Polyarylene sulfide resin composition, molded article and method for manufacturing them

Abstract

To provide a PAS resin molded article which is excellent in damping property while maintaining mechanical characteristics of a polyarylene sulfide (PAS) resin, a PAS resin composition which enables provision of the molded article, and a method for manufacturing them.SOLUTION: There are provided a PAS resin composition which is formed by compounding a PAS resin (A) and a thermoplastic elastomer (B), wherein the thermoplastic elastomer (B) is a styrenic thermoplastic elastomer whose terminal is amine-modified and the styrene content is within the range of 10 to 40 pts.mass, and the compounding amount of the thermoplastic elastomer (B) is 10 to 70 pts.mass with respect to 100 pts.mass of the PAS resin (A); a molded article; and a manufacturing method therefor.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyarylene sulfide resin composition, a molded article, and a method for producing the same. [Background technology]

[0002] In recent years, polyarylene sulfide (PAS) resins, such as polyphenylene sulfide (PPS) resin, have been increasingly used as metal replacement materials for electrical and electronic equipment, automotive components, and other components because of their excellent heat resistance, mechanical strength, chemical resistance, moldability, and dimensional stability, as well as their light weight.

[0003] On the other hand, in order to prevent deterioration of the components due to vibration and to improve the soundproofing of vehicles and electronic devices equipped with the components, there is a demand for improved vibration-damping properties of PAS resin components. For example, Patent Document 1 discloses a resin composition containing 50-90% by weight of polyamide resin and / or polyphenylene sulfide resin, 1-30% by weight of polyphenylene ether resin, and a copolymer having a substantially block structure composed of a vinyl aromatic monomer and a conjugated diene monomer. Patent Document 2 discloses a vibration-damping resin composition containing a liquid crystal polymer and a PPS resin. However, when a liquid crystal polymer is added, mechanical properties may be reduced or processability may be poor due to burrs, etc., and a new vibration-damping PAS resin composition has been demanded. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 5-287197 [Patent Document 2] JP 2002-294041 A Summary of the Invention [Problem to be solved by the invention]

[0005] The problem to be solved by the present invention is to provide a PAS resin molded article that has excellent vibration damping properties while maintaining the mechanical properties of PAS resin, a PAS resin composition capable of providing such a molded article, and a method for producing the same. [Means for solving the problem]

[0006] As a result of intensive research aimed at solving the above problems, the present inventors discovered that by blending an amine-terminated styrene-based thermoplastic elastomer, the resulting PAS resin composition and molded article have excellent vibration damping properties and maintain their mechanical properties, and thus completed the present invention.

[0007] That is, the present disclosure relates to a PAS resin composition comprising a PAS resin (A) and a thermoplastic elastomer (B), wherein the thermoplastic elastomer (B) is a styrene-based thermoplastic elastomer having an amine-modified end and has a styrene content in the range of 10 to 40 parts by mass, and the amount of the thermoplastic elastomer (B) is 10 to 70 parts by mass per 100 parts by mass of the PAS resin (A).

[0008] The present disclosure also relates to a molded article obtained by melt molding the above-described resin composition. Effect of the Invention

[0009] According to the present invention, it is possible to provide a PAS resin molded article that has excellent vibration damping properties while maintaining the mechanical properties of a PAS resin, a PAS resin composition capable of providing such a molded article, and a method for producing the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] An embodiment of the present disclosure will be described in detail below, but the scope of the present disclosure is not limited to the embodiment described here, and various modifications can be made without departing from the spirit of the present disclosure. In addition, when multiple upper and lower limit values ​​are described for a specific parameter, any upper and lower limit values ​​can be combined to form a suitable numerical range.

[0011] <Resin Composition> The resin composition according to this embodiment is a PAS resin composition prepared by blending a PAS resin (A) and a thermoplastic elastomer (B), wherein the thermoplastic elastomer (B) is a styrene-based thermoplastic elastomer having an amine-modified end, and the styrene content is in the range of 10 to 40 parts by mass, and the blending amount of the thermoplastic elastomer (B) is 10 to 70 parts by mass with respect to 100 parts by mass of the PAS resin (A). This will be described in detail below.

[0012] <PAS Resin (A)> The PAS resin composition according to this embodiment is prepared by blending a PAS resin as an essential component.

