is preferably 0.1 to 15 parts by weight based on 100 parts by weight of the PAS resin, from the viewpoint of obtaining a PAS composition excellent in impact resistance, mechanical strength and low in mold fouling.

The PAS composition of the present invention may further contain a mold release agent (E) in order to improve mold releasability and appearance when molded articles are produced. As the release agent (E), for example, polyethylene wax, polypropylene wax, and fatty acid amide wax are suitably used. As the polyethylene wax and the polypropylene wax, general commercial products can be used. The fatty acid amide wax is a polycondensate composed of a higher aliphatic monocarboxylic acid, a polybasic acid and a diamine, and any of these can be used as long as they fall into the category, and examples thereof include: and LIGHT AMIDE WH-255 (trade name) which is a polycondensate composed of stearic acid, sebacic acid and ethylenediamine (manufactured by co-mingling chemical Co., ltd.).

From the viewpoint of excellent dimensional accuracy and rigidity, the PAS composition of the present invention preferably contains a non-fibrous filler (F), and examples of the non-fibrous filler 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 phosphate, magnesium phosphate, hydrotalcite, glass powder, glass spheres, glass flakes, and the like are preferable from the viewpoint of forming a PAS composition excellent in dimensional accuracy and rigidity. In addition, calcium carbonate or glass flakes having an average particle diameter of 2 to 800 μm are preferred from the viewpoint of forming a PAS composition excellent in mechanical strength, impact resistance and flowability. In addition, from the viewpoint of excellent balance of rigidity, dimensional accuracy and fluidity, the total amount of the fibrous filler (C) and the non-fibrous filler (F) is preferably an amount corresponding to 30 to 220 parts by weight relative to 100 parts by weight of the total amount of the PAS (a) and the PCR amide (B).

The PAS composition of the present invention preferably contains the thermoplastic elastomer (G) from the viewpoint of excellent adhesion to a metal member and air tightness, and any thermoplastic elastomer may be used as long as it is generally called a thermoplastic elastomer, and may be a thermoplastic elastomer having a reactive functional group, a thermoplastic elastomer having no reactive functional group, or a mixture of a thermoplastic elastomer having the reactive functional group and a thermoplastic elastomer having no reactive functional group. Examples of the reactive functional group include: examples of the thermoplastic elastomer having the reactive group include epoxy group, maleic anhydride group, carboxylic acid group, amino group, isocyanate group, and the like: ethylene- α, β -unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, ethylene- α, β -unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer, ethylene- α, β -unsaturated carboxylic acid glycidyl ester- α, β -unsaturated carboxylic acid alkyl ester copolymer, maleic anhydride graft modified ethylene- α -olefin copolymer, and other modified ethylene copolymers; examples of the hydrogenated copolymer of the styrene-butadiene-styrene block copolymer include a copolymer obtained by modifying a hydrogenated product of the styrene-butadiene block copolymer with maleic anhydride or a derivative thereof, a copolymer obtained by modifying a hydrogenated product of the styrene-isoprene block copolymer with maleic anhydride or a derivative thereof, and a hydrogenated product of a vinyl aromatic block copolymer such as a copolymer obtained by modifying a hydrogenated product of the styrene-isoprene-styrene block copolymer with maleic anhydride or a derivative thereof, and further include an elastomer having a functional group reactive with a PAS resin: polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, nitrile rubber-based thermoplastic elastomers, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, and the like. Among these, the modified ethylene copolymer is preferable from the viewpoint of forming a PAS composition excellent in toughness.

On the other hand, examples of the thermoplastic elastomer having no reactive functional group include: among the thermoplastic elastomers, thermoplastic elastomers having no functional group are preferred, and among them, olefin-acrylate copolymers are preferred from the viewpoint of forming a PAS composition having an excellent balance between flowability and toughness. Further, examples of the olefin in this case include ethylene and an α -olefin having 3 or more carbon atoms, and examples of the acrylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, and isobutyl acrylate.

The blending amount of the thermoplastic elastomer (G) is preferably 1 to 50 parts by weight relative to 100 parts by weight of the total amount of the PAS (a) and the PCR polyamide (B) from the viewpoint of forming a PAS composition excellent in balance of toughness, adhesion to metal and fluidity.

In addition, from the viewpoint of forming a PAS composition excellent in balance of toughness, adhesion to metal and fluidity and also in heat and cold resistance, PAS (A) is preferably PAS having a melt viscosity of 100 to 2000 poise, and fibrous filler (C) is preferably glass fiber.

