JP2007070587A - Polyarylene sulfide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyarylene sulfide composition having excellent dimensional stability, heat resistance, metal mold releasability, low gas properties (a small volume of an emitted gas) and melt fluidity and small anisotropy of thermal conductivity and thermal expansivity and useful for especially applications of electrical parts such as electrical/electronic parts or automotive instrumentation parts. <P>SOLUTION: The polyarylene sulfide composition comprises (a) a polyarylene sulfide, (b) a low-melting alloy, (c) metal powder having ≥400°C melting point and/or carbon fibers having ≥100 W/m K thermal conductivity, (d) scaly boron nitride powder, (e) coated magnesium oxide powder and (f) carnauba wax. (b) The low-melting alloy has ≥300°C liquid phase line temperature and ≥150 to ≤250°C solid phase line temperature. (d) The scaly boron nitride powder has a hexagonal crystal structure. (e) The coated magnesium oxide powder is coated with a double oxide of silicon and magnesium and/or a double oxide of aluminum and magnesium. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is excellent in thermal conductivity, dimensional stability, heat resistance, mold releasability, and melt fluidity, generates a small amount of gas during melting (hereinafter referred to as low gas property), and has thermal conductivity. In particular, the present invention relates to a polyarylene sulfide composition having low thermal expansion and low anisotropy, and more particularly to a polyarylene sulfide composition particularly useful for electrical parts such as electrical / electronic parts or automotive electrical parts. .

  Polyarylene sulfide is a resin that exhibits excellent properties such as heat resistance, chemical resistance, and moldability, and is used widely in electrical and electronic equipment members, automotive equipment members, OA equipment members, etc. by taking advantage of its superior properties. ing.

  However, since polyarylene sulfide has low thermal conductivity, for example, when an electronic component with heat generation is sealed, the generated heat cannot be efficiently diffused, dimensional change due to thermal expansion, deformation due to heat, Alternatively, problems such as gas generation may occur.

  Several attempts have been made to improve the thermal conductivity of polyarylene sulfide. For example, (a) polyphenylene sulfide, (b) alumina powder having an average particle size of 5 μm or less, and (c) fiber. There has been proposed a resin composition containing a reinforcing material (see, for example, Patent Document 1). One type selected from (a) polyarylene sulfide, (b) carbon fiber having a specific tensile modulus, and (c) graphite, metal powder, alumina, magnesia, titania, dolomite, boron nitride, and aluminum nitride. Resin composition containing the above filler (see, for example, Patent Document 2), (a) matrix resin, (b) thermally conductive filler dispersed in matrix resin, and (c) low melting point alloy having a melting point of 500 ° C. or lower A resin composition comprising (a) a resin comprising polyphenylene sulfide and polyphenylene ether, (b) a carbon fiber having a specific thermal conductivity, and (c) graphite. The thing is proposed (for example, refer patent document 4). Furthermore, a silicone composition containing scaly boron nitride powder having a hexagonal crystal structure has been proposed (see, for example, Patent Document 5).

Japanese Patent Laid-Open No. 04-033958 JP 2002-129015 A WO2003-029352 JP 2004-137401 A JP 2000-345039 A

  However, in the methods proposed in Patent Documents 1 to 4, the thermal conductivity of the composition is low, the thermal conductivity is anisotropic, and the thermal expansion of the composition is anisotropic. There is a problem that the dimensional stability is large and sufficient dimensional stability cannot be obtained. In addition, in order to obtain sufficiently high thermal conductivity in these proposed methods, a high filler content is essential, so that the mechanical strength of the composition is significantly reduced, and the mold releasability and appearance of the molded product are deteriorated. It was deteriorating. That is, in all of these proposed methods, it is difficult to simultaneously obtain high thermal conductivity, high mechanical strength, good mold releasability, and molded product appearance. Furthermore, in the method proposed in Patent Document 5, the scaly boron nitride powder itself having a hexagonal crystal structure has a very large thermal conductivity and is useful as a thermally conductive filler. As described in the above, there is a problem that since it is a scaly filler, it is easily oriented, and the thermal conductivity anisotropy between a plane parallel to the orientation and a plane perpendicular to the orientation is large.

  Therefore, the present invention is a polyarylene sulfide having excellent thermal conductivity, dimensional stability, heat resistance, mold releasability, low gas property and melt fluidity and low thermal conductivity and thermal expansion anisotropy. An object of the present invention is to provide a polyarylene sulfide composition that is particularly useful for electrical component applications such as electrical / electronic components or automotive electrical components.

  As a result of intensive studies to solve the above problems, the present inventors have found that polyarylene sulfide has a low melting point alloy having a specific liquidus temperature and a solidus temperature, a specific metal powder and / or carbon fiber, Scalar boron nitride powder having a specific structure, coated magnesium oxide powder coated with a specific double oxide, and a polyarylene sulfide composition comprising carnauba wax have low anisotropy and high thermal conductivity. It has been found that the composition can be a composition having low thermal expansion and excellent mold releasability, thereby completing the present invention.

  That is, the present invention includes (a) polyarylene sulfide, (b) a low melting point alloy having a liquidus temperature of 300 ° C. or higher and a solidus temperature of 150 ° C. or higher and 250 ° C. or lower, and (c) a metal having a melting point of 400 ° C. or higher. Powder and / or carbon fiber having a thermal conductivity of 100 W / m · k or more, (d) flaky boron nitride powder having a hexagonal crystal structure, (e) a double oxide of silicon and magnesium and / or aluminum and magnesium The present invention relates to a polyarylene sulfide composition comprising a coated magnesium oxide powder coated with a double oxide and (f) carnauba wax.

  Hereinafter, the present invention will be described in detail.