[0013] The 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, the following general formula (1)

[0014] [Chemical Formula] (In the formula, R 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group.) and, if necessary, further the following general formula (2)

[0015] [Chemical Formula] and a trifunctional structural moiety represented by, as repeating units. The trifunctional structural moiety represented by formula (2) is preferably in the range of 0.001 to 3 mol% with respect to the total number of moles of other structural moieties, and particularly preferably in the range of 0.01 to 1 mol%.

[0016] Here, the structural moiety represented by the general formula (1) is particularly R 1 and R 2is preferably a hydrogen atom from the viewpoint of the mechanical strength of the PAS resin, and in that case, examples include those bonded at the para position represented by the following formula (3) and those bonded at the meta position represented by the following formula (4).

[0017] [ka] Among these, a structure in which the bond between the sulfur atom and the aromatic ring in the repeating unit is at the para position represented by the general formula (3) is particularly preferred in terms of the heat resistance of the PAS resin.

[0018] The PAS resin may include not only the structural moieties represented by the general formula (1) or (2) but also the structural moieties represented by the following structural formulae (5) to (8):

[0019] [ka] The structural moiety represented by the general formula (1) and the structural moiety represented by the general formula (2) may be contained in an amount of 30 mol % or less of the total of the structural moieties represented by the general formula (1) and the general formula (2). In particular, in the present disclosure, it is preferable that the structural moieties represented by the general formulae (5) to (8) are 10 mol % or less in terms of the heat resistance and mechanical strength of the PAS. When the structural moieties represented by the general formulae (5) to (8) are contained in the PAS resin, the bonding mode thereof may be either a random copolymer or a block copolymer.

[0020] The PAS resin may have naphthyl sulfide bonds or the like in its molecular structure, but the amount of such bonds is preferably 3 mol % or less, and particularly preferably 1 mol % or less, relative to the total number of moles including other structural portions.

[0021] The physical properties of the PAS resin are not particularly limited as long as they do not impair the effects of the present invention, but are as follows.

[0022] (Melt Viscosity) The melt viscosity of the PAS resin used in the present disclosure is not particularly limited, but in order to obtain a good balance between fluidity and mechanical strength, the melt viscosity (V6) measured at 300°C is preferably in the range of 35 Pa·s or more, more preferably in the range of 175 Pa·s or more, and preferably in the range of 40 Pa·s or less, more preferably in the range of 150 Pa·s or less. However, the melt viscosity (V6) is measured by using a Shimadzu flow tester, CFT-500D, at 300°C, load: 1.96×10 6 The melt viscosity is measured after holding the sample for 6 minutes at a pressure of 1 Pa and L / D = 10 (mm) / 1 (mm).

[0023] (Non-Newtonian Exponents) The non-Newtonian index of the PAS resin used in the present disclosure is not particularly limited, but is preferably in the range of 0.90 or more to 2.00 or less. When a linear PAS resin is used, the non-Newtonian index is preferably in the range of 0.90 or more, more preferably 0.95 or more, and preferably 1.50 or less, more preferably 1.20 or less. Such a PAS resin is excellent in mechanical properties, fluidity, and abrasion resistance. However, in the present disclosure, the non-Newtonian index (N value) is a value calculated using the following formula by measuring the shear rate (SR) and shear stress (SS) using a capillary rheometer under the conditions of a melting point of +20°C and a ratio of the orifice length (L) to the orifice diameter (D) of L / D=40. The closer the non-Newtonian index (N value) is to 1, the closer the structure is to a linear structure, and the higher the non-Newtonian index (N value), the more branched the structure is.

[0024]

