Polyarylene sulfide resin composition, method for producing polyarylene sulfide resin composition, molded article, method for producing molded article

Abstract

Provided is a polyarylene sulfide resin composition that has excellent resistance to heat and humidity and molding properties without reducing mechanical strength and the like. More specifically, the present invention is characterized by comprising a polyarylene sulfide resin, glass fibers that have been surface-treated with a sizing agent comprising an epoxy resin and a polyether resin, and a silane coupling agent having a functional group, the total content of the epoxy resin and the polyether resin in the aforementioned sizing agent being 65 to 100 mass%, and the isothermal crystallization time of the polyarylene sulfide resin composition being 9 seconds or less.

Description

Technical Field

[0001] This invention relates to polyarylene sulfide resin compositions, methods for manufacturing polyarylene sulfide resin compositions, molded articles, and methods for manufacturing molded articles. Background Technology

[0002] In recent years, engineering plastics with excellent productivity and moldability have been developed. Due to their light weight, they are widely used as alternatives to metal materials in components for electrical and electronic equipment, automotive applications, etc. Among these, polyphenylene sulfide (PPS) resin and polyarylene sulfide (PAS) resin, represented by PPS resin, are mainly used in electrical / electronic equipment components and automotive parts materials due to their excellent mechanical strength, heat resistance, chemical resistance, molding processability, dimensional stability, and flame retardancy.

[0003] Furthermore, in recent years, led by the automotive industry, there has been a trend towards miniaturization and high-output of equipment, resulting in an increasing amount of heat dissipation. Consequently, the requirements for the resistance to damp heat in components such as automotive cooling parts and wading components are becoming more stringent, leading to the development of various technologies to improve damp heat resistance.

[0004] One known technique for improving the resistance of PAS resin compositions to damp heat is the formulation of amino-containing silane coupling agents.

[0005] For example, Patent Document 1 discloses a PAS-based composition comprising: PAS resin; glass fiber surface-treated with a slugging agent containing epoxy resin, urethane resin and silane coupling agent; a silane coupling agent having at least one functional group selected from the group consisting of amino and epoxy groups; and synthetic zeolite.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2016-132710 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] However, although the technology in Patent Document 1 can improve the resistance to damp heat to a certain extent, the molding properties (release properties) of the resin composition are deteriorated due to the influence of the bridging agent and silane coupling agent.

[0011] Therefore, the purpose of this application is to provide a PAS resin composition with excellent resistance to damp heat and moldability without reducing physical properties such as mechanical strength, and a method for manufacturing the PAS resin composition.

[0012] Furthermore, the purpose of this application is to provide molded articles with excellent resistance to damp heat and moldability without reducing physical properties such as mechanical strength, and a method for manufacturing molded articles.

[0013] Solution for solving the problem

[0014] In order to solve the above-mentioned problems, the inventors have repeatedly conducted in-depth research and found that by including glass fibers that have been surface-treated with a slugging agent and a silane coupling agent in the PAS resin, and increasing the total amount of epoxy resin and polyether resin in the slugging agent, it is possible to maintain mechanical strength and other physical properties at a high level, and make the bonding at the interface between the PAS resin and the glass fiber stronger. Therefore, the resistance to damp heat can be improved. Furthermore, the isothermal crystallization time of the obtained PAS resin is as short as less than 9 seconds, and therefore, the moldability (release properties) are also excellent.

[0015] That is, this application relates to a polyarylene sulfide resin composition, characterized in that it comprises:

[0016] PAS resin;

[0017] Glass fibers surface-treated with a slugging agent comprising epoxy resin and polyether resin; and

[0018] Silane coupling agents with functional groups,

[0019] The total content of epoxy resin and polyether resin in the aforementioned bundler is 65-100% by mass.

[0020] The isothermal crystallization time of the polyarylene sulfide resin composition is less than 9 seconds.

[0021] By incorporating the above-mentioned components, it is possible to improve resistance to damp heat and formability without reducing physical properties such as mechanical strength.

[0022] In addition, this application relates to a method for manufacturing a PAS resin composition, characterized by comprising the following steps: mixing PAS resin, glass fibers surface-treated with a slugging agent, and a silane coupling agent having functional groups, and then performing melt mixing.

[0023] The aforementioned bundler comprises epoxy resin and polyether resin, and the total content of epoxy resin and polyether resin in the aforementioned bundler is 65% to 100% by mass.

[0024] The isothermal crystallization time of the obtained resin composition is less than 9 seconds.

[0025] By having the above-described structure, it is possible to obtain a PAS resin composition that exhibits excellent resistance to damp heat and moldability without reducing physical properties such as mechanical strength.

[0026] The molded article of the present application is formed by molding the PAS resin composition of the present application.

[0027] By having the above-described configuration, excellent heat and humidity resistance and moldability can be achieved without reducing physical properties such as mechanical strength.

[0028] The manufacturing method of the molded article of the present application is characterized by having the following steps: melt-molding the PAS resin composition obtained by the manufacturing method of the PAS resin composition of the present application.

[0029] By having the above-described configuration, a molded article having excellent heat and humidity resistance and moldability without reducing physical properties such as mechanical strength can be obtained.

[0030] Effects of the Invention

[0031] According to the present application, a PAS resin composition and a manufacturing method of the PAS resin composition, which have excellent heat and humidity resistance and moldability without reducing physical properties such as mechanical strength, can be provided.

[0032] In addition, according to the present application, a molded article and a manufacturing method of the molded article, which have excellent heat and humidity resistance and moldability without reducing physical properties such as mechanical strength, can be provided. Detailed Description of the Embodiment

[0033] Hereinafter, an embodiment of the PAS resin composition, the manufacturing method of the PAS resin composition, the molded article, and the manufacturing method of the molded article of the present invention will be exemplified and described.

[0034] <PAS Resin Composition>

[0035] The PAS resin composition according to the present embodiment contains a PAS resin, glass fibers surface-treated with a bundling agent, and a silane coupling agent having a functional group.

[0036] Hereinafter, each component constituting the PAS resin composition in the present embodiment will be described.

[0037] (Polyarylene Sulfide Resin)

[0038] The PAS resin composition according to the present embodiment contains a PAS resin.

