Poly(arylene sulfide) resin composition for recycle materials

Abstract

Provided is a poly(arylene sulfide) resin composition which, during recycling, can be inhibited from forming burrs. The poly(arylene sulfide) resin composition (X) for recycle materials comprises (A) 100 parts by mass of a linear poly(arylene sulfide) resin having a carboxy group and (B) 0.3-10 parts by mass of an alkoxysilane compound.

Description

Polyarylene sulfide resin composition for recycled materials

[0001] The present disclosure relates to a polyarylene sulfide resin composition for recycled materials.

[0002] Technologies for recycling and utilizing plastic waste are being investigated to build a sustainable recycling-based society. Polyarylene sulfide resins, typified by polyphenylene sulfide resins, are widely used in electrical and electronic equipment component materials, automotive component materials, chemical equipment component materials, and the like, due to their excellent heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame retardancy. Therefore, recycling and utilizing materials containing polyarylene sulfide resins can help build a sustainable recycling-based society. However, polyarylene sulfide resins have a problem in that flash is frequently generated during injection molding, even when virgin pellets that have never undergone a molding process are used (see, for example, Patent Document 1).

[0003] Japanese Patent Application Laid-Open No. 2006-45451

[0004] When recycling materials containing polyarylene sulfide resins, molded products or items discharged after a long residence time in a cylinder during molding (hereinafter collectively referred to as "recycled products") are crushed and used as recycled material, and if necessary, further re-pelletized and then injection molded again. However, the recycled material may have decomposed matrix polymers, deteriorated additives, and pulverized fillers due to shearing during crushing of the recycled products and thermal history caused by undergoing one or more molding processes. In such cases, flash formation is more pronounced than when virgin pellets that have not undergone a molding process are injection molded.

[0005] An object of the present disclosure is to provide a polyarylene sulfide resin composition that can suppress the generation of burrs during recycling.

[0006] The present disclosure includes the following aspects: (1) A polyarylene sulfide resin composition (X) for recycled materials, comprising (A) 100 parts by mass of a linear polyarylene sulfide resin having a carboxy group, and (B) 0.3 to 10 parts by mass of an alkoxysilane compound. (2) A recycled material (R) of a polyarylene sulfide resin composition comprising (A) 100 parts by mass of a polyarylene sulfide resin having a carboxy group, and (B) 0.3 to 10 parts by mass of an alkoxysilane compound. (3) A method for producing a repellet material, comprising: obtaining a pulverized product of a molded product of the polyarylene sulfide resin composition (X) comprising (A) 100 parts by mass of a polyarylene sulfide resin having a carboxy group and (B) 0.3 to 10 parts by mass of an alkoxysilane compound; and melt-kneading the pulverized product at 260 to 380°C to obtain a repellet material.

[0007] According to the present disclosure, it is possible to provide a polyarylene sulfide resin composition that can suppress the generation of burrs during recycling.

[0008] An embodiment of the present disclosure will be described in detail below. However, the scope of the present disclosure is not limited to the embodiment described herein, and various modifications can be made without departing from the spirit of the present disclosure. Each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Furthermore, when multiple upper and lower limit values ​​are described for a specific parameter, any of these upper and lower limit values ​​can be combined to form a suitable numerical range. Furthermore, the lower and / or upper limit values ​​of a numerical range described in this disclosure are numerical values ​​within that numerical range and may be replaced with numerical values ​​shown in the examples. The expression "X to Y" indicating a numerical range means "X or more and Y or less." If a specific description described for one embodiment also applies to other embodiments, that description may be omitted in other embodiments.

[0009] [Polyarylene sulfide resin composition (X)] The polyarylene sulfide resin composition (X) according to the present disclosure (hereinafter also simply referred to as "resin composition (X)") is a polyarylene sulfide resin composition (X) for recycled materials, and contains (A) 100 parts by mass of a linear polyarylene sulfide resin having a carboxy group, and (B) 0.3 to 10 parts by mass of an alkoxysilane compound. The "polyarylene sulfide resin composition" means a composition containing a polyarylene sulfide resin.

[0010] Among polyarylene sulfide resins, linear polyarylene sulfide resins without branches in their chemical structure are prone to main chain decomposition and molecular weight reduction when heated and melted during pelletization or molding processes. Therefore, when an article containing linear polyarylene sulfide resin is crushed and re-injected into injection molding or other processes as recycled material, it is more likely to produce longer burrs than when virgin pellets that have never undergone a molding process are used. On the other hand, branched polyarylene sulfide resins with branches in their chemical structure tend to maintain their high molecular weight even when heated, which is expected to reduce burrs during molding. Therefore, a small amount of ultrahigh molecular weight gel-like branched polyarylene sulfide resin, which more easily maintains its high molecular weight, is sometimes added to linear polyarylene sulfide resins as a burr suppressant. However, even when branched polyarylene sulfide resins are added as a burr suppressant, it was found that although burrs were suppressed in injection-molded virgin materials, burrs increased when the material was crushed after one molding process and then re-injection-molded. Therefore, the present inventors conducted extensive research into polyarylene sulfide resin compositions that can suppress burrs even during recycling. The present inventors were surprised to discover that by incorporating a predetermined amount of (B) an alkoxysilane compound into (A) a linear polyarylene sulfide resin having carboxy groups, burrs can be suppressed even when the resin is pulverized after a molding process and then injection-molded again, thereby completing the present invention. The mechanism behind this is unclear at this stage, but a non-limiting mechanism is thought to be that by incorporating a predetermined amount of alkoxysilane compound, when the polyarylene sulfide resin is heated and melted during the re-pelletizing process or the injection molding process during recycling, the main chain of the polyarylene sulfide resin is decomposed while the reaction between the carboxy groups of the polyarylene sulfide resin and the alkoxysilane compound proceeds, thereby increasing the degree of crosslinking of the polyarylene sulfide resin. It is believed that increasing the degree of crosslinking of the polyarylene sulfide resin increases or maintains the molecular weight of the polyarylene sulfide resin, thereby suppressing burrs.

[0011] "Recycled material" means a material obtained by crushing an article such as a molded body (a recycled product) and regenerating it as a material for use in manufacturing a molded body. The term "recycled material of a polyarylene sulfide resin composition" can include crushed material of an article containing a polyarylene sulfide resin composition, repelletized material obtained by repelletizing the crushed material, and the like. "For recycled material" means that the material is used to manufacture recycled material.

[0012] In contrast, raw materials that are not used in the production of molded bodies (raw materials that have not undergone a molding process) are sometimes called "virgin materials," virgin materials of polyarylene sulfide resins are sometimes called "virgin polyarylene sulfide resins," and virgin materials of polyarylene sulfide resin compositions are sometimes called "virgin polyarylene sulfide resin compositions."

[0013] (A) Linear Polyarylene Sulfide Resin Having Carboxy Group) The polyarylene sulfide resin is a resin having a repeating unit represented by the following general formula (I): -(Ar-S)- (I) (where Ar represents an arylene group).