  The polyarylene sulfide composition of the present invention comprises (a) polyarylene sulfide, (b) a low melting point alloy (hereinafter referred to simply as “b”) having a liquidus temperature of 300 ° C. or higher and a solidus temperature of 150 ° C. or higher and 250 ° C. or lower. ) A low melting point alloy), (c) a metal powder having a melting point of 400 ° C. or higher (hereinafter simply referred to as (c) metal powder) and / or a carbon fiber having a thermal conductivity of 100 W / m · k or higher ( Hereinafter, simply referred to as (c) carbon fiber), (d) scaly boron nitride powder having a hexagonal crystal structure (hereinafter simply referred to as (d) scaly boron nitride powder), and (e) silicon and magnesium. Coated magnesium oxide powder coated with a double oxide and / or a double oxide of aluminum and magnesium (hereinafter simply referred to as (e) coated magnesium oxide powder), and (f) a carnauba wax A.

  As the polyarylene sulfide (a) constituting the polyarylene sulfide composition of the present invention, any polyarylene sulfide may be used as long as it belongs to the category called polyarylene sulfide. Since the composition was excellent in mechanical strength and moldability, it was measured with a Koka flow tester using a die having a diameter of 1 mm and a length of 2 mm under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg. Polyarylene sulfide having a melt viscosity of 50 to 3000 poise is preferable, and one having a melt viscosity of 60 to 1500 poise is particularly preferable.

  The polyarylene sulfide (a) preferably contains 70 mol% or more, particularly 90 mol% or more of a p-phenylene sulfide unit represented by the following general formula (1) as a structural unit.

そして、他の構成成分としては、例えば下式の一般式（２）に示されるｍ−フェニレンスルフィド単位、

And as another component, for example, m-phenylene sulfide unit represented by the following general formula (2),

一般式（３）に示されるｏ−フェニレンスルフィド単位、

O-phenylene sulfide unit represented by the general formula (3),

一般式（４）に示されるフェニレンスルフィドスルホン単位、

A phenylene sulfide sulfone unit represented by the general formula (4),

一般式（５）に示されるフェニレンスルフィドケトン単位、

A phenylene sulfide ketone unit represented by the general formula (5),

一般式（６）に示されるフェニレンスルフィドエーテル単位、

A phenylene sulfide ether unit represented by the general formula (6),

一般式（７）に示されるジフェニレンスルフィド単位、

A diphenylene sulfide unit represented by the general formula (7),

一般式（８）に示される置換基含有フェニレンスルフィド単位、

A substituent-containing phenylene sulfide unit represented by the general formula (8),

（ここで、ＲはＯＨ，ＮＨ_２，ＣＯＯＨ，ＣＨ_３を示し、ｎは１又は２を示す。）
一般式（９）に示される分岐構造含有フェニレンスルフィド単位、

(Here, R represents OH, NH ₂ , COOH, CH ₃ , and n represents 1 or 2)
A branched structure-containing phenylene sulfide unit represented by the general formula (9):

等を含有していてもよく、中でもポリ（ｐ−フェニレンスルフィド）が好ましい。

In particular, poly (p-phenylene sulfide) is preferable.

  The method for producing the (a) polyarylene sulfide is not particularly limited. For example, the polyarylene sulfide may be produced by a method in which an alkali metal sulfide and a dihaloaromatic compound are reacted in a generally known polymerization solvent. Possible alkali metal sulfides include, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof, which may be used in the form of hydrates. These alkali metal sulfides can be obtained by reacting an alkali metal hydrosulfide with an alkali metal base. However, these alkali metal sulfides can be prepared in situ prior to addition of the dihaloaromatic compound into the polymerization system. You can use the one adjusted in. Examples of the dihaloaromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-4-bromobenzene, 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorodiphenyl ether, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl and the like. The charging ratio of the alkali metal sulfide and the dihaloaromatic compound is preferably in the range of alkali metal sulfide / dihaloaromatic compound (molar ratio) = 1.00 / 0.90 to 1.10.

  As the polymerization solvent, a polar solvent is preferable, and an organic amide which is aprotic and stable to alkali at high temperature is particularly preferable. Examples of the organic amide include N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, N-methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, and N-methyl-2-pyrrolidone. 1,3-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane, tetramethylurea and mixtures thereof. Moreover, it is preferable to use this polymerization solvent in 150-3500 weight% with respect to the polymer produced | generated by superposition | polymerization, and it is preferable to use especially in the range used as 250-1500 weight%. The polymerization is preferably carried out at 200 to 300 ° C., particularly 220 to 280 ° C. for 0.5 to 30 hours, particularly 1 to 15 hours with stirring.

  Furthermore, even if the (a) polyarylene sulfide is linear or is treated and crosslinked at a high temperature in the presence of oxygen, a slight amount of trihalo or higher polyhalo compound is added to form a slight crosslink. Alternatively, a branched structure may be introduced, a heat treatment may be performed in a non-oxidizing inert gas such as nitrogen, or a mixture of these structures may be used.

  The blending amount of (a) polyarylene sulfide constituting the polyarylene sulfide composition of the present invention is 15 to 50% by weight because it becomes a polyarylene sulfide composition particularly excellent in mechanical strength, moldability and thermal conductivity. It is preferable that

  The (b) low melting point alloy constituting the polyarylene sulfide composition of the present invention is a low melting point alloy that simultaneously satisfies the two conditions of a liquidus temperature of 300 ° C. or higher and a solidus temperature of 150 ° C. or higher and 250 ° C. or lower. There is no particular limitation as long as the condition is satisfied. Examples of the (b) low melting point alloy include a Sn—Cu alloy having a liquidus temperature of 300 ° C. or higher and a solidus temperature of 150 ° C. or higher and 250 ° C. or lower, a liquidus temperature of 300 ° C. or higher, and a solidus temperature of 150 ° C. Sn-Al alloy having a liquidus temperature of 300 ° C or higher and a solidus temperature of 150 ° C or higher and 250 ° C or lower, a liquidus temperature of 300 ° C or higher, and a solidus temperature of 150 ° C. Sn-Ag alloy with a liquidus temperature of 300 ° C or higher and a solidus temperature of 150 ° C or higher and 250 ° C or lower, a liquidus temperature of 300 ° C or higher, and a solidus temperature of 150 ° C. Sn-Sb alloy with a liquidus temperature of 300 ° C or higher and a solidus temperature of 150 ° C or higher and 250 ° C or lower, a liquidus temperature of 300 ° C or higher and a solidus temperature of 150 ° C. Li-Z between ℃ and 250 ℃ Alloy, Sn—Cu—Ni alloy having a liquidus temperature of 300 ° C. or higher and a solidus temperature of 150 ° C. or higher and 250 ° C. or lower, Sn having a liquidus temperature of 300 ° C. or higher and a solidus temperature of 150 ° C. or higher and 250 ° C. or lower -Cu-Ag alloy etc. are mentioned.