[0039] This PAS resin has a resin structure having a structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit. Specifically, it is a resin having a structural part represented by the following general formula (1) and, if necessary, a further trifunctional structural part represented by the following general formula (2) as a repeating unit.

[0040]

[0041] (In the formula, R1 and R 2 Each of these groups independently represents an alkyl, nitro, amino, phenyl, methoxy, or ethoxy group with 1 to 4 carbon atoms.

[0042]

[0043] It should be noted that the number of moles of the trifunctional structural part shown in the above general formula (2) relative to the total number of moles of it and other structural parts is preferably in the range of 0.001 to 3 mol%, and particularly preferably in the range of 0.01 to 1 mol%.

[0044] Here, in the structural portion shown in the above general formula (1), especially from the viewpoint of the mechanical strength of the aforementioned PAS resin, R in the formula 1 and R 2 Preferably, hydrogen atoms are used. In this case, structural sites with bonding at the para position as shown in equation (3) and structural sites with bonding at the meta position as shown in equation (4) can be listed.

[0045]

[0046] Among these, especially considering the aforementioned PAS resin's resistance to damp heat and crystallinity, the sulfur atom in the repeating unit is preferably bonded to the aromatic ring in the para position as shown in the above general formula (3).

[0047] In addition, the aforementioned PAS resin may include not only the structural parts shown in the aforementioned general formulas (1) and (2), but may also include the structural parts shown in the following structural formulas (5) to (8) in a total of less than 30 mol% of the structural parts shown in the aforementioned general formulas (1) and (2).

[0048]

[0049] Furthermore, from the viewpoint of the resistance to damp heat and mechanical strength of PAS resin, the structural portions shown in the above general formulas (5) to (8) are preferably 10 mol% or less. When the aforementioned PAS resin contains the structural portions shown in the above general formulas (5) to (8), their bonding mode can be either random copolymer or block copolymer.

[0050] As described above, regarding the aforementioned PAS resin, it is preferable to use a high molecular weight polymer with a substantially linear structure obtained by polycondensation of a monomer with a difunctional halogenated aromatic compound as the main body shown in the above general formula (1). In addition to using a PAS resin with a linear structure, a polymer that partially forms a branched or cross-linked structure can also be used by using a small amount of monomers such as polyhalogenated aromatic compounds having three or more halogenated functional groups as shown in the above general formula (2) during its polycondensation. Alternatively, a PAS resin with improved molding processability can be used by heating a low molecular weight linear polymer at high temperature in the presence of oxygen or an oxidant and increasing its melt viscosity through oxidative cross-linking or thermal cross-linking.

[0051] When using a combination of linear and cross-linked PAS resins, from a moldability point of view, the preferred weight ratio of linear to cross-linked PAS resin is 1:3 to 3:1. This is because, within this range, the isothermal crystallization time of the resulting PAS resin composition is shorter, resulting in good moldability.

[0052] Furthermore, the melt viscosity, non-Newtonian index, and sodium content of the aforementioned PAS resin are not particularly limited as long as they do not impair the effects of the present invention, as shown below.

[0053] The melt viscosity of the aforementioned PAS resin is not particularly limited. From the viewpoint of balancing fluidity and mechanical strength, the melt viscosity (V6) measured at 300°C is preferably in the range of 2 Pa·s or more, preferably in the range of 1000 Pa·s or less, more preferably in the range of 500 Pa·s or less, and even more preferably in the range of 200 Pa·s or less.

[0054] It should be noted that the melt viscosity (V6) of PAS resin was measured using a Shimadzu CFT-500D flow tester, set at 300℃ and a load of 1.96 × 10⁻⁶. 6 The measured melt viscosity is obtained after holding the sample for 6 minutes under the conditions of Pa and L / D = 10 (mm) / 1 (mm).

[0055] The non-Newtonian index of the aforementioned PAS resin is not particularly limited, but is preferably in the range of 0.90 or higher and 2.00 or lower. Furthermore, when using linear PAS resin as the aforementioned PAS resin, the non-Newtonian index is preferably in the range of 0.90 or higher, more preferably in the range of 0.95 or higher, and further preferably in the range of 1.50 or lower, more preferably in the range of 1.20 or lower. PAS resins with such a non-Newtonian index exhibit excellent mechanical properties, flowability, and abrasion resistance.

[0056] It should be noted that in this embodiment, the non-Newtonian index (N value) is as follows: using a Capilograph, under the conditions of melting point +20°C and orifice length (L) to orifice diameter (D) ratio L / D = 40, the shear rate (SR) and shear stress (SS) are measured, and the value is calculated using the following formula:

[0057] SR = K·SS N

[0058] (Here, SR represents the shear rate (seconds)) -1 SS represents shear stress (dynes / cm) 2 (And K represents a constant.)

[0059] The closer the non-Newtonian exponent (N value) is to 1, the more linear the structure is; the higher the non-Newtonian exponent (N value), the more branched the structure is.

[0060] Furthermore, in the PAS resin used in this embodiment, the sodium atom content derived from the vulcanizing agent or the like from the raw materials is preferably in the range of 400 ppm or less, more preferably in the range of 350 ppm or less, and particularly preferably in the range of 300 ppm or less. This is because, within this range, the isothermal crystallization time of the resulting PAS resin composition is shorter, resulting in good moldability. On the other hand, the lower limit of sodium concentration is preferably lower than the detection limit, but excessive reduction can sometimes reduce productivity; therefore, it is preferably 40 ppm or more, more preferably 50 ppm or more, and particularly preferably 70 ppm or more.

[0061] It should be noted that the sodium atom content in the aforementioned PAS resin refers to the following concentration: the sodium atom concentration (mass standard) when the resin is calcined at 500°C, then calcined at 530°C for 6 hours, the resulting ash is dissolved in hydrochloric acid, and measured using an atomic absorption spectrophotometer AA-6300 (manufactured by Shimadzu Corporation).