[0014] The arylene group is not particularly limited, but examples thereof include a p-phenylene group, an m-phenylene group, an o-phenylene group, a substituted phenylene group, a p,p'-diphenylene sulfone group, a p,p'-biphenylene group, a p,p'-diphenylene ether group, a p,p'-diphenylene carbonyl group, and a naphthalene group.

[0015] The polyarylene sulfide resin can be a homopolymer using the same repeating unit represented by the general formula (I) above, or a copolymer containing different repeating units. A preferred homopolymer has a p-phenylene group as the arylene group, that is, a p-phenylene sulfide group as the repeating unit. This is because homopolymers having a p-phenylene sulfide group as the repeating unit have extremely high heat resistance and exhibit high strength, high rigidity, and high dimensional stability over a wide temperature range. By using such homopolymers, molded articles with excellent physical properties can be obtained.

[0016] As the copolymer, a combination of two or more different arylene sulfide groups among the above-mentioned arylene group-containing arylene sulfide groups can be used. Among these, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is preferred from the viewpoint of obtaining a molded product with high physical properties such as heat resistance, moldability, and mechanical properties. A polymer containing 70 mol% or more of p-phenylene sulfide groups is more preferred, and a polymer containing 80 mol% or more is even more preferred. The polyarylene sulfide resin containing phenylene sulfide groups is a polyphenylene sulfide resin (PPS resin).

[0017] Polyarylene sulfide resins are generally known to have a substantially linear molecular structure without branching or crosslinking (hereinafter referred to as "straight-chain"), or a structure with branching or crosslinking (hereinafter referred to as "branched"), depending on the production method. The polyarylene sulfide resin composition (X) for recycled materials according to the present disclosure contains at least (A) a linear polyarylene sulfide resin having a carboxy group.

[0018] By including (A) a linear polyarylene sulfide resin having a carboxy group, the carboxy group reacts with (B) an alkoxysilane compound described below when the resin is re-pelletized and / or re-injection molded, thereby suppressing the generation of burrs during recycling. The presence of a carboxy group in the linear polyarylene sulfide resin can be confirmed by FT-IR measurement.

[0019] The carboxy group content in the (A) linear polyarylene sulfide resin having carboxy groups is preferably 5 to 100 μmol / g, more preferably 7 to 70 μmol / g, and even more preferably 10 to 50 μmol / g. By having the carboxy group content in the (A) linear polyarylene sulfide resin having carboxy groups be 5 to 100 μmol / g, the reaction with the (B) alkoxysilane compound described below can proceed more easily, and the generation of burrs during recycling can be more easily suppressed.

[0020] The amount of carboxy groups can be measured as follows. That is, by FT-IR measurement, the peak heights of the absorption peak of the benzene ring of benzoic acid and the absorption peak of the carboxy group are measured, and the relative intensity of the absorption peak of the carboxy group to the C-H bond of the benzene ring is measured. From the relative intensity, the content (mol %) of carboxy groups relative to the benzene ring is determined. The amount of carboxy groups contained in 1 kg of resin composition is calculated from the amount of repeating units -(Ar-S)- (Ar is a benzene ring) contained in 1 kg of resin composition.

[0021] The method for producing the linear polyarylene sulfide resin (A) having a carboxy group can be, for example, polymerizing the linear polyarylene sulfide resin using a monomer that can constitute the above-mentioned structural unit, and then washing with an acidic aqueous solution of appropriate acidity.In this case, the acid used as the acidic aqueous solution can be inorganic acids such as hydrochloric acid, sulfuric acid, ammonium chloride, etc.; saturated fatty acids such as acetic acid, formic acid, propionic acid, butyric acid, valeric acid, caproic acid, etc.; unsaturated fatty acids such as acrylic acid, crotonic acid, oleic acid, etc.; aromatic carboxylic acids such as benzoic acid, phthalic acid, salicylic acid, etc.; dicarboxylic acids such as oxalic acid, maleic acid, fumaric acid, etc.; methanesulfonic acid, paratoluenesulfonic acid, etc., among which hydrochloric acid, acetic acid, and ammonium chloride are preferred.In addition, before and after washing with the acidic aqueous solution, if necessary, washing with an organic solvent such as acetone or water can be used.

[0022] Another example of a method for producing (A) a linear polyarylene sulfide resin having a carboxy group includes a method of polymerizing a linear polyarylene sulfide resin using a monomer having a carboxy group as a monomer capable of constituting the structural unit. In this case, too, washing with an acidic aqueous solution of appropriate acidity after polymerization is preferred. For example, a method of polymerizing using, as a monomer, one or more monomers having one or more carboxy groups selected from p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p,p'-diphenylene sulfone group, p,p'-biphenylene group, p,p'-diphenylene ether group, p,p'-diphenylenecarbonyl group, and naphthalene group is included.

[0023] The polyarylene sulfide resin composition (X) for recycled materials may contain a linear polyarylene sulfide resin other than the linear polyarylene sulfide resin having a carboxy group (A), or may contain a branched polyarylene sulfide resin. In one embodiment, from the viewpoint of increasing the reactivity with the alkoxysilane compound (B), from the viewpoint of easily obtaining a molded product having an excellent appearance, and / or from the viewpoint of preventing a decrease in moldability due to the addition of the alkoxysilane compound (B), the content of the linear polyarylene sulfide resin having a carboxy group (A) in the total amount (100% by mass) of the polyarylene sulfide resin contained in the polyarylene sulfide resin composition for recycled materials (X) is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 98% by mass or more. In one embodiment, the polyarylene sulfide resin contained in the polyarylene sulfide resin composition (X) for recycled materials preferably consists solely of (A) a linear polyarylene sulfide resin having a carboxy group.

[0024] The content of (A) linear polyarylene sulfide resin having carboxy groups in the resin component (100% by mass) contained in the polyarylene sulfide resin composition (X) for recycled materials is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 98% by mass or more. In one embodiment, the resin component contained in the polyarylene sulfide resin composition (X) for recycled materials preferably consists solely of (A) linear polyarylene sulfide resin having carboxy groups.

[0025] The content of (A) linear polyarylene sulfide resin having carboxy groups in the polyarylene sulfide resin composition (X) (100% by mass) for recycled materials is preferably 30% by mass or more, more preferably 35% by mass or more. In one embodiment, from the viewpoint of further shortening the burr length during recycling, the content of (A) linear polyarylene sulfide resin having carboxy groups in the polyarylene sulfide resin composition (X) (100% by mass) for recycled materials is preferably 30 to 50% by mass, more preferably 35 to 45% by mass. In another embodiment, from the viewpoint of further suppressing the generation of burrs compared to injection-molded articles made from virgin materials, the content of (A) linear polyarylene sulfide resin having carboxy groups in the polyarylene sulfide resin composition (X) (100% by mass) for recycled materials is preferably 50% by mass or more, more preferably more than 50% by mass, and even more preferably 55 to 70% by mass.

[0026] The melt viscosity of the polyarylene sulfide resin composition (X) for recycled materials is preferably 20 to 600 Pa·s, more preferably 50 to 500 Pa·s, and even more preferably 100 to 400 Pa·s, from the viewpoint of improving moldability and toughness.