  Here, in a general alloy, the liquidus temperature is a temperature at which the alloy exists in the liquid phase at a temperature exceeding the temperature, and the solidus temperature is the temperature at a temperature lower than the temperature. Indicates the temperature present in the solid phase. An alloy under a temperature condition not lower than the solidus temperature and not higher than the liquidus temperature exists in a state where the liquid phase and the solid phase coexist. In the polyarylene sulfide composition of the present invention, in order to achieve high thermal conductivity, which is one of the objects of the present invention, the (b) low melting point alloy is in a state where the liquid phase and the solid phase coexist. It is necessary to form a composition in the temperature range, and the requirements for achieving this condition are the liquidus temperature of 300 ° C. or higher and the solidus temperature of 150 ° C. or higher and 250 ° C. or lower. Here, when the liquidus temperature is less than 300 ° C., or when the solidus temperature exceeds 250 ° C., the liquid phase and the solid phase under the melt kneading or molding process conditions of a general polyarylene sulfide composition It is difficult to exist as a coexisting state, and high thermal conductivity cannot be achieved. On the other hand, when the solidus temperature is less than 150 ° C., it is difficult to completely solidify the polyarylene sulfide composition at the shape retention temperature, which is a condition for molding the polyarylene sulfide composition. Problems can occur.

  The blending amount of the (b) low melting point alloy constituting the polyarylene sulfide composition of the present invention is 5 to 40% by weight because it becomes a polyarylene sulfide composition excellent in mechanical strength, formability and thermal conductivity. It is preferable that

  The polyarylene sulfide composition of the present invention contains (c) metal powder and / or (c) carbon fiber.

  As the metal powder (c), any metal powder having a melting point of 400 ° C. or higher can be used, and a mixture of a plurality of kinds of metal powders or a powder of a plurality of kinds of metals can be used. Absent. Among them, since (b) the familiarity with the low melting point alloy is good, the polyarylene sulfide composition is particularly excellent in thermal conductivity. Therefore, (c) the metal powder constitutes (b) the low melting point alloy. A metal powder of another component excluding the metal having the lowest melting point among the metal components, a powder mixture of the metal powder and one or more metal powders of the metal other than the metal powder, It is preferable to use a powder of an alloy with one or more metals other than the metal to be excluded, and among them, (b) a Sn-Cu alloy or a Sn-Cu-Ni alloy is used as the low melting point alloy, and (c) a metal powder. It is preferable to use Cu powder, mixed powder of Cu powder and one or more metal powders of metals other than the Cu powder, and powder of alloy of Cu and one or more metals other than the metal, and (b ) Sn- as low melting point alloy When an n alloy is used, (c) as a metal powder, Zn powder, a mixture powder of Zn powder and one or more metal powders of metals other than the Zn powder, Zn and one or more metals other than the metal, It is preferable to use a powder of the alloy.

  Here, when the metal powder has a melting point of less than 400 ° C., when the polyarylene sulfide composition is produced, the metal powder is easily melted, and the heat conduction component hardly forms a continuous phase due to the melting of the metal powder. The composition is inferior in thermal conductivity.

Since the metal powder (c) is a polyarylene sulfide composition having particularly excellent mechanical properties and thermal conductivity, the average particle diameter (D ₅₀ ) measured by the laser diffraction scattering method is 0.05 to 100 μm. Are preferable, and those having a thickness of 0.1 to 50 μm are particularly preferable.

  Further, the shape of the metal powder (c) is not particularly limited, and examples thereof include dendritic powder, flake powder, square powder, spherical powder, granular powder, acicular powder, irregular powder, and spongy powder. It is done. Moreover, the mixture of these shapes may be sufficient. Examples of the method for producing the metal powder (c) include an electrolysis method, a mechanical pulverization method, an atomization method, a heat treatment method, a chemical production method, and the like, and are not limited to these production methods.

  In the case of using the (c) metal powder, the blending amount is preferably 5 to 40% by weight, since it becomes a polyarylene sulfide composition excellent in mechanical strength, moldability, and thermal conductivity. Since it becomes a polyarylene sulfide composition excellent in thermal conductivity, it is preferable to use (b) low melting point alloy / (c) metal powder = 1/8 to 8/1 (weight ratio).

  Further, the (c) carbon fiber is a carbon fiber having a thermal conductivity of 100 W / m · k or more, and the (c) carbon fiber satisfies a condition of a thermal conductivity of 100 W / m · k or more. It can be used without any restrictions. Carbon fibers can be broadly classified into polyacrylonitrile, pitch, rayon, polyvinyl alcohol and the like, and any of these may be used as long as the thermal conductivity is 100 W / m · k or more, preferably the pitch system. Carbon fiber. When carbon fibers having a thermal conductivity of less than 100 W / m · k are used to form a polyarylene sulfide composition, (b) a low melting point alloy, (d) a flaky boron nitride powder having a hexagonal crystal structure, and (e ) Even if blended in combination with the coated magnesium oxide powder, a polyarylene sulfide composition having high thermal conductivity cannot be obtained, and the object of the present invention cannot be achieved.

  Examples of the shape of the carbon fiber (c) include a chopped fiber having a fiber diameter of 5 to 20 μm and a fiber length of 2 to 8 mm, a milled fiber having a fiber diameter of 5 to 20 μm and a fiber length of 30 to 150 μm. Chopped fiber is preferred because it provides an excellent polyarylene sulfide composition.