[0062] There are no particular limitations on the manufacturing methods of the aforementioned PAS resin, and the following methods can be listed as examples: (Manufacturing Method 1) A method in which a dihaloaromatic compound is added, and if necessary, a polyhaloaromatic compound and / or other copolymer components are added, in the presence of sulfur and sodium carbonate, and the mixture is polymerized; (Manufacturing Method 2) A method in which a dihaloaromatic compound is added, and if necessary, a polyhaloaromatic compound and / or other copolymer components are added, in the presence of a vulcanizing agent in a polar solvent, and the mixture is polymerized; (Manufacturing Method 3) A method in which p-chlorothiophenol is added, and if necessary, other copolymer components are added, and the mixture is self-condensed; (Manufacturing Method 4) A method in which a diiodoaromatic compound and elemental sulfur are melt-polymerized under reduced pressure in the presence of a polymerization inhibitor having optional functional groups such as carboxyl or amino groups, etc.

[0063] Of these manufacturing methods, method (2) is the most common and therefore preferred. During the reaction, alkali metal salts of carboxylic acids and sulfonic acids, or alkali hydroxides, can be added to adjust the degree of polymerization.

[0064] Furthermore, in method (manufacturing method 2), a substance obtained by the following method is particularly preferred: an aqueous sulfiding agent is introduced into a mixture containing a heated organic polar solvent and a dihaloaromatic compound at a rate capable of removing water from the reaction mixture; a polyhaloaromatic compound is added as needed; the dihaloaromatic compound reacts with the sulfiding agent in the organic polar solvent; and the water content in the reaction system is controlled to be in the range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent. This method for manufacturing PAS resin (see Japanese Patent Application Laid-Open No. 07-2) (Publication No. 28699); A method for reacting an alkali metal hydrogen sulfide with an organic acid alkali metal salt in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, by adding a dihaloaromatic compound and, as needed, a polyhaloaromatic compound and / or other copolymerizing components, while controlling the organic acid alkali metal salt to a range of 0.01 to 0.9 mol relative to 1 mol of the sulfur source and the water content in the reaction system to a range of less than 0.02 mol relative to 1 mol of the aprotic polar organic solvent (see WO2010 / 058713).

[0065] Specific examples of the aforementioned dihaloaromatic compounds include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p,p'-dihalodiphenyl ether, and 4,4'-dihalodiphenyl ether. Ketones, 4,4'-dihalodiphenyl sulfones, 4,4'-dihalodiphenyl sulfoxides, 4,4'-dihalodiphenyl sulfides, and compounds having alkyl groups having 1 to 18 carbon atoms on the aromatic ring of the above compounds, as polyhalogenated aromatic compounds, include 1,2,3-trihalobenzenes, 1,2,4-trihalobenzenes, 1,3,5-trihalobenzenes, 1,2,3,5-tetrahalobenzenes, 1,2,4,5-tetrahalobenzenes, 1,4,6-trihalonaphthalenes, etc. It should be noted that the halogen atoms contained in the above compounds are preferably chlorine or bromine atoms.

[0066] Furthermore, there are no particular limitations on the post-treatment methods for the reaction mixture containing PAS resin obtained through the polymerization process. Examples of such methods include: (Post-treatment 1) After the polymerization reaction, the reaction mixture is first distilled off the solvent directly under reduced pressure or normal pressure, or after adding an acid or alkali, the solvent is distilled off under reduced pressure or normal pressure. Then, the solid residue after solvent distillation is washed once or twice or more with solvents such as water, the reaction solvent (or an organic solvent with solubility equivalent to that of the low molecular weight polymer), acetone, methyl ethyl ketone, or alcohols, followed by neutralization, washing, filtration, and drying; (Post-treatment 2) After the polymerization reaction, water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, or other solvents (solvents soluble in the polymerization solvent used and at least unsuitable for PAS) are added to the reaction mixture as a settling agent to cause solid products such as PAS and inorganic salts to undergo settling. Methods for settling, filtering, washing, and drying; (Post-treatment 3) After the polymerization reaction is completed, adding a reaction solvent (or an organic solvent with the same solubility relative to the low molecular weight polymer) to the reaction mixture and stirring, filtering to remove the low molecular weight polymer, washing once or twice or more with solvents such as water, acetone, methyl ethyl ketone, or alcohols, followed by neutralization, water washing, filtration, and drying; (Post-treatment 4) After the polymerization reaction is completed, adding water to the reaction mixture for water washing and filtration, adding acid during water washing as needed for acid treatment, and drying; or (Post-treatment 5) After the polymerization reaction is completed, filtering the reaction mixture, washing once or twice or more with a reaction solvent as needed, followed by water washing, filtration, and drying, etc.

[0067] It should be noted that in the post-treatment methods exemplified in (post-treatment 1) to (post-treatment 5) above, the drying of PAS resin can be carried out in a vacuum, or in an air atmosphere or an inactive gas atmosphere such as nitrogen.

[0068] (Glass fibers that have undergone surface treatment using a bubbling agent)

[0069] The PAS resin composition described in this embodiment, in addition to containing the above-mentioned PAS resin, also contains glass fibers (hereinafter sometimes referred to as "surface-treated glass fibers") that have been surface-treated using a slugging agent containing epoxy resin and polyether resin.

[0070] Furthermore, in this embodiment, the total amount of epoxy resin and polyether resin in the aforementioned bridging agent needs to be 65-100% by mass.

[0071] In PAS resin compositions, glass fibers surface-treated with a binder primarily composed of epoxy resin and polyether resin are used as fillers to strengthen the bond between the PAS resin and glass fibers, thereby improving mechanical strength and resistance to damp heat. Without the aforementioned binder surface treatment or with different binder compositions, the bond strength at the PAS resin-glass fiber interface decreases, resulting in insufficient mechanical strength and resistance to damp heat.

[0072] Furthermore, in the PAS resin composition described in this embodiment, the aforementioned bridging agent is mainly composed of epoxy resin and polyether resin, which can shorten the crystallization time of the resin composition and thus improve moldability (release properties).

[0073] Here, the shape of the glass fiber used for the aforementioned surface treatment is not particularly limited as long as it is fibrous. The fiber diameter, fiber length, and aspect ratio can be appropriately adjusted according to the intended use of the molded article. From the viewpoint of exhibiting superior mechanical strength and toughness, the fiber diameter is preferably in the range of 1 μm or more, more preferably 6 μm or more, and preferably 50 μm or less, more preferably 20 μm or less.

