JP4747731B2 - Polyarylene sulfide composition - Google Patents

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. The present invention relates to a polyarylene sulfide composition having low anisotropy and thermal expansibility. More particularly, the present invention relates to a polyarylene sulfide composition that is particularly useful for electric parts such as electric / electronic parts or automobile electric 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. The resin composition which mix | blends the above filler is proposed (for example, refer patent document 2), (a) Matrix resin, (b) The heat conductive filler disperse | distributed to matrix resin, and (c) Melting | fusing point of 500 degrees C or less. A resin composition made of a low melting point alloy has been proposed (see, for example, Patent Document 3). Furthermore, a resin composition in which (a) a resin composed of polyphenylene sulfide and polyphenylene ether, (b) carbon fiber having a specific thermal conductivity, and (c) graphite is proposed (see, for example, Patent Document 4). .)

Japanese Patent Laid-Open No. 04-033958 JP 2002-129015 A WO2003-029352 JP 2004-137401 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 large. Sufficient dimensional stability could not 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 obtain high thermal conductivity, high mechanical strength, good mold releasability, and molded product appearance at the same time.

  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 anisotropy and thermal expansion. 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, carbon fiber having a specific thermal conductivity, a low melting point alloy having both a specific liquidus temperature and a solidus temperature, By using a polyarylene sulfide composition comprising metal powder, coated magnesium oxide powder coated with a specific double oxide, and carnauba wax, it has low anisotropy and high thermal conductivity and low thermal expansion. Moreover, it discovered that it could become a composition excellent in mold releasability, and came to complete this invention.

That is, the present invention comprises (a) 15 to 50% by weight of polyarylene sulfide, (b) 5 to 50% by weight of carbon fiber having a thermal conductivity of 100 W / m · k or more, and (c) a liquidus temperature of 300 ° C. 5 to 40% by weight of a low melting point alloy having a solidus temperature of 150 ° C. or more and 250 ° C. or less, (d) 5 to 40% by weight of metal powder having a melting point of 400 ° C. or more, (e) a double oxide of silicon and magnesium, and And / or a coated magnesium oxide powder coated with a double oxide of aluminum and magnesium, 15 to 50% by weight , (f) carnauba wax 0.05 to 5% by weight, and (g) 5 to 40% by weight of graphite. It relates to a polyarylene sulfide composition characterized.

  Hereinafter, the present invention will be described in detail.

  The polyarylene sulfide composition of the present invention comprises (a) polyarylene sulfide, (b) carbon fiber having a thermal conductivity of 100 W / m · k or more (hereinafter simply referred to as (b) carbon fiber), (c). ) 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 (hereinafter simply referred to as (c) low melting point alloy), (d) Metal powder having a melting point of 400 ° C. or higher. (Hereinafter simply referred to as (d) metal powder), (e) coated magnesium oxide powder coated with silicon and magnesium double oxide and / or aluminum and magnesium double oxide (hereinafter simply referred to as (e) coating) (Referred to as magnesium oxide powder), and (f) carnauba wax.

  As the (a) polyarylene sulfide 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 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、

Examples of other components include m-phenylene sulfide units 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 of reacting an alkali metal sulfide and a dihaloaromatic compound 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, but may 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. In addition, 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) carbon fiber constituting the polyarylene sulfide composition of the present invention is a carbon fiber having a thermal conductivity of 100 W / m · k or more, and the (b) carbon fiber has a thermal conductivity of 100 W / m. As long as it satisfies the condition of m · k or more, it can be used without any limitation. 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 a carbon fiber having a thermal conductivity of less than 100 W / m · k is used to form a polyarylene sulfide composition, a combination of (c) a low melting point alloy, (d) a metal powder, and (e) a coated magnesium oxide powder Even if it mix | blends by, the polyarylene sulfide composition which has high heat conductivity cannot be obtained, and the objective of this invention cannot be achieved.

  Examples of the shape of the carbon fiber (b) include a chopped fiber having a fiber diameter of 5 to 20 μm and a fiber length of 2 to 8 mm, and 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.

  Further, the blending amount of the carbon fiber (b) is preferably 5 to 50% by weight because a polyarylene sulfide composition excellent in mechanical strength, moldability and thermal conductivity is obtained.