  In addition, when (c) carbon fiber is used in constituting the polyarylene sulfide composition of the present invention, it is particularly excellent in mechanical strength, moldability, and thermal conductivity. % Is preferred.

The (d) scaly boron nitride powder constituting the polyarylene sulfide composition of the present invention has a hexagonal crystal structure, and any material can be used as long as it satisfies the conditions. (D) As a scaly boron nitride powder, for example, a crude boron nitride powder is heat-treated in a nitrogen atmosphere in the presence of an alkali metal or alkaline earth metal borate at 2000 ° C. for 3 to 7 hours to form boron nitride. It can be produced by sufficiently developing the crystals and, after pulverization, purifying with a strong acid such as nitric acid as necessary. The (d) scaly boron nitride powder is a polyarylene sulfide composition having excellent dispersibility and mechanical properties in the polyarylene sulfide composition of the present invention. The measured average particle diameter (D ₅₀ ) is preferably 3 to 30 μm. Further, the (d) scaly boron nitride powder exhibits high crystallinity and can be a polyarylene sulfide composition having particularly excellent thermal conductivity, and thus is determined by a powder X-ray diffraction method. (102) G represented by the ratio of the sum of the integrated intensity values of (100) diffraction line and (101) diffraction line [I _{(100) + (101)} ] to the integrated intensity value [I ₍₁₀₂₎ ] of the diffraction line . It is preferable that I value (GI = [I _{(100) + (101)} ] / [I ₍₁₀₂₎ ]) is in the range of 0.8-10.

  As the blending amount of (d) flaky boron nitride powder in the polyarylene sulfide composition of the present invention, it is possible to obtain a polyarylene sulfide composition having high thermal conductivity and low thermal conductivity anisotropy. From 5 to 25% by weight is preferable.

  (E) The coated magnesium oxide powder constituting the polyarylene sulfide composition of the present invention is a coated magnesium oxide powder coated with a double oxide of silicon and magnesium and / or a double oxide of aluminum and magnesium. Any material can be used as long as it belongs to the category of magnesium oxide powder, and for example, it can be obtained from the method described in JP-A-2004-027177. Here, when a magnesium oxide powder whose surface is not coated with any of the double oxides is used to form a polyarylene sulfide composition, (b) a low melting point alloy, (c) a metal powder, and (d) a scaly shape. Even when blended with boron nitride powder, a polyarylene sulfide composition having high thermal conductivity cannot be obtained, and the object of the present invention cannot be achieved.

Here, examples of the double oxide of silicon and magnesium include silicon oxides represented by forsterite (Mg ₂ SiO ₄ ) and the like, metal oxides containing magnesium and oxygen, and composites of magnesium oxide and silicon oxide. Examples of the double oxide of aluminum and magnesium include aluminum represented by spinel (Al ₂ MgO ₄ ) and the like, metal oxides containing magnesium and oxygen, and composites of magnesium oxide and aluminum oxide.

  The (e) coated magnesium oxide powder may be further surface-treated with a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent as necessary. Examples thereof include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like. Examples of the coupling agent include isopropyl triisostearoyl titanate, and examples of the aluminate coupling agent include acetoalkoxyaluminum diisopropylate.

Since the (e) coated magnesium oxide powder is a polyarylene sulfide composition particularly excellent in mechanical properties and thermal conductivity, the average particle diameter (D ₅₀ ) measured by the laser diffraction scattering method is 1 to ₅₀₀ μm. It is preferable that it has, and it is especially preferable that it is 3-100 micrometers.

  In addition, the blending amount of the (e) coated magnesium oxide powder is preferably 15 to 50% by weight because a polyarylene sulfide composition excellent in mechanical strength, moldability and thermal conductivity is obtained.

  The (f) carnauba wax constituting the polyarylene sulfide composition of the present invention is blended to improve mold releasability and product appearance when the polyarylene sulfide composition is molded as a molded product. As the (f) carnauba wax, a general commercial product can be used. The blending amount of the (f) carnauba wax is less likely to cause problems such as mold contamination during the molding process, and becomes a polyarylene sulfide composition excellent in mold releasability and molded article appearance. It is preferable that it is 05 to 5 weight%.

  Moreover, since the polyarylene sulfide composition of the present invention has a smaller thermal conductivity anisotropy, it is preferable to blend (g) graphite. The (g) graphite is not particularly limited, and any graphite can be used as long as the thermal conductivity anisotropy can be reduced. Graphite is roughly classified into natural graphite and artificial graphite. Natural graphite includes, for example, earthy graphite, scaly graphite, scaly graphite, and any of these may be used. (G) The fixed carbon content of the graphite is a graphite having a fixed carbon content of 95% or more because it becomes a polyarylene sulfide composition having particularly excellent thermal conductivity and low anisotropy. It is preferable. The particle size of the (g) graphite is preferably a polyarylene sulfide composition having particularly excellent thermal conductivity, so that the average particle size of primary particles is 0.5 to 400 μm.

  When the polyarylene sulfide composition of the present invention is formed by blending the (g) graphite, the blending amount is a polyarylene sulfide composition having a particularly low mechanical strength, moldability, and thermal conductivity anisotropy. Therefore, the content is preferably 5 to 40% by weight.

  Furthermore, the polyarylene sulfide composition of the present invention can be used in various thermosetting resins and thermoplastic resins, such as epoxy resins, cyanate ester resins, phenol resins, polyimides, silicone resins, polyolefins, without departing from the object of the present invention. One or more of polyester, polyamide, polyphenylene oxide, polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, etc. can be mixed and used.

  As the method for producing the polyarylene sulfide composition of the present invention, a conventionally used hot melt kneading method can be used, for example, a hot melt kneading method using a single or twin screw extruder, a kneader, a mill, a Brabender, or the like. In particular, a melt-kneading method using a twin screw extruder excellent in kneading ability is preferable. Moreover, the kneading | mixing temperature in this case is not specifically limited, Usually, it can select arbitrarily from 280-400 degreeC. Moreover, the polyarylene sulfide composition of the present invention can be molded into an arbitrary shape using an injection molding machine, an extrusion molding machine, a transfer molding machine, a compression molding machine, or the like.