[0074] Furthermore, regarding the aforementioned types of glass fibers, glass fibers obtained from alkali-containing glass, low-alkali glass, and alkali-free glass (E-glass) can be used. Among these, alkali-free glass is preferred from the perspective of less degradation over time and stable mechanical properties.

[0075] The bridging agent used in the aforementioned surface treatment of glass fibers contains epoxy resin and polyether resin, with a total content of 65-100% by mass. When their total content is 65% by mass or more, the bonding at the interface between the PAS resin and the glass fiber is stronger, thus improving mechanical strength and resistance to damp heat. Furthermore, by setting the main components of the aforementioned bridging agent to epoxy resin and polyether resin, the content of highly volatile components that deteriorate mold release properties is reduced (or eliminated), thus improving the moldability of the resin composition. The total content of the aforementioned epoxy resin and polyether resin is preferably 65-100% by mass, more preferably 75-100% by mass, even more preferably 85-100% by mass, and particularly preferably 95-100% by mass.

[0076] Furthermore, there is no particular limitation on the content of epoxy resin and polyether resin in the aforementioned bridging agent. The content of the epoxy resin is preferably 55-98% by mass, and the content of the polyether resin is preferably 2-35% by mass. This is because by including the aforementioned epoxy resin and polyether resin within the above range, a higher level of mechanical strength and resistance to damp heat can be achieved. From the same viewpoint, the content of the epoxy resin is more preferably 60% by mass or more, and more preferably 95% by mass or less. Furthermore, the content of the polyether resin is preferably 5% by mass or more, and more preferably 30% by mass or less.

[0077] There are no particular limitations on the epoxy resins contained in the aforementioned bundlers; they can be appropriately selected based on the required performance. Examples of suitable epoxy resins include bisphenol A type epoxy resins, bisphenol A, bisphenol F, etc.; phenolic varnish type epoxy resins, ethylphenolic varnish type epoxy resins, butylphenolic varnish type epoxy resins, octylphenolic varnish type epoxy resins, o-cresol varnish type epoxy resins, etc.; resorcinol varnish type epoxy resins, bisphenol A varnish type epoxy resins, bisphenol F varnish type epoxy resins, bisphenol AD ​​varnish type epoxy resins, bisphenol S varnish type epoxy resins, etc. Substances obtained by reacting a portion of the epoxy groups in these resins with carboxylic acids to open the ring and form hydroxyl groups can also be used.

[0078] Among these, phenolic varnish-type epoxy resins, cresol varnish-type epoxy resins, or bisphenol A type epoxy resins with hydroxyl groups are preferred as the aforementioned epoxy resins. This is because the mechanical strength of the resin composition can be further improved.

[0079] In addition, the epoxy equivalent of the aforementioned epoxy resin is not particularly limited, but is preferably 100 to 4000 g / equivalent, more preferably 100 to 1000 g / equivalent, even more preferably 100 to 750 g / equivalent, and particularly preferably 100 to 500 g / equivalent.

[0080] There are no particular limitations on the polyether resin contained in the aforementioned bundlers; they can be selected appropriately based on the required performance.

[0081] Examples of polyether resins include polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethyleneoxypropylene glycol, polyoxytetramethylene glycol, and bisphenol-based alkylene oxide adducts with 2 to 4 carbon atoms. Among these, those with 3 to 5 carbon atoms and alkylene oxides are preferred, and polyoxypropylene glycol, polyoxyethyleneoxypropylene glycol, and polyoxytetramethylene glycol are particularly preferred.

[0082] It should be noted that as long as the aforementioned bundlers contain epoxy resin and polyether resin, and their total amount is in the range of 65% to 100% by mass, they may contain a small amount of other bundler components as needed.

[0083] Regarding the aforementioned other bridging agent components, there are no particular limitations, and examples include at least one polymer selected from the group consisting of silane compounds, titanate compounds, acrylic resins, and urethane resins having functional groups such as amino, epoxy, isocyanate, and vinyl groups.

[0084] Furthermore, the content of the surface-treated glass fiber in the PAS resin composition described in this embodiment is not particularly limited. From the viewpoint of obtaining superior mechanical strength and resistance to damp heat, it is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, further preferably 30 parts by weight or more, and particularly preferably 40 parts by weight or more, relative to 100 parts by weight of the aforementioned PAS resin. Moreover, from the viewpoint of obtaining superior flowability, processability, and surface smoothness of the molded article of the resin composition, the content of the surface-treated glass fiber in the PAS resin composition described in this embodiment is preferably 150 parts by weight or less, more preferably 130 parts by weight or less, and further preferably 110 parts by weight or less, relative to 100 parts by weight of the aforementioned PAS resin.

[0085] (Silane coupling agent)

[0086] The PAS resin composition described in this embodiment, in addition to including the above-mentioned PAS resin, surface-treated glass fiber, and an inorganic filler as an optional component, also includes a silane coupling agent having functional groups.

[0087] By including the aforementioned silane coupling agent with functional groups in the PAS resin composition, the adhesion between the aforementioned PAS resin and the aforementioned surface-treated glass fiber can be improved, thereby obtaining superior resistance to damp heat and mechanical strength.

[0088] Here, the aforementioned silane coupling agent having functional groups is not particularly limited as long as it does not impair the effects of the present invention. Preferred examples include silane coupling agents having functional groups that react with carboxyl groups, such as epoxy, isocyanate, amino, or hydroxyl groups. Examples of such silane coupling agents include, for instance, alkoxysilane compounds containing epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; and γ-isocyanopropyltrimethoxysilane, γ-isocyanopropyltriethoxysilane, γ-isocyanopropylmethyldimethoxysilane, γ-isocyanopropylmethyldiethoxysilane, and γ-isocyanopropylethyldimethoxysilane. Alkoxysilane compounds containing isocyanate groups, such as γ-isocyanopropylethyldiethoxysilane and γ-isocyanopropyltrichlorosilane; alkoxysilane compounds containing amino groups, such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane; and alkoxysilane compounds containing hydroxyl groups, such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane.

[0089] Furthermore, the content of the aforementioned silane coupling agent with functional groups in the PAS resin composition described in this embodiment is not particularly limited. From the viewpoint of obtaining better resistance to damp heat and mechanical strength, it is preferably 0.3 parts by mass or more, more preferably 0.4 parts by mass or more, and even more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the aforementioned PAS resin.