  The (c) 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 (c) 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 (c) 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 (c) 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 particularly excellent in mechanical strength, formability and thermal conductivity. It is preferable that

  The metal powder constituting the polyarylene sulfide composition of the present invention may be any metal powder as long as the metal powder has a melting point of 400 ° C. or higher. A powder of an alloy of a plurality of types of metals can be used. Among them, since (c) the familiarity with the low-melting point alloy is good, the polyarylene sulfide composition is particularly excellent in thermal conductivity. Therefore, (d) the metal powder constitutes (c) 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 kinds of metals other than the metal to be removed, and among these, (c) when a Sn—Cu alloy or a Sn—Cu—Ni alloy is used as the low melting point alloy, (d) a metal powder It is preferable to use Cu powder, a powder mixture of Cu powder and one or more metal powders except the metal, and an alloy powder of Cu and one or more metal other than the metal, and (c ) Sn- as low melting point alloy In the case of using an n alloy, (d) 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 of the other metals 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 (d) metal powder 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.

  The shape of the metal powder (d) is not particularly limited, and examples thereof include dendritic powder, flake powder, horn 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 (d) 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.

  The blending amount of the metal powder (d) is preferably 5 to 40% by weight because it becomes a polyarylene sulfide composition having excellent mechanical strength, moldability, and thermal conductivity, and particularly thermal conductivity. Therefore, it is preferable to use (c) low melting point alloy / (d) metal powder = 1/8 to 8/1 (weight ratio).

  The (e) coated magnesium oxide powder constituting the polyarylene sulfide composition of the present invention is a 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 powder, and for example, it can be obtained by 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, even if (b) carbon fiber, (c) low melting point alloy, and (d) metal powder Even if it mix | blends, the polyarylene sulfide composition which has high heat conductivity cannot be obtained, and the objective of this 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. Yes, 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%.

  Furthermore, in the polyarylene sulfide composition of the present invention, (g) graphite is preferably blended in order to make the thermal conductivity anisotropy smaller. 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, scale-like graphite, scale-like graphite, and any of these may be used. The fixed carbon content of the (g) graphite is a graphite having a fixed carbon content of 95% or more because it is 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 (g) graphite is blended with the polyarylene sulfide composition of the present invention, the blending amount thereof should be a polyarylene sulfide composition with particularly low mechanical strength, moldability, and thermal conductivity anisotropy. From 5 to 40% by weight is preferable.

  Furthermore, the polyarylene sulfide composition of the invention is within a range not departing from the object of the present invention, various thermosetting resins, thermoplastic resins such as epoxy resins, cyanate ester resins, phenol resins, polyimides, silicone resins, polyolefins, One or more of polyester, polyamide, polyphenylene oxide, polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone and the like 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 include 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 wiring 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 properties and melt fluidity, and low thermal conductivity anisotropy and thermal expansion. The polyarylene sulfide composition is particularly useful for electrical parts such as electrical / electronic parts or automotive electrical parts.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention, this invention is not restrict | limited to these examples at all.

  (A) polyarylene sulfide used in Examples and Comparative Examples, (b) carbon fiber having a thermal conductivity of 100 W / m · k or more, and (b ′) carbon having a thermal conductivity of less than 100 W / m · k. Fiber, (c) low melting point alloy, (d) metal powder, (e) coated magnesium oxide powder, (e ′) magnesium oxide powder not coated with double oxide, (f) carnauba wax and (g) graphite. It is 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 of 300 poise.
(A-3) Poly (p-phenylene sulfide) (hereinafter simply referred to as PPS (a-3)): Melt viscosity poise 350 poise.

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

<(B ′) Carbon fiber having a thermal conductivity of less than 100 W / m · k>
(B′-1) Carbon fiber having a thermal conductivity of less than 100 W / m · k (hereinafter simply referred to as “low thermal conductivity carbon fiber (b′-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.

<(C) Low melting point alloy>
(C-1) Low melting point alloy (hereinafter simply referred to as low melting point alloy (c-1)); Ishikawa Metal Co., Ltd., (trade name) Evasol R25; Cu 5 wt% Sn-Cu alloy, liquid phase Line temperature 358 ° C., solidus temperature 227 ° C.
(C-2) Low melting point alloy (hereinafter, simply referred to as low melting point alloy (c-2)); manufactured by 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.
(C-3) Low melting point alloy (hereinafter simply referred to as low melting point alloy (c-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.

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

<(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 ~
Using a thermal conductivity measuring device (manufactured by ULVAC, (trade name) TC7000; ruby laser), measurement was performed by a laser flash method at 23 ° C. 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 conductivity 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 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 the thermal conductivity, the ratio (thickness direction) / (plane direction) of the 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.