  In the polyarylene sulfide composition of the present invention, fibrous or non-fibrous reinforcing materials can be used without departing from the object of the present invention. Examples of the fibrous reinforcing material include glass fiber, alumina fiber, potassium titanate whisker, aluminum borate whisker, and zinc oxide whisker. Examples of the non-fibrous reinforcing material include calcium carbonate, mica, silica, talc, calcium sulfate, kaolin, clay, wollastonite, zeolite, glass beads, and glass powder. These reinforcing materials can be used in combination of two or more, and can be used after surface treatment with a silane-based or titanium-based coupling agent if necessary. Particularly preferred reinforcing materials are glass fibers for fibrous reinforcing materials and calcium carbonate and talc for non-fibrous reinforcing materials.

  Furthermore, the polyarylene sulfide composition of the present invention is further provided with a conventionally known release agent, lubricant, heat stabilizer, antioxidant, ultraviolet absorber, crystal nucleating agent, foaming agent within the range not departing from the object of the present invention. In addition, one or more additives such as mold corrosion inhibitors, flame retardants, flame retardant aids, colorants such as dyes and pigments, and antistatic agents may be used in combination.

  The polyarylene sulfide composition of the present invention is particularly suitable for a semiconductor element having high exothermic property, a sealing resin such as a resistor, or a component that generates high frictional heat, as well as a generator, an electric motor, a transformer, a current transformer. Especially suitable for electrical equipment parts applications such as transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, knife switches, other pole rods, electrical parts cabinets, sockets, resistors, relay cases Sensors, LED lamps, connectors, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetics Head base, power module, semiconductor, liquid crystal, FDD carriage, FDD Chassis, hard disk drive parts (hard disk drive hubs, actuators, hard disk substrates, etc.), DVD parts (optical pickups, etc.), motor brush holders, parabolic antennas, computer-related electronic parts; VTR parts, TV parts, irons , Hair dryer, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs (registered trademark) / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Home, office electrical product parts; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriters, etc. Representative machine-related parts: Optical instruments such as microscopes, binoculars, cameras, watches, precision machine-related parts: Alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, exhaust gas valves, etc. Valves, fuel-related / exhaust / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad Wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, warm air flow -Control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve Coils, fuse connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, etc. It can be applied to various purposes.

  The present invention is a polyarylene sulfide composition having excellent thermal conductivity, dimensional stability, heat resistance, mold releasability, low gas property and melt fluidity, and low thermal conductivity and thermal expansion anisotropy. The polyarylene filled composition is particularly useful for electrical component applications such as electrical / electronic components or automotive electrical components.

  Next, although an example and a comparative example explain the present invention, the present invention is not limited to these examples.

  (A) polyarylene sulfide, (b) low melting point alloy, (c) metal powder, (c) carbon fiber having a thermal conductivity of 100 W / m · k or more, and (c ′) 100 W / carbon fiber having a thermal conductivity of less than m · k, (d) scaly boron nitride powder, (e) coated magnesium oxide powder, (e ′) magnesium oxide powder not coated with a double oxide, (f) carnauba The wax and (g) graphite are shown below.

<(A) Polyarylene sulfide>
(A-1) Poly (p-phenylene sulfide) (hereinafter simply referred to as PPS (a-1)): Melt viscosity 110 poise (a-2) Poly (p-phenylene sulfide) (hereinafter simply referred to as PPS (a -2)): Melt viscosity 300 poise (a-3) Poly (p-phenylene sulfide) (hereinafter simply referred to as PPS (a-3)): Melt viscosity poise 350 poise <(b) Low melting point Alloy>
(B-1) Low melting point alloy (hereinafter, simply referred to as low melting point alloy (b-1)); manufactured by Ishikawa Metal Co., Ltd., (trade name) Evasol R25; Cu 5 wt% Sn-Cu alloy, liquid phase Line temperature 358 ° C., solidus temperature 227 ° C.
(B-2) Low melting point alloy (hereinafter simply referred to as low melting point alloy (b-2)); Fukuda Metal Foil Industry Co., Ltd., (trade name) Sn-Cu-Ni-At-150; Cu4 weight %, Ni 2 wt% Sn—Cu—Ni alloy, liquidus temperature 460 ° C., solidus temperature 220 ° C.
(B-3) Low melting point alloy (hereinafter simply referred to as low melting point alloy (b-3)); Ishikawa Metal Co., Ltd., (trade name) Evasol F2; Ag 1.5 wt%, Cu 0.85 wt% Bi 2 wt% Sn-Ag-Cu-Bi alloy, liquidus temperature 223 ° C, solidus temperature 210 ° C.

<(C) Metal powder>
(C-1) Metal powder (hereinafter simply referred to as metal powder (c-1)); manufactured by Fukuda Metal Foil Industry Co., Ltd., (trade name) FCC-115: Cu powder, average particle size 20 μm, melting point 1083 ° C.

<(C) Carbon fiber having a thermal conductivity of 100 W / m · k or more>
(C-1) Carbon fiber having a thermal conductivity of 100 W / m · k or more (hereinafter simply referred to as high thermal conductivity carbon fiber (c-1)); (trade name) DIALEAD, manufactured by Mitsubishi Chemical Corporation K6331T; thermal conductivity 140 W / m · k, chopped fiber, fiber diameter 10 μm, fiber length 6 mm.

<(C ′) Carbon fiber having a thermal conductivity of less than 100 W / m · k>
(C′-1) Carbon fiber having a thermal conductivity of less than 100 W / m · k (hereinafter simply referred to as low thermal conductivity carbon fiber (c′-1)); manufactured by Mitsubishi Chemical Corporation (trade name) DIALEAD K223SE; thermal conductivity 20 W / m · k, chopped fiber, fiber diameter 10 μm, fiber length 6 mm.