[0027] The temperature-decreasing crystallization temperature (Tc) of the (A) linear polyarylene sulfide resin having a carboxy group is preferably 215°C or higher, more preferably greater than 215°C, even more preferably 216°C or higher, still more preferably 217°C or higher, and particularly preferably 218°C or higher. The temperature-decreasing crystallization temperature (Tc) of the (A) polyarylene sulfide resin is 215°C or higher, thereby enabling the impact strength of the molded article to be further increased. The upper limit of the temperature-decreasing crystallization temperature (Tc) of the (A) polyarylene sulfide resin is preferably 260°C or lower, more preferably 250°C or lower, and particularly preferably 240°C or lower.

[0028] The temperature-decreasing crystallization temperature (Tc) is defined as the exothermic peak temperature associated with crystallization observed when (A) a linear polyarylene sulfide resin having a carboxy group is heated to 340°C by a differential scanning calorimeter to melt the resin, and then cooled at a rate of 10°C / min.

[0029] Methods for increasing the temperature-decreasing crystallization temperature (Tc) of the (A) linear polyarylene sulfide resin having carboxy groups include, but are not limited to, a method of adjusting the molecular weight of the (A) linear polyarylene sulfide resin having carboxy groups, and a method of washing the polymer after polymerization with an acidic aqueous solution of appropriate acidity. In this case, examples of the acid used as the acidic aqueous solution include those described in the above-mentioned method for introducing carboxy groups. When the molecular weight of the (A) linear polyarylene sulfide resin having carboxy groups is low, the temperature-decreasing crystallization temperature (Tc) tends to be high. Therefore, when the temperature-decreasing crystallization temperature (Tc) is too low, the temperature-decreasing crystallization temperature (Tc) can be increased by blending a (A) linear polyarylene sulfide resin having carboxy groups with a low molecular weight.

[0030] ((B) Alkoxysilane Compound) The polyarylene sulfide resin composition (X) for recycled materials contains (B) an alkoxysilane compound. By containing the (B) alkoxysilane compound, it is possible to obtain a polyarylene sulfide resin composition that can suppress the generation of burrs during recycling.

[0031] The alkoxysilane compound (B) preferably contains one or more alkoxysilane compounds having one or more groups selected from an epoxy group, an amino group, a vinyl group, a (meth)acrylic group, an isocyanate group, and a mercapto group.

[0032] In one embodiment, the alkoxysilane compound (B) is preferably represented by the following formula (II): １ ｎ Si(OR ２ ) ４－ｎ (II) In formula (II), R １ is an alkyl group having 1 to 18 (preferably 1 to 10) carbon atoms and having an epoxy group, an amino group, a vinyl group, a (meth)acrylic group, an isocyanate group, or a mercapto group, and R ２ is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3.

[0033] Examples of the alkoxysilane compound (B) include alkoxysilanes such as epoxyalkoxysilanes, aminoalkoxysilanes, vinylalkoxysilanes, (meth)acrylicalkoxysilanes, isocyanatealkoxysilanes, and mercaptoalkoxysilanes, and it is preferable to include one or more of these. The number of carbon atoms in the alkoxy group is preferably 1 to 10, and particularly preferably 1 to 4.

[0034] Examples of epoxyalkoxysilanes include γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane.

[0035] Examples of aminoalkoxysilanes include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane, and γ-diallylaminopropyltriethoxysilane.

[0036] Examples of vinylalkoxysilanes include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(β-methoxyethoxy)silane.

[0037] Examples of (meth)acrylalkoxysilanes include γ-acryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropylmethyldiethoxysilane.

[0038] Examples of the isocyanate alkoxysilane include γ-isocyanate propyl triethoxysilane and γ-isocyanate propyl trimethoxysilane.

[0039] Examples of mercaptoalkoxysilanes include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

[0040] Of these, epoxyalkoxysilane and aminoalkoxysilane are more preferred, and γ-aminopropyltriethoxysilane is particularly preferred.

[0041] The content of the (B) alkoxysilane compound is 0.3 to 10 parts by mass, preferably 0.6 to 8 parts by mass, and more preferably 0.7 to 4.5 parts by mass, per 100 parts by mass of the (A) linear polyarylene sulfide resin having a carboxy group. By having the (B) alkoxysilane compound content of 0.3 to 10 parts by mass per 100 parts by mass of the (A) linear polyarylene sulfide resin having a carboxy group, a polyarylene sulfide resin composition can be obtained that can suppress the generation of burrs during recycling. Furthermore, a polyarylene sulfide resin composition that has excellent moldability during recycling can be obtained.

[0042] In one embodiment, from the viewpoint of further shortening the length of burrs generated during recycling, the content of the (B) alkoxysilane compound is preferably more than 1.0 part by mass and not more than 10 parts by mass, more preferably 1.1 to 4.5 parts by mass, even more preferably 1.3 to 2.0 parts by mass, and particularly preferably 1.4 to 1.8 parts by mass, relative to 100 parts by mass of the (A) linear polyarylene sulfide resin having a carboxy group.

[0043] In another embodiment, from the viewpoint of further suppressing the generation of burrs compared to virgin material, the content of the (B) alkoxysilane compound is preferably 0.3 to 1.4 parts by mass, more preferably 0.6 to 1.3 parts by mass, even more preferably 0.7 to 1.2 parts by mass, and particularly preferably 0.8 to 1.1 parts by mass relative to 100 parts by mass of the (A) linear polyarylene sulfide resin having a carboxy group.

[0044] (C) Inorganic Filler The polyarylene sulfide resin composition (X) for recycled materials preferably contains (C) an inorganic filler. By containing (C) an inorganic filler, the mechanical strength of a recycled product obtained by injection molding the recycled material can be increased.

[0045] Examples of the inorganic filler (C) include a fibrous inorganic filler (C1), a plate-like inorganic filler (C2), and a particulate inorganic filler (C3), and it is preferable to include at least one selected from these.

[0046] Examples of the (C1) fibrous inorganic filler include glass fiber, carbon fiber, zinc oxide fiber, titanium oxide fiber, wollastonite, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel fiber, aluminum fiber, titanium fiber, copper fiber, brass fiber, etc. The (C1) fibrous inorganic filler may be used alone or in combination of two or more.

[0047] Examples of the plate-like inorganic filler (C2) include mica, glass flakes, talc (plate-like), mica, kaolin, clay, alumina (plate-like), various metal foils, etc. The plate-like inorganic filler (C2) may be used alone or in combination of two or more.

[0048] Examples of the (C3) granular inorganic filler include carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloons, glass powder, talc (granular), silicates such as calcium silicate, aluminum silicate, and diatomaceous earth, metal oxides such as iron oxide, titanium oxide, zinc oxide, and alumina (granular), metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, silicon carbide, silicon nitride, boron nitride, and various metal powders. The (C3) granular inorganic filler may be used alone or in combination of two or more.