number

[0025] (Manufacturing method) The method for producing the PAS resin is not particularly limited, but examples thereof include (production method 1) a method in which a dihalogeno aromatic compound is polymerized in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogeno aromatic compound or other copolymerization component is added, (production method 2) a method in which a dihalogeno aromatic compound is polymerized in a polar solvent in the presence of a sulfidizing agent or the like, and if necessary, a polyhalogeno aromatic compound or other copolymerization component is added, (production method 3) a method in which p-chlorothiophenol is added, and if necessary, other copolymerization components are added, and self-condensation is performed, and (production method 4) a method in which a diiodo aromatic compound and elemental sulfur are melt-polymerized under reduced pressure in the presence of a polymerization inhibitor that may have a functional group such as a carboxy group or an amino group. Among these methods, (production method 2) is preferred because it is versatile. During the reaction, an alkali metal salt of a carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above-mentioned (Production Method 2) methods, there is a method for producing a PAS resin by introducing a water-containing sulfidizing agent into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at a rate at which water can be removed from the reaction mixture, and then reacting the dihalogeno aromatic compound and the sulfidizing agent in the organic polar solvent, and optionally adding a polyhalogeno aromatic compound, and controlling the amount of water in the reaction system to within a range of 0.02 to 0.5 mol per mol of the organic polar solvent (see JP-A-07-228699). Particularly preferred is a method in which a dihalogeno-aromatic compound and, if necessary, a polyhalogeno-aromatic compound or other copolymerization component are added in the presence of potassium metal sulfide and an aprotic polar organic solvent, and an alkali metal hydrosulfide and an organic acid alkali metal salt are reacted while controlling the organic acid alkali metal salt in the range of 0.01 to 0.9 mol per mol of the sulfur source and the amount of water in the reaction system to 0.02 mol or less per mol of the aprotic polar organic solvent (see WO2010 / 058713 pamphlet).Specific examples of the dihalogenoaromatic compound 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, 4,4'-dihalobenzophenone, 4,4'-di Examples of the polyhalogeno aromatic compounds include 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene, etc. The halogen atoms contained in the above compounds are preferably chlorine atoms or bromine atoms.

[0026] The method for post-treating the reaction mixture containing the PAS resin obtained by the polymerization step is not particularly limited, but for example, (post-treating 1) after the completion of the polymerization reaction, first, the solvent is distilled off under reduced pressure or normal pressure, either as is or after adding an acid or base, and then the solid matter remaining after the solvent distillation is washed once or twice or more times with a solvent such as water, the reaction solvent (or an organic solvent having a similar solubility to the low molecular weight polymer), acetone, methyl ethyl ketone, or alcohols, and then neutralized, washed with water, filtered, and dried; or (post-treating 2) after the completion of the polymerization reaction, the reaction mixture is dissolved in a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, or aliphatic hydrocarbons (soluble in the polymerization solvent used and poorly soluble in at least PAS). or (post-treatment 3) after the polymerization reaction is completed, a reaction solvent (or an organic solvent having a solubility equivalent to that of the low molecular weight polymer) is added to the reaction mixture, the mixture is stirred, the mixture is filtered to remove the low molecular weight polymer, the mixture is washed once or twice or more times with a solvent such as water, acetone, methyl ethyl ketone, or an alcohol, and then the mixture is neutralized, washed with water, filtered, and dried; (post-treatment 4) after the polymerization reaction is completed, water is added to the reaction mixture, the mixture is washed with water, filtered, and if necessary, an acid is added during the water washing to perform an acid treatment, and then the mixture is dried; or (post-treatment 5) after the polymerization reaction is completed, the reaction mixture is filtered, and if necessary, the mixture is washed once or twice or more times with the reaction solvent, and then the mixture is washed with water, filtered, and dried.

[0027] In the post-treatment methods exemplified above in (Post-treatment 1) to (Post-treatment 5), the PAS resin may be dried in a vacuum, or in air or in an inert gas atmosphere such as nitrogen.

[0028] The PAS resin used in this embodiment may be a PAS resin newly polymerized by the above method, or a recycled PAS resin. For example, a PAS resin recovered from a PAS resin composition or a PAS resin molded product may be used. Specifically, a PAS resin obtained by heating a PAS resin composition or a PAS resin molded product in an organic polar solvent to dissolve the PAS contained therein and then performing the above-mentioned post-treatment on the solution may be used.

[0029] <Thermoplastic elastomer (B)> The PAS resin composition of this embodiment is composed of, in addition to the above-mentioned PAS resin (A), a thermoplastic elastomer (B) having an amine-modified terminal, which is a styrene-based thermoplastic elastomer (hereinafter, sometimes simply referred to as elastomer), blended as an essential component.