<(D) Scale-like boron nitride powder>
(D-1) Scaly boron nitride powder (hereinafter simply referred to as boron nitride powder (d-1)); manufactured by Denki Kagaku Kogyo Co., Ltd., (trade name) DENKABORON NITRIDE SGP; 0 μm, specific surface area 2 m ² / g, G.I. I value of 0.9.
(D-2) scaly boron nitride powder (hereinafter simply referred to as boron nitride powder (d-2)); manufactured by Denki Kagaku Kogyo Co., Ltd., (trade name) DENKABORON NITRIDE SP-2; average particle diameter 4.0 μm, specific surface area 34 m ² / g, G.I. I value 7.5.

<(E) Coated magnesium oxide powder>
(E-1) Coated magnesium oxide powder coated with forsterite (hereinafter simply referred to as coated magnesium oxide powder (e-1)); manufactured by Tateho Chemical Co., Ltd. (trade name) Cool filler CF2-100 Surface coating with forsterite, average particle size 20 μm.

<(E ') Magnesium oxide powder not coated with double oxide>
(E′-1) Magnesium oxide powder not coated with a double oxide (hereinafter simply referred to as magnesium oxide powder (e′-1)); manufactured by Kyowa Chemical Industry Co., Ltd. (trade name) Pyroxuma 3320; Average particle size 17 μm.

<(F) Carnauba wax>
(F-1) Carnauba wax (hereinafter simply referred to as Carnauba wax (f-1)); Nikko Fine Products, (trade name) refined Carnauba No. 1 powder.

<(G) Graphite>
(G-1) Graphite (hereinafter, simply referred to as graphite (g-1)); manufactured by Showa Denko KK, (trade name) UFG-30; artificial graphite, fixed carbon content 99.4%.

  Evaluation and measurement methods used in Examples and Comparative Examples are shown below.

~ Measurement of bending strength ~
A test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 3.2 mm was prepared by injection molding, and the bending strength was measured using the test piece according to ASTM D-790 Method-1 (three-point bending method). did. Using a measuring device (manufactured by Shimadzu Corporation, (trade name) AG-5000B), the test was performed under the test conditions of a distance between supporting points of 50 mm and a measurement speed of 1.5 mm / min.

~ Measurement of thermal conductivity ~
It measured by the laser flash method on 23 degreeC conditions using the thermal conductivity measuring apparatus (the ULVAC company make, (brand name) TC7000; ruby laser). For the thermal conductivity in the thickness direction, the heat capacity Cp and the thermal diffusivity α in the thickness direction are obtained by a one-dimensional method, and for the thermal conductivity in the plane direction, the thermal diffusivity α ′ in the plane direction is obtained by a two-dimensional method. Thus, the thermal diffusivity was calculated from the following equation.
Thermal conductivity in the thickness direction = ρ × Cp × α
Thermal conductivity in the plane direction = ρ × Cp × α ′
Here, the density ρ was measured according to the ASTM D-792 A method (underwater substitution method). Moreover, the test piece used for a measurement cut from the flat plate used for the following linear expansion coefficient. Furthermore, in order to evaluate the anisotropy of thermal conductivity, the ratio of (thickness direction) / (plane direction) of thermal conductivity was calculated. The closer the value was to 100%, the smaller the anisotropy. Conversely, when the value was close to 0% or greatly exceeded 100%, the anisotropy was judged to be large.

~ Measurement of linear expansion coefficient ~
A flat plate having a length of 70 mm, a width of 70 mm, and a thickness of 2 mm is produced by injection molding. From the flat plate, a width of 5 mm and a length of 15 mm are respectively obtained in the resin flow direction (MD) and the direction perpendicular to the resin flow direction (TD). A strip-shaped plate was cut out and used as a test piece for measuring the linear expansion coefficient. Next, the test piece was attached to a measuring device ((trade name) DL7000, manufactured by ULVAC, Inc.), and the linear expansion coefficient was measured in the range of 30 to 200 ° C. under a temperature rising condition of 2 ° C./min. Furthermore, in order to evaluate the anisotropy of the linear expansion coefficient, the (MD) / (TD) ratio of the linear expansion coefficient is calculated. The closer the value is to 100%, the smaller the anisotropy is. When near or greatly exceeding 100%, the anisotropy was judged to be large.

~ Measurement of melt flow rate (MFR) ~
Using a Koka flow tester, the weight (g unit) of the composition flowing out in 10 minutes was measured under the conditions of a temperature of 315 ° C., a load of 5 kg, and a die inner diameter of 2.0 mm, and a melt flow rate (hereinafter referred to as MFR). It was written.)

<Synthesis Example 1 (Synthesis of PPS (a-1), PPS (a-2))>
A 15 liter autoclave equipped with a stirrer was charged with 1866 g of Na ₂ S · 2.8H ₂ O and 5 liters of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and gradually heated to 205 ° C. while stirring under a nitrogen stream. The temperature was raised and 407 g of water was distilled off. After cooling the system to 140 ° C., 2280 g of p-dichlorobenzene and 1500 g of NMP were added, and the system was sealed under a nitrogen stream. The system was heated to 225 ° C. and polymerized at 225 ° C. for 2 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the polymer was isolated using a centrifuge. The polymer was washed repeatedly with warm water and dried at 100 ° C. for a whole day and night to obtain poly (p-phenylene sulfide).

  The melt viscosity of the obtained poly (p-phenylene sulfide) (PPS (a-1)) was 110 poise.

  Further, PPS (a-1) was heat-cured at 235 ° C. in an air atmosphere.

  The melt viscosity of the obtained poly (p-phenylene sulfide) (PPS (a-2)) was 300 poise.

<Synthesis Example 2 (Synthesis of PPS (a-3))>
A 15 liter titanium autoclave equipped with a stirrer was charged with 3232 g of NMP, 1682 g of a 47% aqueous sodium hydrogen sulfide solution and 1142 g of a 48% aqueous sodium hydroxide solution, and gradually heated to 200 ° C. with stirring under a nitrogen stream, Distilled. The system was cooled to 170 ° C., 2118 g of p-dichlorobenzene and 1783 g of NMP were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C., polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. and polymerized at 250 ° C. for 2 hours. Furthermore, 451 g of water was injected at 250 ° C., the temperature was raised again to 255 ° C., and polymerization was performed at 225 ° C. for 2 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the polymerization slurry was subjected to solid-liquid separation. The polymer was washed successively with NMP, acetone and water, and dried at 100 ° C. for a whole day and night to obtain poly (p-phenylene sulfide).