The PAS composition of the present invention may be used by mixing various additives within a range not departing from the object of the present invention, and for example, 1 or more conventionally known plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds may be added; an antioxidant; a heat stabilizer; an ultraviolet ray inhibitor; a foaming agent; pigments such as carbon black, and the like. Further, 1 or more kinds of thermosetting resins may be mixed; thermoplastic resins such as cyanate resin, phenolic resin, polyimide, silicone resin, polyester, polyphenylene oxide, polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, polyamideimide, and polyalkylene oxide are used.

As a method for producing the PAS composition of the present invention, a conventionally used method of heating, melting and kneading can be used. Examples include: the method of heat-melting kneading by a single-screw or twin-screw extruder, kneader, mill, brabender or the like is particularly preferably a method of melting kneading by a twin-screw extruder excellent in kneading ability. The screws used in the twin-screw extruder in this case preferably have kneading blocks of 2 or more. Further, from the viewpoint of forming a PAS composition excellent in toughness such as impact resistance by sufficiently making PAS (A) compatible with PCR polyamide (B), it is preferable that the ratio (L/D) of the screw length (L) to the screw diameter (D) is 30 or more, particularly 40 or more.

Further, from the viewpoint of sufficiently improving the compatibility between PAS (A) and PCR polyamide (B) and easily suppressing the thermal decomposition of PCR polyamide (B), the barrel temperature in the kneading zone of the extruder is preferably set to 280℃to 330℃and particularly preferably set to 290℃to 320 ℃. Further, from the viewpoint of improving dispersibility and dispensability of the PCR polyamide in the PAS phase of the PAS composition, and as a result, a PAS composition excellent in toughness such as impact resistance is formed, the peripheral speed of the screw is preferably 50 to 400 mm/sec, and particularly preferably 150 to 300 mm/sec. The residence time of the molten resin in the extruder is preferably 30 seconds to 100 seconds, particularly preferably 30 seconds to 80 seconds, from the viewpoint of sufficiently melting and kneading time of the PAS (A) and the PCR polyamide (B) and easily suppressing thermal decomposition of the polyamide (B).

The PAS composition obtained by melt kneading may be produced into pellets by a method such as hot cutting or spray cutting, or by a method such as cold cutting, and particularly, from the viewpoint that pellets excellent in quality and color can be obtained stably and efficiently, it is preferable to cool the melt kneaded product by a method such as water cooling or air cooling to produce strands, and cut the strands to produce cold or hot cut pellets. The pellets in this case are preferably pellets having a cylindrical shape with a diameter of 0.5 to 2.5mm and a length of 1.5 to 4mm or spherical pellets with a diameter of 1 to 3mm, from the viewpoint of excellent processability in injection molding of various molded articles, and particularly preferably pellets having a light brown or brown color from the viewpoint of obtaining molded articles excellent in product appearance.

The PAS composition of the present invention may be formed into a molded article having any shape using an injection molding machine, an extrusion molding machine, a transfer molding machine, a compression molding machine, a blow molding machine, or the like.

The PAS composition of the present invention can be suitably used as an insert molded article or a metal member-PAS composition member composite excellent in thermal shock resistance and adhesion to a metal. The metal member-PAS composition member complex can be obtained by injection insert molding the PAS composition into a metal member, and the following method is preferable as the injection insert molding, particularly from the viewpoints of excellent bondability and productivity: a PAS composition member is produced by filling a molten PAS composition into a metal member, and the metal member and the PAS composition member are directly integrated.

The melting temperature of the PAS composition at this time is 280 to 340℃and the injection molding machine is preferably used for injection insert molding from the viewpoint of excellent productivity. In particular, from the viewpoint of efficiently producing a metal member-PAS composition member composite excellent in bondability, the mold temperature at the time of insert molding is preferably 130 ℃ or higher, and particularly preferably 140 to 160 ℃. The mold holding pressure is preferably 1MPa or more, particularly preferably 30MPa or more and 100MPa or less.

As a method of roughening the surface of the metal member, a method of physically treating and/or chemically treating the surface is exemplified. Examples of the physical treatment include: a method of bringing fine solid particles into contact with or collision with a surface, a method of irradiating a high-energy electromagnetic wire, and the like, more specifically, there are: sand blasting, liquid honing, laser processing, etc. Further, examples of the polishing agent used in the blasting treatment and the liquid honing treatment include: sand grains, steel grit, steel shot, steel wire (cut wire), aluminum oxide, silicon carbide, metal slag, glass beads, plastic beads, and the like. Further, as the laser processing treatment, there may be mentioned: international publication No. WO2007/072603, japanese patent application laid-open No. 2015-142960, and the like.