[0090] On the other hand, from the viewpoint of ensuring better flowability and processability of the resin composition, the content of the aforementioned reinforcing fiber in the PAS resin composition described in this embodiment is more preferably 10 parts by weight or less, more preferably 8 parts by weight or less, and particularly preferably 6 parts by weight or less, relative to 100 parts by weight of the aforementioned PAS resin.

[0091] (elastomer)

[0092] The PAS resin composition described in this embodiment may further include an elastomer in addition to the PAS resin and surface-treated glass fiber.

[0093] By further including the aforementioned elastomer, the toughness and resistance to thermal shock of the PAS resin composition can be improved. From the same point of view, a thermoplastic elastomer is preferred as the aforementioned elastomer.

[0094] Examples of thermoplastic elastomers include polyolefin-based elastomers, fluorinated elastomers, and silicone-based elastomers, with polyolefin-based elastomers being preferred. When these elastomers are added, the mixing amount is not particularly limited, but is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and even more preferably 1 part by weight or more, relative to 100 parts by weight of the aforementioned PAS resin. On the other hand, the mixing amount of the aforementioned thermoplastic elastomer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 15 parts by weight or less. Within this range, the resulting PAS resin composition exhibits improved softness, and is therefore preferred.

[0095] For example, the aforementioned polyolefin-based elastomers may include homopolymers of α-olefins, copolymers of two or more α-olefins, and copolymers of one or more α-olefins with vinyl polymerizable compounds having functional groups. In this case, α-olefins with 2 to 8 carbon atoms, such as ethylene, propylene, and 1-butene, may be listed as examples. Furthermore, the aforementioned functional groups may include carboxyl groups, anhydride groups (-C(=O)OC(=O)-), epoxy groups, amino groups, hydroxyl groups, mercapto groups, isocyanate groups, and oxazoline groups. Furthermore, examples of vinyl polymeric compounds having the aforementioned functional groups include vinyl acetate; α,β-unsaturated carboxylic acids such as (meth)acrylic acid; alkyl esters of α,β-unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, and butyl acrylate; metal salts of α,β-unsaturated carboxylic acids such as ionomers (as metals, alkali metals such as sodium, alkaline earth metals such as calcium, zinc, etc.); glycidyl esters of α,β-unsaturated carboxylic acids such as glycidyl methacrylate; α,β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and one or more derivatives (monoesters, diesters, anhydrides) of the aforementioned α,β-unsaturated dicarboxylic acids. The above-mentioned thermoplastic elastomers can be used alone or in combination of two or more.

[0096] (Other inorganic fillers)

[0097] The PAS resin composition described in this embodiment may further include an inorganic filler in addition to the above-mentioned PAS resin and surface-treated glass fiber.

[0098] By further including the aforementioned inorganic filler, the mechanical strength and thermal conductivity of the PAS resin composition can be further improved.

[0099] There is no particular limitation on the types of inorganic fillers mentioned above. Glass fibers are not included.

[0100] As for the aforementioned inorganic fillers, other fillers can be made of commonly known materials as long as they do not impair the effects of the present invention. Examples of fillers of various shapes include granular and plate-shaped fillers. Fiber-like fillers such as carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, etc., and natural fibers can be used. Additionally, non-fibrous fillers such as glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, mica, talc, palygorskite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, abrasive fibers, and calcium sulfate can be used.

[0101] It should be noted that these inorganic fillers can also undergo surface treatment, such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, borane treatment, ceramic coating, etc., as needed.

[0102] Furthermore, regarding the aforementioned inorganic filler, from the viewpoint of being able to achieve a good balance between the mechanical properties and dimensional stability of the PAS resin composition, calcium carbonate is preferably used as the aforementioned inorganic filler.

[0103] Furthermore, the content of the aforementioned inorganic filler in the PAS resin composition described in this embodiment is not particularly limited. From the viewpoint of superior mechanical properties and dimensional stability, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, relative to 100 parts by mass of the aforementioned PAS resin.

[0104] Furthermore, from the viewpoint of obtaining superior fluidity, processability, and surface smoothness of the molded article of the resin composition, the content of the aforementioned inorganic filler in the PAS resin composition of this embodiment is more preferably 350 parts by weight or less, more preferably 300 parts by weight or less, and particularly preferably 250 parts by weight or less, relative to 100 parts by weight of the aforementioned PAS resin.

[0105] The content of the inorganic filler (hereinafter sometimes referred to as "all inorganic filler") obtained by combining the aforementioned surface-treated glass fiber with the aforementioned inorganic filler in the PAS resin composition described in this embodiment is not particularly limited. For example, from the viewpoint of excellent isothermal crystallization rate of the resin composition, it is preferable to have 20 parts by mass or more, more preferably 25 parts by mass or more, and even more preferably 30 parts by mass or more, relative to the total amount of the aforementioned PAS resin and all inorganic filler (100 parts by mass). This is because, within this range, the isothermal crystallization time is shorter, resulting in good moldability.

[0106] (Other ingredients)

[0107] The PAS resin composition described in this embodiment, in addition to the aforementioned PAS resin, surface-treated glass fiber, silane coupling agent, and optional elastomer and inorganic filler, may include, depending on the required performance, synthetic resins, coloring materials, antistatic agents, antioxidants, heat stabilizers, ultraviolet stabilizers, ultraviolet absorbers, foaming agents, flame retardants, flame retardant additives, rust inhibitors, coupling agents, and other additives (hereinafter referred to as "other components"). The aforementioned other components are preferably in the range of 0.01 parts by weight or more, and more preferably in the range of 100 parts by weight or less, relative to, for example, the aforementioned PAS resin, as long as they are appropriately adjusted and used according to the purpose and application without impairing the effects of the present invention.

[0108] Examples of synthetic resins mentioned above include polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyetherketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoroethylene resin, polystyrene resin, ABS resin, phenolic resin, urethane resin, liquid crystal polymer, and other synthetic resins.