  The obtained poly (p-phenylene sulfide) (PPS (a-3)) was linear, and its melt viscosity was 350 poise.

Example 1
PPS (a-2) 29% by weight, low melting point alloy (b-1) 10% by weight, metal powder (c-1) 20% by weight, boron nitride powder (d-1) 10% by weight, coated magnesium oxide powder ( e-1) 30% by weight and carnauba wax (f-1) 1% by weight, each compounded and heated to 310 ° C. (Toshiba Machine, (trade name) TEM-35-102B) The molten composition flowing out from the die was cooled and cut to obtain a pellet-shaped polyarylene sulfide composition.

  The polyarylene sulfide composition was put into a hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75S) heated to 310 ° C., and a test piece for measuring bending strength, and thermal conductivity Each flat plate for measuring the linear expansion coefficient was molded.

  Bending strength, thermal conductivity, and linear expansion coefficient were measured from the test piece and the flat plate. Further, the polyarylene sulfide composition was charged into a Koka flow tester and MFR was measured. These results are shown in Table 1.

  The obtained polyarylene sulfide composition had a sufficiently high bending strength, a high thermal conductivity, and a small anisotropy. Moreover, the linear expansion coefficient was small and the anisotropy was also small. Furthermore, MFR also showed a practically sufficient value.

Examples 2-11
PPS (a-1, 2, 3), low melting point alloy (b-1, 2), metal powder (c-1), boron nitride powder (d-1, 2), coated magnesium oxide powder (e-1) A polyarylene sulfide composition and a test piece for evaluation were prepared and evaluated by the same method as in Example 1 except that the blending ratio of carnauba wax (f-1) shown in Table 1 was used. The evaluation results are shown in Table 1.

  All the obtained polyarylene sulfide compositions had high thermal conductivity and low linear expansion coefficient. Moreover, each anisotropy was also small.

比較例１〜７
ＰＰＳ（ａ−１，２）、低融点合金（ｂ−１，３）、金属粉末（ｃ−１）、窒化ホウ素粉末（ｄ−１）、被覆酸化マグネシウム粉末（ｅ−１）、酸化マグネシウム粉末（ｅ’−１）及びカルナバワックス（ｆ−１）を表２に示す配合割合とした以外は、実施例１と同様の方法により、組成物、評価用試験片を作成し、評価した。評価結果を表２に示す。

Comparative Examples 1-7
PPS (a-1, 2), low melting point alloy (b-1, 3), metal powder (c-1), boron nitride powder (d-1), coated magnesium oxide powder (e-1), magnesium oxide powder A composition and a test piece for evaluation were prepared and evaluated in the same manner as in Example 1 except that (e′-1) and carnauba wax (f-1) were mixed in the proportions shown in Table 2. The evaluation results are shown in Table 2.

  (B) a composition containing no low melting point alloy obtained in Comparative Example 1, (c) a composition containing no metal powder obtained in Comparative Example 2, and (d) scaly nitriding obtained in Comparative Example 3 Composition containing no boron powder, composition obtained in Comparative Example 4 (e) composition containing no coated magnesium oxide powder, low melting point alloy having a liquidus temperature of less than 300 ° C. obtained in Comparative Example 5 And the composition containing the magnesium oxide powder (e′-1) obtained in Comparative Example 6 had a low thermal conductivity and a large anisotropy. Moreover, the linear expansion coefficient was also large. The composition (f) obtained by Comparative Example 7 that does not contain carnauba wax has poor mold releasability, so that the test piece and flat plate used for each evaluation cannot be molded, bending strength, thermal conductivity, and The linear expansion coefficient could not be evaluated.

実施例１２
ＰＰＳ（ａ−２）２４重量％、低融点合金（ｂ−１）１０重量％、窒化ホウ素粉末（ｄ−１）１０重量％、被覆酸化マグネシウム粉末（ｅ−１）３０重量％及びカルナバワックス（ｆ−１）１重量％となる割合で配合し、３１０℃に加熱した二軸押出機（東芝機械製、（商品名）ＴＥＭ−３５−１０２Ｂ）のホッパーに、一方、高熱伝導炭素繊維（ｃ−１）を該二軸押出機サイドフィーダーのホッパーに、それぞれ投入し、スクリュー回転数２００ｒｐｍにて溶融混練し、ダイより流出する溶融組成物を冷却後裁断し、ペレット状のポリアリーレンスルフィド組成物を作製した。その際、高熱伝導炭素繊維（ｃ−１）は配合割合が２５重量％となるように供給を行った。

Example 12
PPS (a-2) 24 wt%, low melting point alloy (b-1) 10 wt%, boron nitride powder (d-1) 10 wt%, coated magnesium oxide powder (e-1) 30 wt% and carnauba wax ( f-1) In a hopper of a twin screw extruder (manufactured by Toshiba Machine, (trade name) TEM-35-102B) blended at a ratio of 1% by weight and heated to 310 ° C., on the other hand, a high thermal conductive carbon fiber (c -1) is put into the hopper of the twin-screw extruder side feeder, melt-kneaded at a screw rotation speed of 200 rpm, the molten composition flowing out from the die is cooled and cut, and then pelletized polyarylene sulfide composition Was made. At that time, the high thermal conductivity carbon fiber (c-1) was supplied such that the blending ratio was 25% by weight.

  The polyarylene sulfide composition was put into a hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75S) heated to 310 ° C., and a test piece for measuring bending strength, and thermal conductivity Each flat plate for measuring the linear expansion coefficient was molded.

  Bending strength, thermal conductivity, and linear expansion coefficient were measured from the test piece and the flat plate. Further, the polyarylene sulfide composition was charged into a Koka flow tester and MFR was measured. These results are shown in Table 3.