[0030] Examples of styrene-based thermoplastic elastomers include styrene-based AB-type diblock copolymers such as styrene-ethylene-butylene copolymer (SEB); styrene-butadiene-styrene copolymer (SBS), hydrogenated SBS (styrene-ethylene-butylene-styrene copolymer (SEBS)), styrene-isoprene-styrene copolymer (SIS), hydrogenated SIS (styrene-ethylene-propylene-styrene copolymer (SEPS)), and styrene-isobutylene-styrene copolymer (SIBS); styrene-based ABAB-type tetrablock copolymers such as styrene-butadiene-styrene-butadiene (SBSB); styrene-based ABABA-type pentablock copolymers such as styrene-butadiene-styrene-butadiene-styrene (SBSBS); styrene-based multiblock copolymers having AB repeat units of these or more; and hydrogenated products obtained by hydrogenating the ethylenic double bonds of styrene-based random copolymers such as styrene-butadiene rubber (SBR). Commercially available styrene-based thermoplastic elastomers may be used. Examples of commercially available products include "Dynaron (registered trademark) 4660P" and "Dynaron (registered trademark) 8660P" manufactured by JSR Corporation, and "Tuftec (registered trademark) MP10" manufactured by Asahi Kasei Corporation.

[0031] The thermoplastic elastomer (B) applicable to this embodiment is an elastomer having a styrene content in the range of 10 to 40 parts by mass. In this range, the elastomer exhibits excellent vibration damping properties while exhibiting excellent mechanical properties, particularly excellent impact resistance. The styrene content in this disclosure indicates the content ratio (mass%) of styrene blocks in the thermoplastic elastomer (B). The styrene content in this disclosure includes not only the styrene unit but also the content of a structural unit in which a hydrogen atom bonded to an aromatic ring of a styrene unit is replaced with another atom or atomic group. The method for calculating the styrene content is not particularly limited, but may be, for example, a method using proton nuclear magnetic resonance spectroscopy or infrared spectroscopy according to JIS K6239.

[0032] The thermoplastic elastomer (B) preferably has a glass transition point of -40°C or less, since it has rubber elasticity even at low temperatures and has excellent resistance to cold and heat shocks and low-temperature shocks. The lower the glass transition point, the more preferable it is, and generally, the glass transition point is preferably in the range of -180 to -40°C, and particularly preferably in the range of -150 to -40°C. The density is 0.95 g / cm. 3 It is preferable that:

[0033] The blending ratio of the thermoplastic elastomer (B) is preferably 10 parts by mass or more, more preferably 15 parts by mass or less, and also preferably 70 parts by mass or less, more preferably 60 parts by mass or less, based on 100 parts by mass of the PAS resin (A). If it is less than this range, excellent vibration damping properties cannot be exhibited, and if it exceeds this range, gas generation during processing may increase, resulting in deterioration of surface appearance and processability.

[0034] (Silane coupling agent) If necessary, a silane coupling agent can be blended as an optional component in the PAS resin composition according to this embodiment for the purpose of improving mechanical properties.

[0035] Here, the silane coupling agent having the functional group is not particularly limited as long as it does not impair the effects of the present invention, but preferred examples include silane coupling agents having a functional group that reacts with a carboxy group, such as an epoxy group, an isocyanato group, an amino group, or a hydroxyl group. Examples of such silane coupling agents include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane; amino group-containing alkoxysilane compounds such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane; and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane.

[0036] In addition, the content of the silane coupling agent having the functional group in the PAS resin composition of the present invention is not particularly limited, but from the viewpoint of obtaining better moist heat resistance and mechanical strength, it is preferably 0.3 parts by mass or more per 100 parts by mass of the PAS resin, more preferably 0.4 parts by mass or more, and even more preferably 0.5 parts by mass or more. On the other hand, from the viewpoint of ensuring better fluidity and processability of the resin composition, the content of the reinforcing fibers in the PAS resin composition of the present invention is more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and particularly preferably 6 parts by mass or less, per 100 parts by mass of the PAS resin (A).

[0037] (Inorganic filler) The PAS resin composition according to this embodiment may further contain an inorganic filler. By further containing the inorganic filler, the mechanical strength and thermal conductivity of the PAS resin composition can be further increased.

[0038] Here, as the inorganic filler, a known and commonly used material can be used as long as it does not impair the effect of the present invention, and examples thereof include fillers of various shapes such as granular and plate-shaped ones. For example, fibrous fillers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, and natural fibers can be used, and non-fibrous fillers such as glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, zeolite, milled fiber, and calcium sulfate can be used. In addition, these inorganic fillers can be surface-treated, and if necessary, epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, borane treatment, ceramic coating, etc. can be applied.