[0049] In one embodiment, the (C) inorganic filler preferably contains a (C1) fibrous inorganic filler, from the viewpoint of easily increasing the impact strength of recycled products obtained by injection molding the recycled material. Examples of the (C1) fibrous inorganic filler include (C1a) a fibrous inorganic filler having a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of 3.0 or more (hereinafter simply referred to as "(C1a) fibrous inorganic filler"), and (C1b) a fibrous inorganic filler having a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of less than 3.0, less than 2.0, or 1.5 or less (hereinafter simply referred to as "(C1b) fibrous inorganic filler").

[0050] The "major axis of a cross section perpendicular to the longitudinal direction" is the longest linear distance in a cross section perpendicular to the longitudinal direction of the fiber, and the "minor axis of a cross section perpendicular to the longitudinal direction" is the longest linear distance in a direction perpendicular to the major axis of the cross section. The diameter difference ratio refers to the diameter difference ratio of the initial shape (shape before melt-kneading). The diameter difference ratio can be calculated using a scanning electron microscope and image processing software, and is the arithmetic average value measured for 10 (C1a) fibrous inorganic fillers. The diameter difference ratio can also be the manufacturer's value (a value published by the manufacturer in a catalog, etc.).

[0051] In one embodiment, the inorganic filler (C) preferably includes, as the fibrous inorganic filler (C1), a fibrous inorganic filler (C1a) having a diameter ratio, which is the ratio of the major axis to the minor axis of a cross section perpendicular to the longitudinal direction, of 3.0 or more. When the polyarylene sulfide resin composition (X) for recycled material includes the fibrous inorganic filler (C1a), the impact strength of a recycled product obtained by injection molding the recycled material can be increased.

[0052] The diameter ratio of the fibrous inorganic filler (C1a) is 3.0 or more, preferably 3.5 or more, more preferably 3.8 or more. The upper limit of the diameter ratio is 10.0 or less, preferably 8.0 or less, more preferably 6.0 or less.

[0053] Examples of the fibrous inorganic filler (C1a) include fibrous inorganic fillers whose cross-sectional shape perpendicular to the longitudinal direction of the fiber is oval, semicircular, cocoon-shaped (an oval shape with a portion of the longitudinal direction recessed inward), rectangular, or similar shapes.

[0054] The major axis of the cross section perpendicular to the longitudinal direction of the (C1a) fibrous inorganic filler is preferably 10 to 40 μm, more preferably 20 to 30 μm. The minor axis of the cross section perpendicular to the longitudinal direction of the (C1a) fibrous inorganic filler is preferably 1 to 20 μm, more preferably 3 to 10 μm. The major axis and minor axis of the cross section perpendicular to the longitudinal direction can both be calculated using a scanning electron microscope and image processing software, and are the arithmetic average values ​​measured for 10 pieces of (C1a) fibrous inorganic filler. In addition, the major axis and minor axis of the cross section perpendicular to the longitudinal direction can both be manufacturer values ​​(values ​​published by the manufacturer in a catalog, etc.).

[0055] In one embodiment, the content of (C1a) fibrous inorganic filler in the inorganic filler (C), which has a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of 3.0 or more, is preferably 50 to 100 mass%, more preferably 80 to 100 mass% or more, and even more preferably 90 to 100 mass% or more, based on the total amount (100 mass%) of the inorganic filler (C). In one embodiment, the inorganic filler (C) can be configured to consist solely of (C1a) fibrous inorganic filler in which a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of 3.0 or more.

[0056] From the viewpoint of further increasing the impact strength of recycled products obtained by injection molding recycled materials, the average fiber length of the (C1) fibrous inorganic filler is preferably 0.01 to 3.5 mm, more preferably 0.05 to 3.5 mm, even more preferably 0.1 to 3.5 mm, and particularly preferably 0.5 to 3 mm, as the average fiber length (cut length) before melt-kneading into the resin composition. The average fiber length can be calculated using a scanning electron microscope and image processing software, and is the arithmetic average value measured for 1,000 pieces of (C1) fibrous inorganic filler. The average fiber length can also be determined by the manufacturer (a value published by the manufacturer in a catalog, etc.).

[0057] The cross-sectional area of ​​the fibrous inorganic filler (C1) is 1 × 10 in terms of ease of production. －５ ~1 x 10 －３ mm ２ It is preferable that the －４ ~5 x 10 －４ mm ２ The "cross-sectional area" can be calculated by multiplying the value obtained by dividing the longest linear distance of the cross section of the fibrous inorganic filler (C1) measured using a scanning electron microscope and image processing software, where the longest linear distance is the major axis and the shortest linear distance is the minor axis, by the value obtained by dividing the major axis by 2 and the value obtained by dividing the minor axis by 2, and then multiplying the result by pi. The cross-sectional area is the arithmetic average value measured for 10 pieces of fibrous inorganic filler (C1).

[0058] The (C) inorganic filler may be surface-treated with various commonly known surface treatment agents such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, and fatty acids. Surface treatment can improve adhesion to the (A) linear polyarylene sulfide resin having a carboxy group. The surface treatment agent may be applied to the (C) inorganic filler in advance to perform surface treatment or convergence treatment before preparing the material, or may be added simultaneously during material preparation. When the (C) inorganic filler has been surface-treated with an alkoxysilane compound, the content of the (B) alkoxysilane compound described above does not include the content of the alkoxysilane compound derived from the surface treatment agent.

[0059] From the viewpoint of making it easier to increase the mechanical strength of recycled products obtained by injection molding recycled materials, the content of the (C) inorganic filler is preferably 30 to 250 parts by mass, more preferably 35 to 200 parts by mass, even more preferably 38 to 180 parts by mass, and particularly preferably 40 to 160 parts by mass, relative to 100 parts by mass of the (A) polyarylene sulfide resin having carboxy groups.

[0060] In one embodiment, from the viewpoint of increasing the mechanical strength while easily shortening the length of burrs generated during recycling, the content of the inorganic filler (C) is preferably 90 to 250 parts by mass, more preferably 100 to 200 parts by mass, even more preferably 120 to 180 parts by mass, and particularly preferably 130 to 170 parts by mass relative to 100 parts by mass of the linear polyarylene sulfide resin (A) having a carboxy group.

[0061] In another embodiment, from the viewpoint of increasing the mechanical strength while further suppressing the generation of burrs compared to virgin material, the content of the inorganic filler (C) is preferably 30 to 90 parts by mass, more preferably 35 to 85 parts by mass, even more preferably 38 to 80 parts by mass, and particularly preferably 40 to 75 parts by mass, relative to 100 parts by mass of the linear polyarylene sulfide resin (A) having a carboxy group,

[0062] (Other Components) The polyarylene sulfide resin composition (X) for recycled materials can contain known additives generally added to thermoplastic resins and thermosetting resins to impart desired properties according to the purpose, within a range that does not impair the effects of the present invention. Examples of additives include burr inhibitors, release agents, lubricants, plasticizers, flame retardants, colorants such as dyes and pigments, crystallization accelerators, crystal nucleating agents, various antioxidants, heat stabilizers, weathering stabilizers, and corrosion inhibitors. The content of the above other components is preferably 5% by mass or less of the total resin composition.