[0109] The aforementioned synthetic resin is not a necessary component, and its mixing ratio is not particularly limited as long as it does not impair the effect of the present invention, and can be appropriately selected according to the respective purpose. For example, in the PAS resin composition described in this embodiment, the ratio relative to 100 parts by weight of the aforementioned PAS resin can be set to a range of 5 parts by weight or more and 15 parts by weight or less. In other words, the proportion of PAS resin relative to the total of the aforementioned PAS resin and synthetic resin is preferably (100 / 115) or more by weight, and more preferably (100 / 105) or more.

[0110] Furthermore, the isothermal crystallization time of the PAS resin composition described in this embodiment is 9 seconds or less.

[0111] By shortening the isothermal crystallization time of the PAS resin composition to 9 seconds or less, the moldability (especially the release property) of the resin composition can be improved. From the same viewpoint, the aforementioned isothermal crystallization time is preferably 8 seconds or less, more preferably 7 seconds or less. On the other hand, if the aforementioned isothermal crystallization time is too short, problems such as reduced flowability during molding may occur; therefore, 3 seconds or more is preferred.

[0112] It should be noted that the aforementioned isothermal crystallization time is as follows: when using Mettler Toledo's "Flash DSC1" to heat from 30°C to 330°C at a heating rate of 100°C / second, hold at 330°C for 1 second, then cool down to 140°C at 6000°C / second (the maximum cooling rate of the device) and hold isothermally, the time until the exothermic peak caused by resin crystallization is generated (peak time) is considered.

[0113] <Method for manufacturing polyarylene sulfide resin compositions>

[0114] Next, the method for manufacturing the PAS resin composition will be described.

[0115] The method for manufacturing the PAS resin composition described in this embodiment is characterized by the following steps: mixing PAS resin, glass fibers that have been surface-treated with a slugging agent, and a silane coupling agent having functional groups, and then performing melt mixing.

[0116] The aforementioned bundler comprises epoxy resin and polyether resin, and the total content of epoxy resin and polyether resin in the aforementioned bundler is 65% to 100% by mass.

[0117] The isothermal crystallization time of the obtained resin composition is less than 9 seconds.

[0118] In the PAS resin composition described in this embodiment, each essential component is blended with optional components as needed. It should be noted that the aforementioned essential and optional components are the same as those described in the PAS resin composition of this embodiment.

[0119] There are no particular limitations on the method of compounding and mixing the aforementioned essential and optional components. The following methods can be listed: a method of compounding the essential components with optional components as needed and performing melt mixing. More specifically, the following methods can be listed: a method of uniformly dry mixing using a drum or Henschel mixer as needed, followed by feeding the mixture into a twin-screw extruder and performing melt mixing.

[0120] Melt mixing can be performed by heating the resin to a temperature range that is above the melting point of the aforementioned PAS resin, preferably above the melting point +10°C, more preferably above the melting point +10°C, even more preferably above the melting point +20°C to preferably below the melting point +100°C, and more preferably below the melting point +50°C.

[0121] From the viewpoint of dispersibility and productivity, a twin-screw compounding extruder is preferred as the aforementioned melt mixing machine. For example, it is preferable to perform melt mixing when the resin component ejection rate is appropriately adjusted to a range of 5 to 500 kg / h and the screw speed is a range of 50 to 500 rpm. More preferably, melt mixing is performed when their ratio (ejection rate / screw speed) reaches a range of 0.02 to 5 kg / h / rpm.

[0122] Furthermore, the addition and mixing of each component into the melt mixer can be carried out simultaneously or in stages. For example, when adding the additives among the aforementioned components, from the viewpoint of dispersibility, it is preferable to feed them into the extruder through the side feeder of the aforementioned twin-screw compounding extruder. Regarding the location of the side feeder, the ratio of the distance from the resin input section (top feeder) of the extruder to the side feeder relative to the total length of the screw of the aforementioned twin-screw compounding extruder is preferably 0.1 or more, more preferably 0.3 or more. In addition, this ratio is preferably 0.9 or less, more preferably 0.7 or less.

[0123] The PAS resin composition of this embodiment, obtained by melt mixing in this manner, has the following morphology: the PAS resin forms a continuous phase, and other essential and optional components are dispersed therein. Preferably, after melt mixing, the PAS resin composition of this embodiment is further processed into granules, flakes, particles, powders, etc., using a known method, such as extruding the molten resin composition into a filament, and then pre-dried at a temperature range of 100–150°C as needed.

[0124] <Molded articles, methods for manufacturing molded articles>

[0125] The molded article described in this embodiment is formed by melt molding the PAS resin composition described in this embodiment. Furthermore, the manufacturing method of the molded article described in this embodiment is characterized by including the following step: melt molding the PAS resin composition obtained by the manufacturing method of the PAS resin composition described in this embodiment.

[0126] The molded article described in this embodiment, by using the PAS resin composition described in this embodiment as a material, exhibits the following effects: maintaining physical properties such as mechanical strength at a high level, and achieving excellent resistance to damp heat and moldability.

[0127] Regarding the molding of the aforementioned PAS resin composition, it can be used for various molding processes such as injection molding, compression molding, extrusion molding, pultrusion molding, blow molding, and transfer molding of composites, sheets, tubes, etc., and is particularly suitable for injection molding applications due to its excellent demolding properties. When using injection molding, there are no particular limitations on the molding conditions, and molding can generally be performed using common methods. For example, in an injection molding machine, after a process of melting the aforementioned PAS resin composition at a temperature above the melting point of the PAS resin, preferably at a temperature above the melting point +10°C, more preferably at a temperature range of melting point +10°C to melting point +100°C, and even more preferably at a temperature range of melting point +20°C to melting point +50°C, the mixture is injected into a mold from a resin nozzle and molded. At this time, the mold temperature is also set to a known temperature range, for example, room temperature (around 23°C) to 300°C, preferably 120°C to 180°C.

[0128] The intended use of the molded articles described in this embodiment is not particularly limited, and they can be used for various products. In particular, they exhibit excellent resistance to damp heat, making them preferred for fluid transfer components that come into contact with fluids and their vapors, such as toilet-related components, oiler-related components, pump-related components, bathtub-related components, and automotive-related components. Furthermore, they are preferably used as water-contact components for aqueous media containing water and water-miscible organic solvents such as ethylene glycol. They can also be used as composite molded articles bonded to metals, molded articles based solely on the PAS resin composition of this invention, etc. As for the method of bonding to metals, methods such as insertion injection molding, vibration bonding, infrared bonding, ultrasonic bonding, electromagnetic induction heating, and combinations thereof can be used.