[0039] The content of the inorganic filler is not particularly limited, but from the viewpoint of better 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 PAS resin. Also, from the viewpoint of obtaining better flowability and processability of the resin composition and smoothness of the surface of the molded product, it is more preferably 350 parts by mass or less, even more preferably 300 parts by mass or less, and particularly preferably 250 parts by mass or less relative to 100 parts by mass of the PAS resin.

[0040] Furthermore, in addition to the above components, the PAS resin composition according to the present embodiment may further contain synthetic resins such as polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyetherketone resin, polyarylate resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoroethylene resin, polystyrene resin, ABS resin, epoxy resin, phenol resin, urethane resin, and liquid crystal polymer as optional components depending on the application. In particular, it is preferable to add a fluorine-based resin because it improves the sliding properties. In the present disclosure, the synthetic resin is not an essential component, but when it is added, the ratio of the synthetic resin is not particularly limited as long as it does not impair the effects of the present invention, and it differs depending on each purpose and cannot be generally defined, but the ratio of the synthetic resin to be added in the resin composition according to the present disclosure is, for example, in the range of 5 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the PAS resin (A). In other words, the ratio of the PAS resin to the total of the PAS resin (A) and the synthetic resin is preferably in the range of (100 / 115) or more, and more preferably in the range of (100 / 105) or more, on a mass basis.

[0041] In addition, the PAS resin composition according to the present embodiment may contain other known and commonly used additives as optional components, such as colorants, antistatic agents, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, foaming agents, flame retardants, flame retardant assistants, rust inhibitors, and release agents (metal salts or esters of fatty acids having 18 to 30 carbon atoms, including stearic acid or montanic acid, polyolefin waxes such as polyethylene, etc.) as needed. These additives are not essential components, and may be used in an amount of, for example, preferably 0.01 parts by mass or more, and preferably 1000 parts by mass or less, more preferably 100 parts by mass or less, based on 100 parts by mass of the PAS resin (A), as appropriate for the purpose or use so as not to impair the effects of the present invention.

[0042] <Method of producing resin composition> The method for producing the PAS resin composition according to the present embodiment includes a step of blending the essential components and melt-kneading them at a temperature range equal to or higher than the melting point of the PAS resin (A). More specifically, the PAS resin composition according to the present embodiment is composed of the essential components and, if necessary, other optional components. The method for producing the resin composition used in the present disclosure is not particularly limited, but includes a method of blending the essential components and, if necessary, the optional components, and melt-kneading them, more specifically, a method of uniformly dry-mixing them in a tumbler or Henschel mixer, if necessary, and then feeding them into a twin-screw extruder to melt-knead them.

[0043] The melt kneading can be carried out by heating the resin to a temperature range in which the resin temperature is equal to or higher than the melting point of the PAS resin (A), preferably equal to or higher than the melting point + 10°C, more preferably equal to or higher than the melting point + 10°C, even more preferably equal to or higher than the melting point + 20°C, preferably equal to or lower than the melting point + 100°C, more preferably equal to or lower than the melting point + 50°C.

[0044] The melt kneader is preferably a twin-screw kneading extruder from the viewpoint of dispersibility and productivity. For example, it is preferable to melt knead while appropriately adjusting the resin component discharge amount in the range of 5 to 500 (kg / hr) and the screw rotation speed in the range of 50 to 500 (rpm), and it is more preferable to melt knead under the condition that the ratio (discharge amount / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). In addition, each component may be added and mixed to the melt kneader simultaneously or in portions. For example, when graphite (B), which is an essential component, or other fibrous fillers are added as necessary among the components, it is preferable to feed them into the extruder from a side feeder of the twin-screw kneading extruder from the viewpoint of dispersibility. The position of the side feeder is preferably such that the ratio of the distance from the extruder resin input part (top feeder) to the side feeder to the total screw length of the twin-screw kneading extruder is 0.1 or more, more preferably 0.3 or more. Moreover, the ratio is preferably 0.9 or less, and more preferably 0.7 or less.