[0063] The polyarylene sulfide resin composition (X) for recycled materials can also be used in small amounts of other auxiliary thermoplastic resin components depending on the purpose. The other thermoplastic resins used here can be any resin stable at high temperatures. Examples include aromatic polyesters composed of aromatic dicarboxylic acids and diols or oxycarboxylic acids, such as polyethylene terephthalate and polybutylene terephthalate, polyamides, polycarbonates, ABS, polyphenylene oxide, polyalkyl acrylates, polysulfones, polyethersulfones, polyetherimides, polyether ketones, fluororesins, liquid crystal polymers, and cyclic olefin copolymers. Two or more of these thermoplastic resins can also be used in combination. The content of the other thermoplastic resin components is preferably 20% by mass or less based on the total amount (100% by mass) of the polyarylene sulfide resin composition (X) for recycled materials. The content of other thermoplastic resin components in the resin components constituting the polyarylene sulfide resin composition (X) for recycled materials is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

[0064] (Method for producing polyarylene sulfide resin composition (X) for recycled material) The method for producing the polyarylene sulfide resin composition (X) for recycled material is not particularly limited, and the composition can be produced by melt-kneading the above-mentioned components by a known method. For example, any of a method in which the components are mixed and then kneaded and extruded in an extruder to prepare pellets, a method in which pellets with different compositions are first prepared, a predetermined amount of the pellets are mixed, and molded to obtain a molded product of the desired composition after molding, and a method in which one or more of the components are directly charged into a molding machine can be used.

[0065] The polyarylene sulfide resin composition (X) for recycled materials was prepared by injection molding at a cylinder temperature of 320°C and a mold temperature of 150°C to obtain an injection-molded product having dimensions of 80 mm length x 80 mm width x 1.0 mm thickness. The injection-molded product was mechanically pulverized to an average particle diameter (D50) of 3 mm (recycled material). The burr length (L Ｒ) is preferably 140 μm or less, more preferably 130 μm or less, even more preferably 110 μm or less, and particularly preferably 100 μm or less. <Condition (1)> Using a mold with a disk-shaped cavity having a burr measurement section with a mold gap of 20 μm provided on the outer periphery, injection molding is performed at a cylinder temperature of 320°C, a mold temperature of 150°C, and the minimum pressure required to completely fill the cavity. The burr length generated in the burr measurement section is measured by enlarging it with a projection projector. The average particle diameter (D50) is the volume-based average particle diameter (D50) measured by laser diffraction scattering. The burr length (L Ｒ When the thickness is 140 μm or less, the generation of burrs during recycling is further suppressed.

[0066] The polyarylene sulfide resin composition (X) for recycled materials has a burr length (L) measured under the above-mentioned condition (1) for a virgin material (V) having the same composition. Ｖ ) relative to the burr length (L Ｒ ) ratio (L Ｒ / L ｖ ) is preferably 1.20 or less, more preferably 1.10 or less, and even more preferably 1.0 or less. Ｒ / L ｖ When the ratio L of the burr length is 1.20 or less, the burr length at the time of recycling can be suppressed to the same level as that of virgin material. Ｒ / L ｖ The burr length ratio L may be less than 1.0. Ｒ / L ｖ When the value is less than 1.0, the burr length during recycling can be made shorter than that during injection molding of virgin material.

[0067] [Recycled Material (R)] The recycled material (R) according to the present disclosure is a recycled material (R) of a polyarylene sulfide resin composition containing (A) 100 parts by mass of a polyarylene sulfide resin having a carboxy group and (B) 0.3 to 10 parts by mass of an alkoxysilane compound. The recycled material (R) may also contain (C) an inorganic filler. The (C) inorganic filler preferably contains (C1) a fibrous inorganic filler, and more preferably contains (C1a) a fibrous inorganic filler having a diameter ratio, which is the ratio of the major axis to the minor axis of a cross section perpendicular to the longitudinal direction, of 3.0 or more. The (A) polyarylene sulfide resin having a carboxy group, the (B) alkoxysilane compound, the (C) inorganic filler that may be contained as needed, the (C1) fibrous inorganic filler, the (C1a) fibrous inorganic filler having a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of 3.0 or more, and other components, as well as their contents, are as described above and therefore will not be described here.

[0068] As described above, "recycled material" refers to a material (recycled material) that is produced by crushing an article such as a molded body (a recycled product) and regenerating it as a material for use in manufacturing a molded body. The recycled material (R) is preferably a recycled material for injection molding.

[0069] The recycled material (R) preferably comprises or consists solely of a pulverized product of an article containing the above-mentioned polyarylene sulfide resin composition (X) for recycled material, and / or a repelletized material obtained by repelleting the pulverized product.

[0070] The article (recycled article) that is the raw material for the recycled material (R) may be a molded product, or may be a product that was discharged after being retained in a cylinder for a long time during molding. Examples include defective products generated during the manufacturing process of molded products, parts other than the product obtained during injection molding (e.g., runners, sprues, etc.), unused products, and chunks of polyethylene sulfide resin material used for purging during molding.

[0071] In one embodiment, the recycled material (R) may be a pulverized product of an article containing the polyarylene sulfide resin composition (X) for recycled material. When the recycled material (R) is a pulverized product, the average particle size of the pulverized product is not limited, and for example, the volume-based cumulative 50% diameter (D50) measured by a laser diffraction scattering method is preferably 0.3 to 20 mm, more preferably 0.4 to 15 mm, even more preferably 1 to 10 mm, and particularly preferably 1 to 3 mm.

[0072] In one embodiment, the recycled material (R) may be a repelletized material. When the recycled material (R) is a repelletized material, the reaction between the carboxyl groups of the polyarylene sulfide resin and the alkoxysilane compound (B) has progressed, making it easier to maintain or produce a high molecular weight polymer. In one embodiment, in the molecular weight distribution of the repelletized material measured by gel permeation chromatography (GPC), the area at a molecular weight of 700,000 or more preferably accounts for 1 to 20% of the total.

[0073] In one embodiment, the recycled material (R) has a burr length (L Ｒ ) is preferably 140 μm or less, more preferably 130 μm or less, even more preferably 110 μm or less, and particularly preferably 100 μm or less. <Condition (1)> Using a mold with a disk-shaped cavity having a burr measurement section with a mold gap of 20 μm provided on the outer periphery, injection molding is performed at a cylinder temperature of 320°C, a mold temperature of 150°C, and the minimum pressure required to completely fill the cavity. The length of the burr generated at the burr measurement section is measured by enlarging it with a projection projector. The burr length (L Ｒ When the thickness is 140 μm or less, the generation of burrs during recycling is further suppressed.

[0074] In one embodiment, the recycled material (R) has a burr length (L) measured according to the above condition (1) for a virgin material (V) having the same composition. Ｖ ) relative to the burr length (L Ｒ ) ratio (L Ｒ / L ｖ) is preferably 1.20 or less, more preferably 1.10 or less, and even more preferably 1.0 or less. Ｒ / L ｖ When the ratio L of the burr length is 1.20 or less, the burr length at the time of recycling can be suppressed to the same level as that of virgin material. Ｒ / L ｖ The burr length ratio L may be less than 1.0. Ｒ / L ｖ When the value is less than 1.0, the burr length during recycling can be made shorter than that during injection molding of virgin material.