~ 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, 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 raised to 205 ° C. while stirring under a nitrogen stream. Warm and distill 407 g of water. 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 polymerization slurry 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 47% sodium hydrogen sulfide aqueous solution and 1142 g of 48% sodium hydroxide aqueous solution, gradually heated to 200 ° C. while stirring under a nitrogen stream, and 1360 g of water was added. 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. The 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 carried out 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. overnight 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
29% by weight of PPS (a-2), 10% by weight of low melting point alloy (c-1), 20% by weight of metal powder (d-1), 20% by weight of coated magnesium oxide powder (e-1) 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 (b- 1) 20% by weight is put into a hopper of a twin-screw extruder side feeder, melted and kneaded at a screw rotation speed of 200 rpm, and the molten composition flowing out from the die is cooled and cut to form a pellet-like polyarylene sulfide composition. I got a thing.

  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. Furthermore, MFR also showed a practically sufficient value.

Examples 2-11
PPS (a-1, 2, 3), high thermal conductivity carbon fiber (b-1), low melting point alloy (c-1, 2), metal powder (d-1), coated magnesium oxide powder (e-1), A polyarylene sulfide composition and a test piece for evaluation were prepared in the same manner as in Example 1 except that carnauba wax (f-1) and graphite (g-1) were mixed in the proportions shown in Table 1. evaluated. The evaluation results are shown in Table 1.

  All the obtained polyarylene sulfide compositions had high thermal conductivity and low linear expansion coefficient.

比較例１〜８
ＰＰＳ（ａ−１，２，３）、高熱伝導炭素繊維（ｂ−１）、低熱伝導炭素繊維（ｂ’−１）、低融点合金（ｃ−１，３）、金属粉末（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 1-8
PPS (a-1, 2, 3), high thermal conductivity carbon fiber (b-1), low thermal conductivity carbon fiber (b'-1), low melting point alloy (c-1, 3), metal powder (d-1) The composition was the same as in Example 1 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 2. A test piece for evaluation was prepared and evaluated. The evaluation results are shown in Table 2.

  (B) a composition not blended with carbon fiber having a thermal conductivity of 100 W / m · k or more obtained in Comparative Example 1, (c) a composition not blended with a low melting point alloy obtained in Comparative Example 2, comparison (D) the composition not containing the metal powder obtained in Example 3, the composition not containing the coated magnesium oxide powder obtained in Comparative Example 4 (e), the low thermal conductive carbon fiber (b′−) obtained in Comparative Example 5 1), a composition containing a low melting point alloy having a liquidus temperature of less than 300 ° C. obtained in Comparative Example 6, and magnesium oxide (e′-1) obtained in Comparative Example 7 Each of the compositions to be blended had low thermal conductivity and large anisotropy. Moreover, since the composition which does not mix | blend the (f) carnauba wax obtained by the comparative example 8 has bad mold releasability, the test piece and flat plate which are used for each evaluation cannot be shape | molded, bending strength, thermal conductivity And the linear expansion coefficient could not be evaluated.

Claims (3)

(A) Polyarylene sulfide 15 to 50% by weight , (b) Carbon fiber 5 to 50% by weight having a thermal conductivity of 100 W / m · k or higher, (c) Liquidus temperature 300 ° C. or higher, and Solid line 5 to 40% by weight of a low melting point alloy having a temperature of 150 ° C. or more and 250 ° C. or less, (d) 5 to 40% by weight of metal powder having a melting point of 400 ° C. or more, (e) a double oxide of silicon and magnesium and / or aluminum and magnesium A polyarylene sulfide comprising 15 to 50% by weight of coated magnesium oxide powder coated with a double oxide, (f) 0.05 to 5% by weight of carnauba wax , and (g) 5 to 40% by weight of graphite. Composition. (C) Low melting point alloy with a liquidus temperature of 300 ° C. or higher and a solidus temperature of 150 ° C. or higher and 250 ° C. or lower / (d) Metal powder with a melting point of 400 ° C. or higher = 1/8 to 8/1 (weight ratio). Oh polyarylene sulfide composition as claimed in claim 1, characterized in Rukoto. ( C) The 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 is a Sn—Cu alloy or a Sn—Cu—Ni alloy, and (d) a metal having a melting point of 400 ° C. or higher. powder polyarylene sulfide composition as claimed in any one of claims 1 or 2, characterized in Cu powder der Rukoto.