[0045] The PAS resin composition according to the present disclosure obtained by melt kneading in this manner is a molten mixture containing the essential components, optional components added as necessary, and components derived therefrom. Therefore, the PAS resin composition according to the present disclosure has a morphology of a sea-island structure in which the PAS resin (A) forms a continuous phase and island phases containing the thermoplastic elastomer (B) and optional components are dispersed. In the PAS resin composition according to the present disclosure, the dispersion diameter of the island phase is preferably 5 μm or less. When the average dispersion diameter of the dispersed phase is as small as 5 μm or less, the resin composition and its molded product exhibit excellent impact resistance and cold and thermal shock resistance. From the same viewpoint, the dispersion diameter is more preferably 5 μm or less, and even more preferably 3 μm or less. The average dispersion diameter of the dispersed phase in the present application is a value measured using the method described in the Examples.

[0046] After the melt-kneading, the PAS resin composition according to the present disclosure is preferably processed into a form such as pellets, chips, granules, powder, etc. by a known method, for example, by extruding the molten resin composition into a strand shape, and then pre-dried at a temperature range of 100 to 150°C as necessary.

[0047] <Molded products and manufacturing methods for molded products> The molded article according to this embodiment is obtained by melt molding the PAS resin composition. The manufacturing method of the molded article according to this embodiment includes a step of melt molding the PAS resin composition obtained by the manufacturing method described above. Therefore, the molded article according to this embodiment has a morphology in which the PAS resin (A) forms a continuous phase and other essential components and optional components are dispersed. The PAS resin composition having such a morphology allows the molded article to have excellent mechanical strength.

[0048] The PAS resin composition according to the present embodiment can be subjected to various molding processes such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, and transfer molding, but is particularly suitable for injection molding because of its excellent releasability. When molding by injection molding, various molding conditions are not particularly limited, and molding can be performed by a normal general method. For example, in an injection molding machine, the PAS resin composition is melted at a resin temperature in a temperature range of the melting point of the PAS resin (A) or higher, preferably in a temperature range of the melting point +10°C or higher, more preferably in a temperature range of the melting point +10°C to the melting point +100°C, and even more preferably in a temperature range of the melting point +20 to the melting point +50°C, and then the resin is injected into a mold from a resin discharge port and molded. At that time, the mold temperature may also be set to a known temperature range, for example, room temperature (23°C) to 300°C, preferably 130 to 190°C.

[0049] The method for producing a molded article according to this embodiment may include a step of annealing the molded article. The optimum conditions for the annealing treatment are selected depending on the application or shape of the molded article, and the annealing temperature is in a temperature range of the glass transition temperature of the PAS resin (A) or higher, preferably in a temperature range of the glass transition temperature +10°C or higher, and more preferably in a temperature range of the glass transition temperature +30°C or higher. On the other hand, it is preferably in a range of 260°C or lower, and more preferably in a range of 240°C or lower. The annealing time is not particularly limited, but is preferably in a range of 0.5 hours or higher, and more preferably in a range of 1 hour or higher. On the other hand, it is preferably in a range of 10 hours or lower, and more preferably in a range of 8 hours or lower. In such a range, not only the distortion of the molded article obtained is reduced and the crystallinity of the resin is improved, but also the dimensional stability, mechanical properties, and chemical resistance are further improved, which is preferable. The annealing treatment may be performed in air, but is preferably performed in an inert gas such as nitrogen gas.

[0050] <Application> The PAS resin molded product of the present disclosure is characterized by excellent vibration-damping properties and mechanical properties, especially impact resistance, and is therefore particularly suitable for in-vehicle parts and the like. Specifically, it can be suitably used for automobile dampers, engine covers, silent spacers, engine and transmission parts, position sensors, liquid level sensors, and the like. In addition, since it is possible to suppress noise and deterioration due to contact between parts by suppressing vibration, it can also be suitably used for components such as gears and modules. In addition, the molded product of the present disclosure is suitable not only for in-vehicle parts, but also for components of equipment that generates vibration, and therefore ultrasonic cleaning devices and the like can also be mentioned. Furthermore, it can be made into the following ordinary resin molded products. For example, protective and supporting materials for box-shaped electric and electronic component integrated modules, multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystal displays, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, and other representative electric and electronic parts; VTR parts, television parts, irons, headsets, etc. Home and office electrical appliance parts such as air dryers, rice cooker parts, microwave oven parts, audio parts, audio / visual equipment parts such as laser discs, compact discs, DVD discs, and Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, and water-related equipment parts such as water heaters, bath water volume and temperature sensors; office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, lighters, typewriters, and other machine related parts; optical equipment and precision machinery related parts such as microscopes, binoculars, cameras, and watches;Alternator terminals, alternator connectors, brush holders, slip rings, IC regulators, potentiometer bases for light dimmers, relay blocks, inhibitor switches, various valves such as exhaust gas valves, various pipes for fuel, exhaust and intake systems, air intake nozzle snorkels, intake manifolds, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, temperature sensors, air flow meters, brake pad wear sensors, thermostat bases for air conditioners, heating hot air flow control valves, radiators Examples of automotive and vehicle related parts include brush holders for motors, water pump impellers, turbine vanes, wiper motor related parts, distributors, starter switches, ignition coils and bobbins, motor insulators, motor rotors, motor cores, starter relays, transmission wire harnesses, windshield washer nozzles, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and other various applications. EXAMPLES