[0075] The recycled material (R) can be reused as a molding material (preferably an injection molding material) either alone or as a mixture with virgin material. When used as a mixture with virgin material, the content of the recycled material (R) in the mixture is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount (100% by mass) of the mixture. The recycled material (R) can suppress the generation of burrs during recycling, so even when the content of the recycled material (R) in the mixture is high, the generation of burrs can be suppressed to the same extent (or more) as with virgin material.

[0076] [Method for Producing Repellet Material] The method for producing repellet material according to the present disclosure includes: obtaining a pulverized product of a molded product of a polyarylene sulfide resin composition (X) containing (A) 100 parts by mass of a polyarylene sulfide resin having a carboxy group and (B) 0.3 to 10 parts by mass of an alkoxysilane compound; and melt-kneading a recycled material containing the pulverized product at 260 to 380°C to obtain a repellet material. The polyarylene sulfide resin composition (X) may contain (C) an inorganic filler. The (C) inorganic filler preferably contains (C1) a fibrous inorganic filler, and more preferably contains (C1a) a fibrous inorganic filler having a diameter ratio, which is the ratio of the major axis to the minor axis of a cross section perpendicular to the longitudinal direction, of 3.0 or more. The (A) polyarylene sulfide resin having a carboxy group, the (B) alkoxysilane compound, the (C) inorganic filler that may be contained as needed, the (C1) fibrous inorganic filler, the (C1a) fibrous inorganic filler having a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of 3.0 or more, and other components, as well as their contents, are as described above and therefore will not be described here.

[0077] The pulverized product may be, for example, a molded product of the polyarylene sulfide resin composition (X) for recycled materials that has been previously pulverized, or may be obtained by mechanical pulverization using a pulverizer, a granulator, or the like. The average particle size of the pulverized product is not limited, and for example, the volume-based cumulative 50% diameter (D50) measured by a laser diffraction scattering method is preferably 0.3 to 20 mm, more preferably 0.4 to 15 mm, even more preferably 1 to 10 mm, and particularly preferably 1 to 3 mm. The molded product of the polyarylene sulfide resin composition (X) for recycled materials may be a molded product, or may be a product that has been retained in a cylinder for a long period of time during molding and then discharged. Examples include defective products generated during the manufacturing process of molded products, parts other than the product obtained during injection molding (e.g., runners, sprues, etc.), unused products, and chunks of the polyarylene sulfide resin material used for purging during molding.

[0078] The recycled material containing the pulverized material is melt-kneaded preferably at 260 to 380°C, more preferably at 280 to 340°C, to obtain a re-pellet material. The re-pellet material can then be used again as a material for injection molding. By re-pelletizing, the reaction between the carboxy groups of the linear polyarylene sulfide resin (A) having carboxy groups and the alkoxysilane compound (B) can be promoted in the re-pelleting process, which makes it easier to suppress the generation of burrs during recycling. In addition, the material can be easily handled during recycling.

[0079] [Method for Suppressing Burrs During Recycling] In one embodiment, there is provided a method for suppressing burrs during recycling of a polyarylene sulfide resin composition, comprising blending 0.3 to 10 parts by mass of (B) an alkoxysilane compound per 100 parts by mass of (A) a linear polyarylene sulfide resin having a carboxy group. This method can suppress burrs when the polyarylene sulfide resin composition is injection-molded at least once, the resulting molded article is pulverized to produce a recycled material, and then injection-molded again. In one embodiment, this method can shorten the burr length generated when the polyarylene sulfide resin composition is injection-molded at least once, the resulting molded article is pulverized to produce a recycled material, and then injection-molded again.

[0080] The (A) polyarylene sulfide resin having a carboxy group, the (B) alkoxysilane compound, the (C) inorganic filler, the (C1) fibrous inorganic filler, the (C1a) fibrous inorganic filler having a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of 3.0 or more, which may be contained as necessary, and other components, as well as their contents, are as described above and therefore will not be described here.

[0081] [Use of Alkoxysilane Compound to Suppress Burrs During Recycling] In one embodiment, there is provided a use of an alkoxysilane compound to suppress burrs during recycling of a polyarylene sulfide resin composition, comprising blending 0.3 to 10 parts by mass of (B) an alkoxysilane compound per 100 parts by mass of (A) a linear polyarylene sulfide resin having a carboxy group. This use can suppress burrs when the polyarylene sulfide resin composition is injection-molded at least once, the resulting molded article is crushed, and, if necessary, re-pelletized to form a recycled material, and then injection-molded again. In one embodiment, this use can reduce the burr length generated when the polyarylene sulfide resin composition is injection-molded at least once, the resulting molded article is crushed to form a recycled material, and then injection-molded again, compared to the burr length generated when a virgin material having the same composition is injection-molded.

[0082] The (A) polyarylene sulfide resin having a carboxy group, the (B) alkoxysilane compound, the (C) inorganic filler, the (C1) fibrous inorganic filler, the (C1a) fibrous inorganic filler having a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of 3.0 or more, which may be contained as necessary, and other components, as well as their contents, are as described above and therefore will not be described here.

[0083] [Use of Polyarylene Sulfide Resin Composition as a Recycled Material] In one embodiment, there is provided use of a polyarylene sulfide resin composition comprising (A) 100 parts by mass of a linear polyarylene sulfide resin having a carboxy group and (B) 0.3 to 10 parts by mass of an alkoxysilane compound as a recycled material. This use can produce a recycled material that can suppress burrs when re-injected into a molding machine. In one embodiment, this use can produce a recycled material in which the burr length generated when re-injected into a molding machine is shorter than the burr length generated when a virgin material having the same composition is injection-molded.

[0084] The (A) polyarylene sulfide resin having a carboxy group, the (B) alkoxysilane compound, the (C) inorganic filler, the (C1) fibrous inorganic filler, the (C1a) fibrous inorganic filler having a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of 3.0 or more, which may be contained as necessary, and other components, as well as their contents, are as described above and therefore will not be described here.

[0085] A non-limiting list of exemplary embodiments and combinations of exemplary embodiments of the present disclosure is disclosed below. [1] A polyarylene sulfide resin composition (X) for recycled materials, comprising: (A) 100 parts by mass of a linear polyarylene sulfide resin having carboxy groups; and (B) 0.3 to 10 parts by mass of an alkoxysilane compound. [2] The polyarylene sulfide resin composition (X) for recycled materials according to [1], wherein the (B) alkoxysilane compound comprises one or more alkoxysilane compounds having one or more selected from an epoxy group, an amino group, a vinyl group, a (meth)acrylic group, an isocyanate group, and a mercapto group. [3] The polyarylene sulfide resin composition (X) for recycled materials according to [1] or [2], comprising 30 to 250 parts by mass of an inorganic filler (C) relative to 100 parts by mass of the polyarylene sulfide resin (A) having carboxy groups. [4] The polyarylene sulfide resin composition (X) for recycled materials according to [3], wherein the inorganic filler (C) comprises a fibrous inorganic filler (C1). [5] The polyarylene sulfide resin composition (X) for recycled materials according to [4], wherein the fibrous inorganic filler (C1) comprises a fibrous inorganic filler (C1a) having a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of 3.0 or more. [6] The polyarylene sulfide resin composition (X) for recycled materials according to [5], wherein the content of the fibrous inorganic filler (C1a) having a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of 3.0 or more is 50 to 100 mass% of the total amount of the fibrous inorganic filler (C1). [7] A recycled material (R) of a polyarylene sulfide resin composition comprising (A) 100 parts by mass of a polyarylene sulfide resin having a carboxy group, and (B) 0.3 to 10 parts by mass of an alkoxysilane compound. [8] The recycled material (R) of the polyarylene sulfide resin composition according to [7], which is a repellet material. [9] A recycled material (R) of the polyarylene sulfide resin composition according to [7], which is a repellet material.