Examples of the chemical treatment include: anodic oxidation treatment, chemical treatment with an aqueous acid or alkali solution, and the like. The anodic oxidation treatment may be a method of forming an oxide film on the surface of a metal member by performing an electrochemical reaction in an electrolyte solution using the metal member as an anode, and a method generally known in the art such as plating may be used as an anodic oxidation method. More specifically, examples thereof include: 1) A direct current electrolytic method of applying a constant direct current voltage to perform electrolysis; 2) Bipolar electrolysis in which a voltage is applied to a dc component and an ac component is superimposed to perform electrolysis. Specific examples of the anodic oxidation method include the method proposed in International publication WO 2004/055248. The method of chemically treating the surface of the metal member by immersing the metal member in an aqueous acid or alkali solution may be a method of chemically treating the surface of the metal member by immersing the metal member in an aqueous acid or alkali solution, and examples of the aqueous acid or alkali solution include: phosphoric acid compounds such as phosphoric acid are used; chromic acid-based compounds such as chromic acid; hydrofluoric acid-based compounds such as hydrofluoric acid; nitric acid compounds such as nitric acid; hydrochloric acid compounds such as hydrochloric acid; sulfuric acid compounds such as sulfuric acid; aqueous alkali such as sodium hydroxide and aqueous ammonia; as a more specific example, an aqueous triazine thiol solution, a method of chemically treating an aqueous triazine thiol derivative solution, or the like can be given: japanese patent application laid-open No. 2017-13243, japanese patent application laid-open No. 2019-188651, international publication No. WO2008/133296, japanese patent application No. 5622785, japanese patent application laid-open No. 10-096088, japanese patent application laid-open No. 10-056263, japanese patent application laid-open No. 04-032585, japanese patent application laid-open No. 04-032583, japanese patent application laid-open No. 02-298284, international publication No. WO2009/151099, international publication No. WO2011/104944, and the like.

The metal member may be any material as long as it is in the category of a metal member, and among them, from the viewpoint of being applicable to various applications when a composite with a PAS composition member is produced, it is preferably a metal member which is an aluminum member, an aluminum alloy member, a copper alloy member, a magnesium alloy member, an iron member, a titanium alloy member, or a stainless steel member, it is preferably a metal member which is an aluminum member, an aluminum alloy member, a magnesium alloy member, a titanium member, or a titanium alloy member, and it is more preferably an aluminum member or an aluminum alloy member. The metal member may be a stretched material represented by a plate, a cast material represented by a die cast, or a metal member composed of a forged material.

The PAS composition of the present invention contains a PCR polyamide without impairing the heat resistance, chemical resistance, fluidity and the like inherent in PAS, and is suitably used for applications such as electric/electronic parts and automobile parts, or for construction piping applications such as piping and joints.

Examples

The present invention will be specifically described below by way of examples, but the present invention is not limited to these.

Hereinafter, PAS (A), PCR polyamide (B), fibrous filler (C), compatibilizer (D), release agent (E), non-fibrous filler (F) and thermoplastic elastomer (G) used in examples and comparative examples are shown.

＜PAS(A)＞

Poly (p-phenylene sulfide) (hereinafter, referred to as PPS (a-1)): the melt viscosity was 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)): the melt viscosity was 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)): the melt viscosity was 80 poise.

< PCR Polyamide (B) >)

PCR Polyamide (hereinafter referred to as PCR (B-1)): REFINVERSE (trade name) RA6G00, waste fishing net regenerated polyamide 6 resin.

PCR Polyamide (hereinafter referred to as PCR (B-2)): REFINVERSE (trade name) RA6R00, manufactured by kava corporation, waste fishing net regenerated polyamide 6 resin.

< Polyamide (B') >

Polyamide 6 (B'): and (trade name) 1013B manufactured by yu xiang co.

Fibrous filler (C) >, and method for producing the same

Glass fiber (C-1): manufactured by Nitro Kabushiki Kaisha, (trade name) T-760H: the fiber diameter was 10 μm and the fiber length was 3mm.

Glass fiber (C-2): chopped strands, (trade name) CSG-3PA 830, manufactured by Nitto spinning Co., ltd., aspect ratio of fiber cross section 4.

Compatibilizing agent (D) >, and method of preparing the same

A trialkoxysilane coupling agent (D-1) having a glycidyl group; KBM-403 (trade name) manufactured by Xinyue chemical industries Co., ltd; 3-glycidoxypropyl trimethoxysilane.

Isocyanurate (D-2); manufactured by Tosoh corporation, (trade name) coronateHXR (isocyanate content 21.8%, molecular weight 504).

An epoxy resin (D-3); mitsubishi chemical corporation, (trade name) 1004.

< Release agent (E) >)

A release agent (E-1); manufactured by co-Rong chemical Co., ltd., (trade name) LIGHT AMIDE WH-255.