[0051] The present invention will be described below using examples and comparative examples, but is not limited to these examples. In the following, unless otherwise specified, "%" and "parts" are based on mass.

[0052] <Example 1 and Comparative Example 1> Each material was mixed according to the composition and mixing amounts shown in Table 1. The mixed materials were then fed into a vented twin-screw extruder "TEX-30α" manufactured by Japan Steel Works, Ltd., and melt-kneaded at a resin component discharge rate of 30 kg / hr, a screw rotation speed of 200 rpm, and a set resin temperature of 320°C to obtain pellets of the resin composition. The glass fiber, which is component (C), was fed from the side feeder (S / T ratio 0.5), and the other materials were mixed uniformly in advance in a tumbler and fed from the top feeder. The pellets of the obtained resin composition were dried in a gear oven at 140°C for 2 hours, and then injection molded to produce various molded products, and the following tests were performed.

[0053] <Evaluation>

[0054] (1) Measurement of melt viscosity (V6) The melt viscosity (V6) was measured using a Shimadzu flow tester "CFT-500D" at 300°C and a load of 1.96 x 10 6 The measurements were taken after maintaining the condition for 6 minutes under the conditions of Pa and L / D = 10 (mm) / 1 (mm). The results are shown in Table 1.

[0055] (2) Measurement of elastomer dispersion diameter The pellets obtained were freeze-fractured and then immersed in chloroform to dissolve and remove the elastomer components. The pellets were then dried and the fracture surfaces were observed at a magnification of 10,000x using a JEOL Ltd. scanning electron microscope "JSM-IT300." The diameter of the holes formed by the removal of the elastomer was measured, and the number average of the diameters of 20 holes was taken as the average dispersion diameter of the elastomer (μm). The results are shown in Table 1.

[0056] (3) Evaluation of vibration damping The obtained pellets were fed into a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) with a cylinder temperature set to 310°C, and injection molding was performed using a UL 1 / 16 inch bar piece molding die with a mold temperature controlled at 140°C to obtain a test piece. The resin was injected from a single gate so that the test piece did not include a welded part. The obtained test piece was fixed with a jig, and a strain gauge was attached 500 mm from the jig. The other conditions were in accordance with ASTM-E756-83, and the loss factor η was obtained by the cantilever method. The loss factor was measured at the secondary resonance frequency. The results are shown in Table 1.

[0057] (4) Measurement of Charpy impact strength at room and low temperatures The obtained pellets were fed into a Sumitomo Heavy Industries injection molding machine (SE-75D-HP) with a cylinder temperature set at 310°C, and injection molding was performed using a mold for molding ISO Type-A dumbbell pieces with a mold temperature controlled at 140°C to obtain ISO Type-A dumbbell pieces. Note that the test pieces were produced by injecting resin from a single gate so that they would not contain welds. The central part of the obtained dumbbell piece was cut into a rod shape of 80 mm in length, 10 mm in width, and 4 mm in thickness, and the one with and without notching was used as an impact resistance test piece. A Charpy impact test was performed in accordance with ISO179-1 / 1eA to measure the impact strength (kJ / mm 2 For measurements at low temperatures, the test pieces were immersed in liquid nitrogen for 5 minutes and then the test was carried out in the same manner. The results are shown in Table 1.