[0129] It should be noted that the articles obtained using the molded articles and composite molded articles described in this embodiment are not limited to the above-mentioned articles, and can also be made into general resin molded articles as follows. Examples include, for instance, box-type electrical / electronic component integrated modules for protection / support members / multiple individual semiconductors or modules, sensors, LEDs, connectors, sockets, resistors, relay boxes, switches, ignition coils, capacitors, variable capacitor boxes, optical pickups, vibrators, various terminal blocks, variable transformers, plugs, printed circuit boards, tuners, amplifiers, microphones, headsets, small motors, and magnetic head supports. Electrical / electronic components such as base, power modules, terminal blocks, semiconductors, LCDs, FDD carriages, FDD chassis, brush holders, parabolic antennas, and computer-related components; household and office electrical components such as VTR components, television components, irons, hair dryers, rice cooker components, microwave oven components, audio components, audio / CD / compressor / DVD / Blu-ray disc and other audio / video equipment components, lighting components, refrigerator components, air conditioner components, typewriter components, word processor components, or water-related equipment components such as water heaters, bathtub hot water volume and temperature sensors; mechanical components such as office computer components, telephone components, fax machine components, copier components, cleaning tools, motor components, recorders, and typewriters; optical machines and precision mechanical components such as microscopes, telescopes, cameras, and watches; alternator terminals, alternator connectors, toothbrush holders, slip rings, IC regulators, dimmer potentiometer brackets, and relays. Components, automatic transmission locking switches, EVO valves and other valves; various pipes related to fuel / exhaust / intake systems, intake nozzle connecting pipes, intake manifolds, fuel pumps, engine coolant connectors, carburetor bodies, carburetor pitch shims, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, air flow meters, brake pad wear sensors, air conditioning thermostat bases, heater hot air flow control valves, radiator motor brush brackets, water pump turbines, turbine blades. This product range includes components related to windshield wiper motors, distributors, starter switches, ignition coils and their coil frames, motor insulators, motor rotors, motor cores, starter relays, transmission wiring harnesses, windshield washer nozzles, air conditioning panel switch base plates, coils for fuel-related solenoid valves, fuse connectors, alarm terminals, electrical component insulation boards, stepper motor rotors, lamp holders, lamp reflectors, lamp housings, brake pistons, solenoid ignition coils, engine oil filters, ignition device housings, and other automotive / vehicle-related components. It can also be used for various other applications.

[0130] The embodiments of the present invention have been described above, but the present invention is not limited to the foregoing embodiments. Various modifications can be made to the present invention without departing from its spirit, and these modifications are also included within the technical scope of the present invention.

[0131] Example

[0132] The present invention will be described in more detail below with examples, but the present invention is not limited to the examples described below. It should be noted that, unless otherwise specified, "%" and "parts" are used as mass units.

[0133] <Examples 1-18, Comparative Examples 1-2>

[0134] The materials were compounded according to the composition and mixing amounts listed in Tables 1 and 2. These compounded materials were then fed into a ventilated twin-screw extruder "TEX-30" (product name) manufactured by Nippon Steel Co., Ltd., and melt-blended under conditions of a resin component ejection rate of 25 kg / h, a screw speed of 200 rpm, and a resin temperature of 320°C to obtain resin composition granules. Glass fiber was then fed through a side feeder, while other materials were pre-mixed uniformly using a rotary drum and fed through a top feeder. The resulting resin composition granules were dried in a gear oven at 140°C for 2 hours and then injection molded to produce various test pieces, which were then evaluated as follows.

[0135] <Evaluation>

[0136] (1) Determination of tensile strength

[0137] As test pieces, ISO TYPE-A dumbbell plates were fabricated, and their tensile strength (MPa) was determined using the "AGS-J" gauge manufactured by Shimadzu Corporation according to ISO 527-1 and 2. It should be noted that the dumbbell plates used were manufactured by injecting resin from a single-point gate to form test pieces excluding welded sections. The test results are shown in Tables 1 and 2.

[0138] (2) Determination of isothermal crystallization time

[0139] Thin sheets (200 μm × 200 μm × 5 μm) were cut from the hot-pressed sheet of the PPS resin composition to serve as test pieces. Subsequently, as a pretreatment step to promote contact between the test piece and the sensor, the test piece was heated from 30 °C to 330 °C at a rate of 3 °C / second, held at 330 °C for 1 second, and then cooled to 30 °C at a rate of 3 °C / second. Then, as a measurement step, the test piece was heated from 30 °C to 330 °C at a rate of 100 °C / second, held at 330 °C for 1 second, then cooled to 140 °C at a rate of 6000 °C / second and held isothermally. The time until the exothermic peak caused by resin crystallization occurred (peak time) was measured. It should be noted that Mettler Toledo's "Flash DSC1" was used to measure the peak time. The measured isothermal crystallization times are shown in Tables 1 and 2.

[0140] (3) Evaluation of resistance to damp heat

[0141] As test pieces, ISO TYPE-A dumbbell plates were manufactured by injection molding and then placed under high temperature and high humidity (121°C, 100% humidity) for 500 hours. Afterward, the test pieces were slowly cooled to room temperature, and their tensile strength (MPa) was determined using methods based on ISO 527-1 and 2. The rate of change in strength relative to test pieces not exposed to high temperature and high humidity was calculated as (tensile strength after exposure to high temperature and high humidity / tensile strength before exposure to high temperature and high humidity × 100 (%)). The calculated retention rate of moisture heat resistance is shown in Tables 1 and 2.

[0142] (4) Evaluation of moldability (release properties)

[0143] Using an ISO TYPE-A dumbbell plate molding die with a single gate, the resin compositions of each embodiment and comparative example were injection molded, and their moldability (release properties) were evaluated. It should be noted that the barrel temperature of the injection molding machine was set to 310°C and the mold temperature was set to 140°C.

[0144] For evaluation, the resin composition granules were injected into the mold and held for at least 15 seconds to allow it to cure. The mold was then opened to check whether the dumbbell plates were still adhered to it. Twenty injection molding cycles were performed, and evaluations were conducted according to the following criteria. The evaluation results are shown in Tables 1 and 2.