< Non-fibrous filler (F) >)

Calcium carbonate (F-1); WHITON P-30 (trade name) manufactured by Baishi Industrial Co., ltd; the average particle diameter was 6. Mu.m.

A glass sheet (F-2); manufactured by Nitro Kabushiki Kaisha, (trade name) REFG-301; the average particle diameter was 160. Mu.m.

Thermoplastic elastomer (G) >, thermoplastic elastomer (A)

Ethylene- α, β -unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (G-1) (hereinafter, simply referred to as thermoplastic elastomer (G-1)): SK global chemical, (trade name) BONDINE AX8390, ethylene residue unit: alpha, beta-unsaturated carboxylic acid alkyl ester residue unit: maleic anhydride residue unit (weight ratio) =69.7: 29:1.3.

Ethylene- α, β -unsaturated carboxylic acid glycidyl ester- α, β -unsaturated carboxylic acid alkyl ester copolymer (G-2) (hereinafter referred to as thermoplastic elastomer (G-2)) and (b) as follows: SK global chemical (trade name) LOTADER AX8700, ethylene residue unit: glycidyl ester residue units of α, β -unsaturated carboxylic acids: alpha, beta-unsaturated carboxylic acid alkyl ester residue unit (weight ratio) =67: 8:25.

Synthesis example 1

A50-liter autoclave equipped with a stirrer was charged with 17000g of Na ₂S·2.9H₂ O6214 and 17000g of N-methyl-2-pyrrolidone, gradually warmed to 205℃while stirring under a nitrogen stream, and 1355g of water was distilled off. After the system was cooled to 140 ℃, 7168g of p-dichlorobenzene, 12g of 3, 5-dichloroaniline, and 5000g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen flow. The system was heated to 225℃over 2 hours, polymerized at 225℃for 2 hours, then heated to 250℃over 30 minutes, and polymerized at 250℃for 3 hours. After the polymerization was completed, the mixture was cooled to room temperature, and the solid content was separated by a centrifugal separator. Washing the solid component with hot water at 180deg.C, and drying at 100deg.C for a day and night to obtain PPS.

The obtained PPS was dried under reduced pressure in a vacuum dryer at 240℃for 4 hours to obtain a linear amino group-containing PPS (hereinafter referred to as PPS (A-1)). PPS (A-1) had a melt viscosity of 470 poise.

Synthesis example 2

A50-liter autoclave equipped with a stirrer was charged with 17000g of Na ₂S·2.9H₂ O6214 and 17000g of N-methyl-2-pyrrolidone, gradually warmed to 205℃while stirring under a nitrogen stream, and 1355g of water was distilled off. After the system was cooled to 140 ℃, 7180g of p-dichlorobenzene, 6g of 3, 5-dichloroaniline, and 5000g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen flow. The system was heated to 225℃over 2 hours, polymerized at 225℃for 2 hours, then heated to 250℃over 30 minutes, and polymerized at 250℃for 3 hours. After the polymerization was completed, the mixture was cooled to room temperature, and the solid content was separated by a centrifugal separator. Washing the solid component with hot water at 180deg.C, and drying at 100deg.C for a day and night to obtain PPS.

The obtained PPS was dried under reduced pressure in a vacuum dryer at 240℃for 6 hours to obtain a linear amino group-containing PPS (hereinafter referred to as PPS (A-2)). PPS (A-2) had a melt viscosity of 820 poise.

Synthesis example 3

PPS was obtained by the same polymerization method as in Synthesis example 1, except that 3, 5-dichloroaniline was not used.

The obtained PPS was cured at 250℃for 3 hours under an air atmosphere to obtain branched PPS (hereinafter referred to as PPS (A-3)). PPS (A-3) had a melt viscosity of 1580 poise.

Synthesis example 4

PPS was obtained by the same polymerization method as in synthesis example 2, except that 3, 5-dichloroaniline was not used.

The obtained PPS was cured at 250℃for 6 hours under an air atmosphere to obtain branched PPS (hereinafter referred to as PPS (A-4)). PPS (A-4) had a melt viscosity of 3220 poise.

Synthesis example 5

To a 15-liter autoclave equipped with a stirrer were added Na ₂S·2.9H₂ O1814 g, granular caustic soda (100% NaOH: and Wako pure chemical industries, ltd.) 8.7g and N-methyl-2-pyrrolidone 3232g, and the mixture was gradually warmed to 200℃with stirring under a nitrogen flow, and 339g of water was distilled off. After cooling the system to 190 ℃, 2085g of p-dichlorobenzene and 1783g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen flow. The system was heated to 225℃over 2 hours, polymerized at 225℃for 1 hour, then heated to 250℃over 25 minutes, and polymerized at 250℃for 2 hours. After the polymerization was completed, the mixture was cooled to room temperature, and the solid content was separated by a centrifugal separator. The solid component was washed with hot water at 180℃and dried at 105℃for one day and night, whereby PPS was obtained.