  The obtained polyarylene sulfide composition had a sufficiently high bending strength, a high thermal conductivity, and a small anisotropy. Moreover, the linear expansion coefficient was small and the anisotropy was also small. Furthermore, MFR also showed a practically sufficient value.

Examples 13-24
PPS (a-1,2,3), low melting point alloy (b-1,2), high thermal conductivity carbon fiber (c-1), boron nitride powder (d-1,2), coated magnesium oxide (e-1) ), Carnauba wax (f-1), and graphite (g-1) were prepared in the same manner as in Example 12 except that the blending ratios shown in Table 3 were used to prepare a polyarylene sulfide composition and an evaluation test piece. And evaluated. The evaluation results are shown in Table 3.

  All the obtained polyarylene sulfide compositions had high thermal conductivity and low linear expansion coefficient. Moreover, each anisotropy was also small.

比較例８〜１５
ＰＰＳ（ａ−１、２）、低融点合金（ｂ−１，３）、高熱伝導炭素繊維（ｃ−１）、低熱伝導炭素繊維（ｃ’−１）、窒化ホウ素粉末（ｄ−１）、被覆酸化マグネシウム粉末（ｅ−１）、酸化マグネシウム粉末（ｅ’−１）及びカルナバワックス（ｆ−１）を表４に示す配合割合とした以外は、実施例１２と同様の方法により、ポリアリーレンスルフィド組成物、評価用試験片を作成し、評価した。評価結果を表４に示す。

Comparative Examples 8-15
PPS (a-1, 2), low melting point alloy (b-1, 3), high thermal conductivity carbon fiber (c-1), low thermal conductivity carbon fiber (c′-1), boron nitride powder (d-1), A polyarylene was produced in the same manner as in Example 12, except that the coated magnesium oxide powder (e-1), the magnesium oxide powder (e'-1) and the carnauba wax (f-1) were mixed in the proportions shown in Table 4. A sulfide composition and a test piece for evaluation were prepared and evaluated. The evaluation results are shown in Table 4.

  (C) a composition not containing high heat conductive carbon fiber obtained by Comparative Example 8, (b) a composition not containing low melting point alloy obtained by Comparative Example 9, and (d) nitriding obtained by Comparative Example 10 A composition containing no boron powder, a composition containing (e) a coated magnesium oxide powder obtained by Comparative Example 11, and a composition containing the low thermal conductive carbon fiber (c′-1) obtained by Comparative Example 12 Each of the composition which mix | blends the low melting-point alloy whose liquidus temperature obtained by the comparative example 13 is less than 300 degreeC, and the composition which mix | blends the magnesium oxide powder (e'-1) obtained by the comparative example 14 All had low thermal conductivity and large anisotropy. Moreover, the linear expansion coefficient was also large. Furthermore, the composition (f) obtained by Comparative Example 15 that does not contain carnauba wax has a poor mold releasability, so that a test piece and a flat plate used for each evaluation cannot be formed, and a bending test, thermal conductivity, And the linear expansion coefficient could not be evaluated.

Claims (6)

(A) polyarylene sulfide, (b) a low melting point alloy having a liquidus temperature of 300 ° C. or higher and a solidus temperature of 150 ° C. or higher and 250 ° C. or lower, (c) a metal powder having a melting point of 400 ° C. or higher, and / or 100 W / coated with carbon fiber having thermal conductivity of m · k or more, (d) flaky boron nitride powder having a hexagonal structure, (e) double oxide of silicon and magnesium and / or double oxide of aluminum and magnesium. A polyarylene sulfide composition comprising: a coated magnesium oxide powder; and (f) carnauba wax. (A) 15 to 50% by weight of polyarylene sulfide, (b) 5 to 40% by weight of a low melting point alloy having a liquidus temperature of 300 ° C. or higher and a solidus temperature of 150 ° C. or higher and 250 ° C. or lower, and (c) a melting point of 400 5 to 40% by weight of a metal powder having a heat conductivity of 100 W / m · k or more, (d) a flaky boron nitride powder having a hexagonal crystal structure and 5 to 25% by weight, (e) It is characterized by comprising 15 to 50% by weight of coated magnesium oxide powder coated with a double oxide of silicon and magnesium and / or a double oxide of aluminum and magnesium, and (f) 0.05 to 5% by weight of carnauba wax. The polyarylene sulfide composition according to claim 1. Furthermore, (g) graphite is mix | blended, The polyarylene sulfide composition in any one of Claim 1 or 2 characterized by the above-mentioned. (A) polyarylene sulfide, (b) a low melting point alloy having a liquidus temperature of 300 ° C. or higher and a solidus temperature of 150 ° C. or higher and 250 ° C. or lower, (c) a metal powder having a melting point of 400 ° C. or higher, (d) hexagonal A scaly boron nitride powder having a crystal structure, (e) a coated magnesium oxide powder coated with a double oxide of silicon and magnesium and / or a double oxide of aluminum and magnesium, and (f) carnauba wax. The polyarylene sulfide composition according to claim 1. (A) 15 to 50% by weight of polyarylene sulfide, (b) 5 to 40% by weight of a low melting point alloy having a liquidus temperature of 300 ° C. or higher and a solidus temperature of 150 ° C. or higher and 250 ° C. or lower, and (c) a melting point of 400 5 to 40% by weight of metal powder at or above C., (d) 5 to 25% by weight of flaky boron nitride powder having a hexagonal crystal structure, (e) double oxide of silicon and magnesium and / or double oxide of aluminum and magnesium 5. The polyarylene sulfide composition according to claim 1, comprising 15 to 50% by weight of a coated magnesium oxide powder coated with 1 and 0.05 to 5% by weight of (f) carnauba wax. (B) Low melting point alloy having a liquidus temperature of 300 ° C or higher and a solidus temperature of 150 ° C or higher and 250 ° C or lower / (c) Metal powder having a melting point of 400 ° C or higher = 1/8 to 8/1 (weight ratio) The polyarylene sulfide composition according to claim 4, wherein the polyarylene sulfide composition is.