[0058] [Table 1]

[0059] <Raw materials used> The raw material components of the PAS resin composition are shown below. ·PPS resin A-1: PPS resin (melt viscosity (V6) 45 Pa·s, linear type

[0060] ·Thermoplastic elastomer B-1: Amine-modified styrene-based thermoplastic elastomer, "Tuftec (registered trademark) MP10" manufactured by Asahi Kasei Corporation, styrene content 30 parts by mass, glass transition temperature -52°C, density 0.91 g / cm 3 b-2: Ethylene-glycidyl methacrylate thermoplastic elastomer, "Bondfast 7L" manufactured by Sumitomo Chemical Co., Ltd., styrene content 0 parts by mass, glass transition temperature -33°C, density 0.96 g / cm 3

[0061] Fillers C-1: Glass fiber (chopped strand, fiber diameter 10.5 μm)

[0062] The results in Table 1 show that the molded article made of the PAS resin composition of Example 1 has better vibration-proofing properties than the molded article of Comparative Example 1, and has equivalent mechanical properties (impact resistance).

Claims

1. A polyarylene sulfide resin composition comprising a polyarylene sulfide resin (A) and a thermoplastic elastomer (B), the thermoplastic elastomer (B) is a styrene-based thermoplastic elastomer whose terminals are amine-modified and has a styrene content in the range of 10 to 40 parts by mass; The polyarylene sulfide resin composition has a blending amount of the thermoplastic elastomer (B) of 10 to 70 parts by mass per 100 parts by mass of the polyarylene sulfide resin (A).

2. 2. The polyarylene sulfide resin composition according to claim 1, wherein the thermoplastic elastomer (B) has a glass transition point of −40° C. or lower.

3. The density of the thermoplastic elastomer (B) is 0.95 g / cm ３ 3. The polyarylene sulfide resin composition according to claim 1 or 2, wherein:

4. 3. The polyarylene sulfide resin composition according to claim 1 or 2, wherein a sea-island structure is formed in which island phases containing the thermoplastic elastomer (B) are dispersed in a continuous phase containing the polyarylene sulfide resin (A), and the dispersed diameter of the island phases is 5 μm or less.

5. The polyarylene sulfide resin composition according to claim 1 or 2, wherein the polyarylene sulfide resin (A) has a melt viscosity (V6) of 35 Pa·s or more and 175 Pa·s or less. (However, the melt viscosity (V6) was measured using a flow tester at 300°C and a load of 1.96 x 10 ６ The values ​​are those measured after holding for 6 minutes at 10 Pa and L / D = 10 mm / 1 mm.

6. A molded article obtained by melt molding the resin composition according to claim 1 or 2.

7. A method for producing a polyarylene sulfide resin composition, comprising a step of blending a polyarylene sulfide resin (A) and a thermoplastic elastomer (B) and melt-kneading the mixture at a temperature equal to or higher than the melting point of the polyarylene sulfide resin, the thermoplastic elastomer (B) is a styrene-based thermoplastic elastomer whose terminals are amine-modified and has a styrene content in the range of 10 to 40 parts by mass; The method for producing a polyarylene sulfide resin composition, wherein the blending amount of the thermoplastic elastomer (B) is 10 to 70 parts by mass per 100 parts by mass of the polyarylene sulfide resin (A).

8. The method for producing a polyarylene sulfide resin composition according to claim 7, wherein the glass transition point of the thermoplastic elastomer (B) is −40° C. or lower.

9. The density of the thermoplastic elastomer (B) is 0.95 g / cm ３ The method for producing the polyarylene sulfide resin composition according to claim 7 or 8, wherein the polyarylene sulfide resin composition is:

10. 9. The method for producing a polyarylene sulfide resin composition according to claim 7 or 8, wherein a sea-island structure is formed in which island phases containing the thermoplastic elastomer (B) are dispersed in a continuous phase containing the polyarylene sulfide resin (A), and the dispersed diameter of the island phases is 5 μm or less.

11. The method for producing a polyarylene sulfide resin composition according to claim 7 or 8, wherein the polyarylene sulfide resin (A) has a melt viscosity (V6) of 35 Pa·s or more and 175 Pa·s or less. (However, the melt viscosity (V6) was measured using a flow tester at 300°C and a load of 1.96 x 10 ６ The values ​​are those measured after holding for 6 minutes at 10 Pa and L / D = 10 mm / 1 mm.

12. A method for producing a molded article, comprising the steps of producing a polyarylene sulfide resin composition by the production method according to claim 7 or 8, and melt-molding the obtained polyarylene sulfide resin composition.

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