The obtained PPS was dried under reduced pressure in a vacuum dryer at 240℃for 6 hours to obtain a linear PPS (hereinafter referred to as PPS (A-5)). PPS (A-5) had a melt viscosity of 80 poise.

The evaluation/measurement method of the obtained PAS composition is shown below.

Measurement of melt viscosity of PAS

The melt viscosity was measured at a measurement temperature of 315℃under a load of 10kg by using a high-rise rheometer (CFT-500, trade name) equipped with a die having a diameter of 1mm and a length of 2mm, manufactured by Shimadzu corporation.

Measurement of Charpy impact Strength (notched) of PAS composition

Test pieces were prepared by an injection molding machine (manufactured by Sumitomo heavy machinery Co., ltd., (trade name) SE-75S) and measured in accordance with ISO 179-1. The Charpy impact strength of 6kJ/m ² or more is regarded as excellent impact resistance.

Measurement of fluidity of PAS composition

A mold having a groove of 1mm in thickness and 10mm in width was mounted on an injection molding machine (manufactured by Sumitomo heavy machinery industries, ltd., (trade name)) and a PAS composition was then introduced into a hopper of the injection molding machine set at a cylinder temperature of 310℃and an injection pressure of 190MPa, an injection speed of maximum, an injection time of 1.5 seconds and a mold temperature of 135℃and injected. Then, the length of the melt flow in the spiral groove in the mold was measured as the molding fluidity. The fluidity was determined to be excellent when the molding fluidity exceeded 70 mm.

Evaluation of the wet heat resistance of PAS composition

A tensile test piece was produced by an injection molding machine (manufactured by Sumitomo heavy machinery Co., ltd., (trade name) SE-75S), and the tensile strength was measured in accordance with ISO 527-1, 2. The tensile test piece obtained as described above was placed in a constant temperature and humidity tank (manufactured by Hitachi Global Life Solutions, trade name, EC 46-HHP) kept at 85 ℃ and 85% humidity for 2000 hours, and then taken out, and the tensile strength was measured in accordance with ISO 527-1, 2. The wet heat resistance was excellent when the ratio (percentage) of the tensile strength measured after leaving the constant temperature and humidity tank for 2000 hours to the tensile strength measured without placing the tank in the constant temperature and humidity tank was 75% or more.

Evaluation of color tone of PAS composition

A flat plate having a width of 70mm, a length of 70mm and a thickness of 1mm was produced by an injection molding machine (product name: SE-75S, manufactured by Sumitomo heavy mechanical Co., ltd.) to visually observe the appearance. The light brown or brown color is excellent in color tone, and the dark green or dark green color is poor in color tone.

Measurement of flexural modulus of PAS composition

Test pieces were produced by an injection molding machine (manufactured by Sumitomo heavy machinery Co., ltd., (trade name) SE-75S) and measured in accordance with ISO 178. The flexural modulus was set to 15kJ/m ² or more to be excellent in rigidity.

Measurement of the molding shrinkage of PAS composition

A test piece having a thickness of 2mm, a width of 70mm and a length of 70mm was produced by injection molding at a cylinder temperature of 310℃and a mold temperature of 135℃using an injection molding machine (manufactured by Sumitomo heavy mechanical industries, ltd., (trade name) SE-75S). Then, the molded test piece was allowed to stand in a thermostatic chamber adjusted to 23 ℃ x 50% rh for 24 hours, and then the dimensions in the MD direction and the TD direction were measured. Then, the molding shrinkage= (mold size-measured value of test piece)/mold size (percentage) was obtained. The dimensional accuracy was determined to be excellent when the molding shrinkage was less than 0.8%.

Measuring the cold and hot impact resistance

Using an injection molding machine (manufactured by sumitomo heavy machinery industries, trade name) SE-75S, insert molding of 30mm×20mm×10mm rectangular steel (carbon steel) shown in fig. 1 was performed at a cylinder temperature of 310 ℃ and a mold temperature of 140 ℃ to prepare 10 test pieces for evaluating thermal shock resistance of PAS composition coated with a PAS composition having a wall thickness of 1 mm. The obtained 10 test pieces were subjected to a thermal cycle in which the test pieces were cooled to-40 ℃ after being held at 150 ℃ for 30 minutes, and then heated again to 150 ℃ for 1 cycle, and the number of thermal cycles until 6 cracks were visually confirmed among the 10 test pieces was evaluated as thermal shock resistance. The number of the cold and hot cycles exceeding 100 is determined to be excellent in the thermal shock resistance.