[0145] 〇: Not glued to the mold, allowing for continuous molding.

[0146] △: Cannot be continuously molded after being pasted 1 to 10 times on the mold.

[0147] ×: Cannot be continuously molded after being pasted 10-20 times on the mold.

[0148] (5) Thermal shock resistance (thermal cycling) test of molded articles with welded parts

[0149] On a straight line parallel to the transverse edge of a steel insert component with a length of 25mm, width of 40mm, and thickness of 10mm, two through holes with a diameter of 3.55mm parallel to the thickness direction are arranged at their centers, with the centers of these through holes offset from the midpoint of the aforementioned straight line by 20mm. Next, the insert component is held inside the injection molding mold using the two through holes and two cylindrical steel pins. Using an injection molding mold designed to cover the entire outer periphery of the insert component with a 1mm thick layer of resin composition during injection molding of the resin composition granules, injection molding is performed on the PPS resin composition granules of each embodiment and comparative example to obtain molded articles for thermal shock resistance (thermal cycling) tests. Using the obtained molded test articles, a thermal shock test was performed in a vapor-phase thermal shock testing machine, with one cycle consisting of holding the product at -40°C for 30 minutes to 150°C for 30 minutes. The number of cycles until cracks appeared and the product fractured was measured. It should be noted that five tests were performed for each example and comparative example (test number n = 5), and the average value was calculated. The average number of cycles until fracture for each sample is shown in Tables 1 and 2.

[0150] [Table 1]

[0151]

[0152] [Table 2]

[0153]

[0154] *1 Polyphenylene sulfide resin (linear type), manufactured by DIC Corporation, melt viscosity (V6) at 300°C: 60 Pa·s

[0155] *2 Polyphenylene sulfide resin (crosslinking type), manufactured by DIC Corporation, melt viscosity (V6) at 300°C: 60 Pa·s

[0156] *3 Surface-treated glass fibers; Bundling agent: 95% epoxy resin, 5% polyether resin; Glass fibers: chopped filaments with a fiber diameter of 10μm and a fiber length of 3mm.

[0157] *4 Surface-treated glass fibers; Bundling agent: 50% epoxy resin, 0% polyether resin, 50% urethane resin; Glass fibers: chopped filaments with a fiber diameter of 10μm and a fiber length of 3mm.

[0158] *5 Surface-treated glass fibers; Bundling agent: 55% epoxy resin, 3% polyether resin, and 42% other components; Glass fibers: chopped strands with a diameter of 10μm and a length of 3mm.

[0159] *6 Surface-treated glass fibers; Bundling agent: 60% epoxy resin, 5% polyether resin, and 35% other components; Glass fibers: chopped filaments with a diameter of 10μm and a length of 3mm.

[0160] *7 3-Aminopropyltriethoxysilane

[0161] *8γ-Epoxypropoxypropyltrimethoxysilane

[0162] *9 Average particle size of calcium carbonate (D) 50 ): 22μm

[0163] *10 Elastomer manufactured by Sumitomo Chemical Co., Ltd. BONDFAST 7L

[0164] As can be seen from Tables 1 and 2, compared with the samples obtained using the PAS resin composition of the comparative example, the samples obtained using the PAS resin composition of the example showed high values ​​in any evaluation item, and were able to achieve excellent results with a good balance.

[0165] Industrial availability

[0166] According to the present invention, a PAS resin composition with excellent resistance to damp heat and moldability without reducing physical properties such as mechanical strength, and a method for manufacturing the PAS resin composition are provided.

[0167] Furthermore, according to the present invention, molded articles with excellent resistance to damp heat and formability without reducing physical properties such as mechanical strength, and a method for manufacturing molded articles, can be provided.

Claims

1. A polyarylene sulfide resin composition, characterized by, Comprise: a polyarylene sulfide resin; a glass fiber subjected to surface treatment with a sizing agent containing an epoxy resin and a polyether resin; and a silane coupling agent having a functional group, the total content of the epoxy resin and the polyether resin in the sizing agent is 65 to 100 mass%, the sizing agent contains 55 to 98 mass% of the epoxy resin and 2 to 35 mass% of the polyether resin, the isothermal crystallization time of the polyarylene sulfide resin composition is 9 seconds or less.

2. The polyarylene sulfide resin composition according to claim 1, wherein the resin composition contains 10 to 150 parts by mass of the glass fiber subjected to surface treatment, and 0.3 to 10 parts by mass of the silane coupling agent, per 100 parts by mass of the polyarylene sulfide resin.

3. The polyarylene sulfide resin composition according to claim 1 or 2, characterized by, further contains an elastomer.

4. The polyarylene sulfide resin composition according to claim 1 or 2, characterized by further contains calcium carbonate.

5. A method for manufacturing a polyaryl sulfide resin composition, characterized in that, has the steps of: compounding a polyarylene sulfide resin, a glass fiber subjected to surface treatment with a sizing agent, and a silane coupling agent having a functional group, and melt-kneading them, the sizing agent contains an epoxy resin and a polyether resin, the total content of the epoxy resin and the polyether resin in the sizing agent is 65 to 100 mass%, and the sizing agent contains 55 to 98 mass% of the epoxy resin and 2 to 35 mass% of the polyether resin, the isothermal crystallization time of the obtained resin composition is 9 seconds or less.

6. The method for producing a polyarylene sulfide resin composition according to Claim 5, characterized by compounding 10 to 150 parts by mass of the glass fiber subjected to surface treatment, and 0.3 to 10 parts by mass of the silane coupling agent, per 100 parts by mass of the polyarylene sulfide resin.

7. The method for producing a polyarylene sulfide resin composition according to claim 5 or 6, characterized by, further compounding an elastomer.

8. The method for producing a polyarylene sulfide resin composition according to claim 5 or 6, characterized by, further compounding calcium carbonate.

9. A molded article which is molded from the polyarylene sulfide resin composition according to any one of claims 1 to 4.

10. A method for producing a molded article, characterized by, has the steps of: melt-molding the resin composition obtained by the production method of the polyarylene sulfide resin composition according to any one of claims 5 to 8.

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