[10] A recycled material (R) of the polyarylene sulfide resin composition according to [7], which is a repellet material.

[11] A recycled material (R) of the polyarylene sulfide resin composition according to

[12] , which is a repellet material.

[12] A recycled material (R) of the polyarylene sulfide resin composition according to

[13] , which is a repellet material.

[13] A recycled material (R) of the polyarylene sulfide resin composition according to

[14] , which is a repellet material.

[14] A recycled material (R) of the polyarylene sulfide resin composition according to

[15] , which is a repellet material.

[15] A recycled material (R) of the polyarylene sulfide resin composition according to

[16] , which is a repellet material.

[16] A recycled material (R) of the polyarylene sulfide resin composition according to

[17] , which is a repellet material.

[17] A recycled material (R) of the polyarylene sulfide resin composition according to

[18] , which is a repellet material.

[18] A recycled material (R) of the polyarylene sulfide resin composition according to

[19] , which is a repellet material. [19 ... ＲThe recycled material (R) of the polyarylene sulfide resin composition according to [7], wherein the average particle size (μm) of the recycled material (R) is 140 μm or less. [Condition (1): Using a mold with a disk-shaped cavity having a flash measurement section with a 20 μm mold gap provided on the outer periphery, injection molding is performed at a cylinder temperature of 320°C, a mold temperature of 150°C, and the minimum pressure required to completely fill the cavity. The length of the flash generated at the flash measurement section is measured under magnification using a projection projector.]

[10] A method for producing a repellet material, comprising: obtaining a pulverized product of a molded product of a polyarylene sulfide resin composition (X) containing (A) 100 parts by mass of a polyarylene sulfide resin having a carboxy group and (B) 0.3 to 10 parts by mass of an alkoxysilane compound; and melt-kneading the recycled material containing the pulverized product at 260 to 380°C to obtain a repellet material. The configurations and combinations thereof in each embodiment are merely examples, and additions, omissions, substitutions, and other modifications of the configurations are possible as appropriate within the scope that does not deviate from the gist of this disclosure.

[0086] The present disclosure will be explained in more detail below by showing examples, but interpretation of the present disclosure is not limited to these examples.

[0087] [Raw Materials] The raw materials used in the Examples and Comparative Examples are as follows: (Polyarylene sulfide resin) PPS1: Linear polyphenylene sulfide resin, manufactured by Kureha Corporation, Fortron (registered trademark) KPS, melt viscosity 30 Pa·s (shear rate 1200 sec －１ , 310°C), Tc: 219°C, carboxyl group content: 35 μmol / g

[0088] (Method for measuring melt viscosity of PPS resin) The melt viscosity of the PPS resin was measured as follows: Using a Capillograph manufactured by Toyo Seiki Seisakusho Co., Ltd., a flat die of 1 mmφ×20 mmL was used as a capillary, and the barrel temperature was 310° C. and the shear rate was 1200 sec －１ The melt viscosity was measured at 100°C.

[0089] (Method for Measuring Tc) The Tc of the polyarylene sulfide resin was measured as follows: Approximately 5 mg of the polyarylene sulfide resin was weighed, and using a PerkinElmer DSC-8500 differential scanning calorimeter, the temperature was increased at a rate of 10°C / min, held at 340°C for 5 minutes, and then decreased at a rate of 10°C / min, and the crystallization peak (exothermic peak) temperature was read from the obtained DSC chart to determine Tc.

[0090] (Method for Measuring Carboxy Group Amount) The carboxyl group content of the polyarylene sulfide resin was measured as follows: (i) By FT-IR measurement, the absorption peak of the benzene ring of benzoic acid was measured at 3065 cm －１ , carboxyl group absorption peak 1704 cm －１ The peak heights at these points are measured. They are 0.023 and 0.293, respectively. Therefore, the relative intensity of the absorption peak of the carboxy group to the C-H bond of the benzene ring is 63.7. (ii) The resin composition is pressed and subjected to FT-IR measurement. When the peak height (absorption intensity) is 3065 cm －１ 0.049, 1704 cm at the position －１ (iii) The peak height (3065 cm) of the resin composition to be measured was measured in the same manner as above. －１ , and 1704 cm －１ From this, the relative intensity of the absorption peak of one carboxy group relative to one C-H bond on the benzene ring was calculated to be 0.24. From the relative intensity of the absorption peak of benzoic acid, in which one carboxy group is substituted on the benzene ring, it was determined that the carboxy group content was 0.38 mol% relative to the benzene ring. (iv) The amount of the repeating unit -(Ar-S)- (Ar is a benzene ring) contained in 1 kg of resin was 9.3 mol / kg, and the carboxy group content in 1 kg of resin composition was 35 μmol / g.

[0091] (Alkoxysilane Compound) Alkoxysilane compound: γ-aminopropyltriethoxysilane, "KBE-903P" manufactured by Shin-Etsu Chemical Co., Ltd. (burr suppressant) Branched PPS resin: Branched PPS resin produced by pre-polymerizing and post-polymerizing monomers in the same manner as in Synthesis Example 3 described in WO 2006 / 068161.

[0092] (Fibrous inorganic fillers) GF1: Chopped strand ECS03T-747H manufactured by Nippon Electric Glass Co., Ltd., approximately circular cross section, average fiber diameter 10.5 μm, major axis / minor axis ratio 1.0, average fiber length 3 mm GF2: Chopped strand ECS03T-747N manufactured by Nippon Electric Glass Co., Ltd., approximately circular cross section, average fiber diameter 17 μm, major axis / minor axis ratio 1.0, average fiber length 3 mm GF3: Flat glass fiber ESC03T-760-FGF manufactured by Nippon Electric Glass Co., Ltd., oval cross section, major axis 28 μm, minor axis 7 μm, major axis / minor axis ratio 4.0, average fiber length 3 mm

[0093] [Examples 1 to 9, Comparative Examples 1 to 9] Using the above materials, polyarylene sulfide resin, alkoxysilane compound, and fibrous inorganic filler were dry-blended in the compositions and content ratios shown in Tables 1 and 2. This was then fed into a twin-screw extruder with a cylinder temperature of 320 ° C and melt-kneaded to obtain virgin pellets. The resulting virgin pellets were injection-molded at a cylinder temperature of 320 ° C and a mold temperature of 150 ° C to obtain injection-molded articles measuring 80 mm long x 80 mm wide x 1.0 mm thick. The resulting injection-molded articles were pulverized using a mechanical pulverizer to an average particle diameter (D50) of 3 mm to obtain pulverized injection-molded articles (recycled materials). The resulting pulverized articles were then fed into a twin-screw extruder with a cylinder temperature of 320 ° C and melt-kneaded to obtain repellet materials (recycled materials) for the Examples and Comparative Examples.