Evaluation of the bondability of the resin Member to the Metal Member

A metal plate having a surface subjected to surface treatment was mounted in a mold of an injection molding machine, and a PAS composition was charged into a hopper of the injection molding machine (manufactured by Sumitomo mechanical industries, trade name: SE 75S) and injection insert molded to obtain a shear tensile test piece having a joint area of 50mm ². Next, the joint strength of the joint surface was measured by using the shear tensile test piece according to ISO19095, and evaluated by using the shear tensile strength. Further, the case where the bonding strength was 30MPa or more was determined to be excellent in bonding property.

Example 1

70 Parts by weight of PCR (B-1) was uniformly mixed with 100 parts by weight of PPS (A-1) obtained in Synthesis example 1, and the mixture was fed into a hopper of a twin screw extruder (manufactured by Nippon Steel Co., ltd., (trade name) TEX-25. Alpha. III, L/D=55) having 4 kneading blocks. On the other hand, the glass fiber (C-1) was fed from a hopper of a side feeder of the twin-screw extruder so that the total 100 parts by weight of PPS (A-1) and PCR (B-1) was 70 parts by weight, and the mixture was melt kneaded at a raw material feed rate of 25 kg/hr and a screw rotation rate of 200rpm (peripheral speed: 258 mm/sec) under the condition that the barrel temperature in the kneading zone was heated to 300℃to obtain a PAS composition, after which the PAS molten composition was discharged from the die after a residence time of 50 seconds, cooled by water to obtain strands, and cut to obtain columnar light-brown pellets having a diameter of 1.5mm and a length of 2.5mm, thereby producing the PAS composition.

Then, the PAS composition obtained was put into an injection molding machine (manufactured by Sumitomo mechanical Co., ltd., (trade name) SE 75S) heated to a cylinder temperature of 300℃and a mold temperature of 140℃and the molding flow length of the PAS composition was measured. Subsequently, the charpy impact strength, the color tone and the wet heat resistance were evaluated by using an injection molded test piece. The results of the measurement and evaluation are shown in table 1.

Examples 2 to 10

A pellet-shaped PAS composition was produced in the same manner as in example 1, except that the blending ratio of PPS (a), PCR polyamide (B), fibrous filler (C), compatibilizer (D), and mold release agent (E) was set to the conditions shown in table 1. Then, evaluation was performed in the same manner as in example 1. The evaluation results are shown in Table 1.

The PAS composition obtained is excellent in impact resistance, flowability, wet heat resistance and color tone.

TABLE 1

Comparative examples 1 to 5 and reference example 1

A pellet-shaped resin composition was produced in the same manner as in example 1, except that the blending ratio of PPS (a), PCR polyamide (B), polyamide (B') and fibrous filler (C) was set to the conditions shown in table 2. Then, evaluation was performed in the same manner as in example 1. The evaluation results are shown in Table 2.

The resin composition obtained in comparative example 2 was poor in impact resistance. The resin compositions obtained in comparative examples 1, 4 and 5 were inferior in wet heat resistance. The pellets obtained in comparative example 1, the test pieces, and the test pieces obtained in comparative examples 3, 4, and 5 were inferior in color tone.

TABLE 2

Example 11

PCR (B-1) was homogeneously mixed in advance with respect to 100 parts by weight of PPS (A-1) obtained in Synthesis example 1

35 Parts by weight and 130 parts by weight of calcium carbonate (F-1) were charged into a hopper of a twin screw extruder (manufactured by Nippon Steel Co., ltd., (trade name) TEX-25. Alpha. III, L/D=55) having 4 kneading blocks. On the other hand, glass fiber (C-1) was fed from a hopper of a side feeder of the twin-screw extruder so that 100 parts by weight of PPS (A-1) was used, and the glass fiber was melt kneaded at a raw material feed rate of 25 kg/hr and a screw rotation rate of 200rpm (peripheral speed: 258 mm/sec) under a condition that the barrel temperature in the kneading zone was heated to 320 ℃, and after a residence time of 50 seconds, the molten composition was discharged from the die, cooled with water to prepare strands, and cut to prepare columnar light brown pellets having a diameter of 1.7mm and a length of 2.0mm, to prepare a PAS composition.

Then, the PAS composition obtained was put into an injection molding machine (manufactured by Sumitomo mechanical Co., ltd., (trade name) SE 75S) heated to a cylinder temperature of 310℃and a mold temperature of 140℃and the molding flow length of the PAS composition was measured. Next, flexural modulus, dimensional change rate, color tone, and wet heat resistance were evaluated using an injection molded test piece. The results of the measurement and evaluation are shown in table 3.

Examples 12 to 20

A pellet-shaped PAS composition was produced in the same manner as in example 11, except that the blending ratio of PPS (a), PCR polyamide (B), fibrous filler (C), non-fibrous filler (F), compatibilizer (D) and release agent (E) was set to the conditions shown in table 3. Then, evaluation was performed in the same manner as in example 11. The evaluation results are shown in Table 3.

All PAS compositions obtained were excellent in rigidity, dimensional accuracy, wet heat resistance, fluidity and color tone.

TABLE 3

Comparative examples 6 to 13 and reference example 2

A pellet-shaped resin composition was produced in the same manner as in example 11, except that the blending ratio of PPS (a), PCR polyamide (B), polyamide (B'), fibrous filler (C), and non-fibrous filler (F) was set to the conditions shown in table 4. Then, evaluation was performed in the same manner as in example 11. The evaluation results are shown in Table 4.

The resin compositions obtained in comparative examples 8, 9, 10, 11 and 13 were inferior in rigidity. The dimensional accuracy of the resin compositions obtained in comparative examples 7, 9 and 11 was poor. The resin composition obtained in comparative example 6 was poor in wet heat resistance. The resin compositions obtained in comparative examples 6,7, 10 and 12 were poor in fluidity. The test pieces obtained in comparative examples 6, 9 and 11 were inferior in hue.

TABLE 4

Example 21

The aluminum alloy (A5052) sheet (50 mm. Times.10 mm. Times.1 mm thickness) was immersed in a degreasing bath containing an aqueous solution (liquid temperature: 60 ℃ C.) containing 7.5% of a degreasing agent for aluminum for 5 minutes, and then washed with ion-exchanged water. Then, the solution was immersed in a tank containing an aqueous solution (liquid temperature: 40 ℃ C.) containing 1.5% caustic soda for 1 minute, washed with ion-exchanged water, and further immersed in a tank containing an aqueous solution (liquid temperature: 40 ℃ C.) containing 3% nitric acid for 1 minute, and washed with ion-exchanged water. Then, the sheet was immersed in a bath containing an aqueous solution containing 3.5% hydrazine hydrate (liquid temperature: 60 ℃ C.) for 1 minute, washed with ion-exchanged water, immersed in a bath containing an aqueous solution containing 0.5% hydrazine hydrate (liquid temperature: 33 ℃ C.) for 3 minutes, washed with ion-exchanged water, and dried in a warm air dryer to obtain a surface-roughened aluminum alloy (A5052) sheet.

PCR (B-1) was homogeneously mixed in advance with respect to 100 parts by weight of PPS (A-1) obtained in Synthesis example 1

30 Parts by weight and 15 parts by weight of the thermoplastic elastomer (G-1) were charged into a hopper of a twin screw extruder (manufactured by Nippon Steel Co., ltd., (trade name) TEX-25. Alpha. III, L/D=55) having 4 kneading blocks. On the other hand, the glass fiber (C-1) was fed from a hopper of a side feeder of the twin-screw extruder so as to be 40 parts by weight relative to 100 parts by weight of PPS (A-1), and the mixture was melt kneaded at a raw material feeding speed of 25 kg/hr and a screw rotation speed of 200rpm (peripheral speed: 258 mm/sec) under a condition that the barrel temperature in the kneading zone was heated to 310℃to leave the molten composition in a mold for 50 seconds, and the molten composition was cooled by water to prepare strands, and then cut to prepare a columnar and pale brown pellet-like PAS composition having a diameter of 1.7mm and a length of 2.3 mm.

Then, the PAS composition obtained was put into an injection molding machine (manufactured by Sumitomo mechanical Co., ltd., (trade name) SE 75S) heated to a cylinder temperature of 310℃and a mold temperature of 140℃and the molding flow length of the PAS composition was measured. Further, the surface roughened aluminum alloy sheet was mounted in a mold, and the PAS composition was insert molded, whereby an aluminum alloy member-PAS composition member composite was obtained as a shear tensile test piece having a joint area of 50mm ². Further, the test piece formed by injection molding and injection insert molding was used to evaluate the thermal shock resistance and wet heat resistance and to measure the bonding strength. The color tone of the test piece was also confirmed. The results of the respective measurements and evaluations are shown in Table 5.