[0094] [Evaluation] The repellet materials obtained in the examples and comparative examples were injection molded by the following method, and the burr length and Charpy impact strength were measured and evaluated. The results are shown in Tables 1 and 2.

[0095] (Evaluation of Burr Generation) The repellet materials obtained in the Examples and Comparative Examples were injection molded using a disk-shaped cavity mold having a burr measurement section on the outer periphery with a mold gap of 20 μm, at a cylinder temperature of 320° C., a mold temperature of 150° C., and the minimum pressure required to completely fill the cavity. The burr length (L Ｒ The burr length (L Ｒ When the burr length (L) is 140 μm or less, the generation of burrs during recycling can be suppressed. Ｒ When the burr length (L) is 130 μm or less, the generation of burrs during recycling can be further suppressed. Ｒ When the burr length (L) is 100 μm or less, the generation of burrs during recycling can be further suppressed. Ｒ When the thickness is 90 μm or less, the generation of burrs during recycling can be particularly suppressed.

[0096] Using the virgin pellets used in the examples and comparative examples, injection molding was carried out in the same manner as above, and the burr length (L Ｖ The obtained values ​​were used to calculate the flash length (L Ｖ ) to the burr length of the pellet material (L Ｒ ) ratio (L Ｒ / L ｖ The burr length ratio (L Ｒ / L ｖ When the ratio of the burr length (L) is 1.40 or less, the occurrence of burrs can be significantly suppressed compared to virgin pellets, and when the ratio is 1.20 or less, the occurrence of burrs can be kept at the same level as virgin pellets. Ｒ / L ｖ ) is less than 1.0, the occurrence of burrs is suppressed more effectively in the repelletized material than in the virgin pellets.

[0097] (Charpy impact strength (notched)) The repellet materials obtained in the examples and comparative examples were dried at 140°C for 3 hours, and then injection molded into test pieces (width 10 mm, thickness 4 mm) in accordance with ISO 316 at a molding cylinder temperature of 320°C and a mold temperature of 150°C. Using these test pieces, the Charpy impact strength (notched) (kJ / m) was measured in accordance with ISO 179-1. ２ ) was measured.

[0098]

[0099] As shown in Table 1, the repellet materials of Examples 1 to 9 had a burr length (L Ｒ The repellet materials of Examples 1, 2, 7, and 8 had a burr length ratio (L Ｒ / L ｖ ) was less than 1.0, and not only could the generation of burrs be suppressed during recycling, but the generation of burrs was also suppressed in the recycled pellets rather than in the virgin pellets. The recycled pellets of Examples 4 and 5 had a burr length ratio (L Ｒ / L ｖ The burr length (L) of the re-pellet materials of Examples 3, 6, 8, and 9 was 1.10 or less, and the burr generation was kept to the same level as that of virgin pellets. Ｒ ) was 90 μm or less, and the occurrence of burrs during recycling was particularly suppressed. The repellet materials of Examples 7 to 9, which used a fibrous inorganic filler with a flat cross-sectional shape as the inorganic filler, were able to produce recycled molded products with high Charpy impact strength. In contrast, as shown in Table 2, when a branched polyarylene sulfide resin was blended as a burr suppressant (Comparative Examples 1 to 9), burrs could be suppressed during injection molding of virgin pellets, but since no alkoxysilane compound was included, a large amount of burrs occurred during injection molding of the repellet material.

[0100] The polyarylene sulfide resin composition for recycled materials of the present embodiment can suppress the generation of burrs during recycling, and therefore can be suitably used as a resin composition for recyclable injection-molded products. Specifically, the polyarylene sulfide resin composition for recycled materials has industrial applicability as, for example, a material for electrical and electronic equipment parts, a material for automobile parts, a material for chemical equipment parts, etc.

Claims

1. A polyarylene sulfide resin composition (X) for recycled materials, comprising: (A) 100 parts by mass of a linear polyarylene sulfide resin having a carboxy group; and (B) 0.3 to 10 parts by mass of an alkoxysilane compound.

2. The polyarylene sulfide resin composition (X) for recycled materials according to claim 1, wherein the (B) alkoxysilane compound comprises one or more alkoxysilane compounds having one or more groups selected from an epoxy group, an amino group, a vinyl group, a (meth)acrylic group, an isocyanate group, and a mercapto group.

3. A polyarylene sulfide resin composition (X) for recycled materials according to claim 1 or 2, which contains 30 to 250 parts by mass of (C) inorganic filler per 100 parts by mass of (A) polyarylene sulfide resin having a carboxy group.

4. A polyarylene sulfide resin composition (X) for recycled materials according to claim 3, wherein the inorganic filler (C) comprises a fibrous inorganic filler (C1).

5. A polyarylene sulfide resin composition (X) for recycled materials as described in claim 4, wherein the (C1) fibrous inorganic filler includes (C1a) a fibrous inorganic filler having a diameter ratio, which is the ratio of the long diameter to the short diameter of a cross section perpendicular to the longitudinal direction, of 3.0 or more.

6. A polyarylene sulfide resin composition (X) for recycled materials according to claim 5, wherein the content of (C1a) a fibrous inorganic filler having a diameter ratio, which is the ratio of the major axis to the minor axis in a cross section perpendicular to the longitudinal direction, of 3.0 or more is 50 to 100 mass% of the total amount of (C1) the fibrous inorganic filler.

7. A recycled material (R) of a polyarylene sulfide resin composition comprising (A) 100 parts by mass of a polyarylene sulfide resin having a carboxy group and (B) 0.3 to 10 parts by mass of an alkoxysilane compound.

8. A recycled material (R) of the polyarylene sulfide resin composition according to claim 7, which is a repellet material.

9. The burr length (L Ｒ The recycled polyarylene sulfide resin composition (R) according to claim 7, wherein the thickness of the recycled polyarylene sulfide resin composition (R) is 140 μm or less. [Condition (1): Using a mold with a disk-shaped cavity having a burr measurement section on the outer periphery with a mold gap of 20 μm, injection molding is performed at a cylinder temperature of 320°C, a mold temperature of 150°C, and the minimum pressure required to completely fill the cavity. The length of the burr generated at the burr measurement section is measured under magnification using an image projector.] 10. A method for producing a repellet material, comprising: obtaining a pulverized product of a molded product of a polyarylene sulfide resin composition (X) containing (A) 100 parts by mass of a polyarylene sulfide resin having a carboxy group and (B) 0.3 to 10 parts by mass of an alkoxysilane compound; and melt-kneading a recycled material containing the pulverized product at 260 to 380°C to obtain a repellet material.