Examples 22 to 29

A granular PAS composition was produced in the same manner as in example 21, except that PPS (a), PCR polyamide (B), glass fiber (C), thermoplastic elastomer (G), compatibilizer (D), and mold release agent (E) were mixed under the conditions shown in table 5. The PAS composition obtained has a pale brown or brown hue. Then, a metal member-PAS composition member complex was produced in the same manner as in example 21, and those evaluations were performed. The evaluation results are shown in Table 5.

The PAS composition obtained has excellent thermal shock resistance, adhesion to metal, wet heat resistance, fluidity and color tone.

TABLE 5

Comparative examples 14 to 18 and reference example 3

A pellet-shaped resin composition was produced in the same manner as in example 21, except that the blending ratio of PPS (a), PCR polyamide (B), polyamide (B'), glass fiber (C), and thermoplastic elastomer (G) was set to the conditions shown in table 6. Then, a composite was produced in the same manner as in example 21, and those evaluations were performed. The evaluation results are shown in Table 6.

The resin compositions obtained in comparative examples 14, 15, 17 and 18 were inferior in thermal shock resistance. The resin compositions obtained in comparative examples 14 to 18 were poor in adhesion to metals. The resin compositions obtained in comparative examples 16 and 18 were inferior in wet heat resistance. The resin compositions obtained in comparative examples 14 and 16 were inferior in color tone.

TABLE 6

The entire contents of the claims, the specification, the drawings, and the abstract of japanese patent application No. 2021-170620, japanese patent application No. 2021-170621, and japanese patent application No. 2021-170623, which are filed on even date 19 in 10 of 2021, are incorporated herein by reference as the disclosure of the specification of the present invention.

Industrial applicability

The PAS composition of the present invention contains a PCR polyamide without impairing the heat resistance, chemical resistance, fluidity and the like inherent in PAS, and is particularly useful for applications such as electric/electronic parts, automobile parts and the like, and applications such as construction piping and joint and the like.

Description of the reference numerals

1: Gate position.

2: And a through hole.

3: And embedding the blocks.

4: Weld formation locations.

Claims (10)

1. A polyarylene sulfide composition comprising 10 to 90 parts by weight of a post-consumer recycled polyamide (B) per 100 parts by weight of a polyarylene sulfide (A), and 20 to 110 parts by weight of a fibrous filler (C) per 100 parts by weight of the total amount of the polyarylene sulfide (A) and the post-consumer recycled polyamide (B), wherein the polyarylene sulfide (A) has a melt viscosity of 100 to 3000 poise measured by a high-pressure rheometer equipped with a die having a diameter of 1mm and a length of 2mm and under conditions of a measured temperature of 315 ℃ and a load of 10 kg.

2. Polyarylene sulfide composition according to claim 1, wherein polyarylene sulfide (a) is a regenerated polyarylene sulfide.

3. The polyarylene sulfide composition according to claim 1 or 2, wherein the post-consumer recycled polyamide (B) is a post-consumer recycled polyamide obtained by collecting and/or recycling at least 1 or more selected from the group consisting of fishing nets, ropes, carpets, mats.

4. The polyarylene sulfide composition according to any one of claims 1 to 3, further comprising a compatibilizer (D) selected from at least 1 or more of isocyanurate, epoxy resin, and silane coupling agent, and/or a mold release agent (E) selected from at least 1 or more of polyethylene wax, polypropylene wax, and fatty acid amide-based wax.

5. The polyarylene sulfide composition according to any one of claims 1 to 4, further comprising a non-fibrous filler (F).

6. The polyarylene sulfide composition according to any one of claims 1 to 5, wherein polyarylene sulfide (a) is a polyarylene sulfide having a melt viscosity of 100 to 2000 poise, the fibrous filler (C) is a glass fiber, and the polyarylene sulfide composition further comprises a thermoplastic elastomer (G).

7. A process for producing the polyarylene sulfide composition according to any one of claims 1 to 6, wherein at least the polyarylene sulfide resin (A), the post-consumer recycled polyamide (B) and the fibrous filler (C) are melt kneaded and extruded under kneading conditions in which the barrel temperature in the kneading zone is 280 to 330 ℃, the peripheral speed of the screw is 50 to 400 mm/sec, and the residence time is 30 to 100 seconds, by using a twin-screw extruder having a screw with a screw length (L) to screw diameter (D) ratio (L/D) of 30 or more and a kneading zone of 2 or more.

8. A pellet comprising the polyarylene sulfide composition according to any one of claims 1 to 6, wherein the pellet has a cylindrical shape having a diameter of 0.5 to 2.5mm and a length of 1.5 to 4mm or a spherical shape having a diameter of 1 to 3 mm.

9. The pellet of claim 8 having a light brown or brown hue.

10. Pellet according to claim 8 or 9, characterized in that it is a cold cut pellet.