JP4407250B2 - Heat sink tablet, heat sink obtained therefrom, and production method - Google Patents

Description

  The present invention relates to a heat sink tablet excellent in heat dissipation, low burr, and weld portion durability, a heat sink comprising the same, and a method of manufacturing the heat sink.

  In recent years, various electrical components have been electronically controlled by computers in order to improve fuel efficiency, weight reduction or safety, and comfort in the automobile field. In the electric / electronic field, as well as improving the performance of personal computers, household electrical appliances such as refrigerators and washing machines are being electronically controlled by computers for the purpose of energy saving.

  Electronic devices such as LSIs and CPUs that perform electronic control have problems such as damage to electronic devices due to increased power consumption due to increased integration of computers and faster operation, and increased heat generation.

  For this reason, the computer needs to take measures against heat dissipation, and conventionally, heat sinks made of aluminum or die-casting are used to dissipate heat, such as a package of electronic parts that are heat sources.

  However, in the future, when parts are further reduced in size, weight, or complicated shape, metal such as die-casting is not productive and the shape is limited.

  In order to solve these problems, polyphenylene sulfide resin is blended with inorganic fillers such as magnesium oxide, aluminum oxide, glass fiber, carbon fiber, wollastonite, potassium titanate, aluminum borate, and the thermal conductivity is reduced. There has been proposed a method (Patent Document 1) for obtaining a molded article having a heat conductivity of 1 W / mK or higher and capable of injection molding. Patent Documents 2 and 3 disclose thermal conductive resin compositions obtained by blending alumina or a plate-like filler with polyphenylene sulfide resin. In addition, attempts have been made to control the particle size of graphite particles for use in fuel cell separators (Patent Document 4).

 However, since the method disclosed in Patent Document 1 is a method for producing a composition by melt-kneading, it is difficult to blend a large amount of inorganic filler, and the thermal conductivity is 1.4 W / mK at most. Only a composition has been obtained, and in order to cope with higher heat generation due to higher integration and higher speed of computers in recent years, heat dissipation is still low, and it is difficult to sufficiently function as a heat sink. Furthermore, in practical use, for example, when used for a member that is expected to undergo a drastic temperature change, the temperature change cannot be followed, and there is a concern that the member may be deformed or cracks may occur. Is done. In particular, there is a problem that the load on the welded portion (resin gathering portion) of the molded product is large, and the welded portion is cracked by a dimensional change due to a drastic temperature change. In addition, the polyarylene sulfide resin molded product tends to generate burrs, and not only a deburring process is required, but also continuous molding causes severe damage to the mold, and the productivity cannot be said to be sufficient.

  Also, in Patent Document 2 and Patent Document 3, it is carried out by the melt-kneading method, and it is difficult to fill a large amount of the filler, and the obtained thermal conductivity is about 2.3 W / mK at most. Heat dissipation is not sufficient.

In addition, Patent Document 4 describes that it is better that the degree of uniformity of the cumulative particle size distribution represented by the ratio (D80 / D20) of the 80% cumulative particle size (D80) to the 20% cumulative particle size (D20) is better. However, when considering the packing properties of the particles, it cannot be said that the dimensional stability is particularly sufficient, and the development is limited.
JP 2001-151905 A (page 2, example) JP 2002-146187 A (page 2, example) JP 2002-256147 A (page 2, example) JP 2001-126744 A (2nd, 4th page, Example)

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Therefore, the present invention is capable of high temperature filling with a heat conductive filler and exhibits its properties with high efficiency, heat dissipation, weld part durability at sudden temperature changes, and excellent melt molding processing with low burr. It is an object of the present invention to provide a heat sink tablet, a heat sink formed by melt-molding the tablet, and a method of manufacturing the heat sink.

  As a result of intensive studies to achieve the above object, the present inventors have reached the present invention.

That is, the present invention
(1) A heat sink tablet comprising a polyarylene sulfide resin (A) and a thermally conductive filler (B) having a thermal conductivity of 20 W / mK or more measured by a laser flash method, wherein (A) and (B) The component (A) 5 to 40% by volume and the component (B) 95 to 60% by volume are uniformly blended in a solid phase with respect to a total of 100% by volume of (B), and then by a tableting machine or a molding machine having a compression roll. A tablet for heat sink, which is a tableted tablet, wherein a heat sink having a thermal conductivity of 5 W / mK or more measured by a laser flash method is obtained by melt-molding the tablet;
(2) Further , monohydric alcohol esters, phosphate esters, aliphatic metal salts, polybasic acid monohydric alcohol esters, polyhydric alcohol fatty acids that change from solid to liquid or gas in a temperature range of 25 to 250 ° C. Ester and derivatives thereof, glycerin fatty acid ester, silicone resin, phenolic compound, benzophenone compound, amide group-containing compound, cyanurate compound and salt thereof (C) component (A) And the tablet for heat sinks of said (1) description which contains 0.01-30 weight part with respect to a total of 100 weight part of (B) component,
(3) Further, a monohydric alcohol ester of a fatty acid having a viscosity of 1 to 10,000 mPa · s at 25 ° C., a monohydric alcohol ester of a polybasic acid, a fatty acid ester of a polyhydric alcohol, and derivatives thereof, a fatty acid ester of glycerin, silicone oil And at least one liquid organic compound (D) selected from phosphite compounds and the like, containing 0.01 to 30 parts by weight with respect to 100 parts by weight as a total of the components (A) and (B) (1) The heat sink tablet according to the description,
(4) The thermal conductive filler (B) is a particle having a cumulative particle size distribution curve in which 25% by volume or more is a particle having a cumulative degree of 50% particle diameter (D50) × 1.5 or more. The heat sink tablet according to any one of (3) ,
(5) A heat sink obtained by melt-molding the heat sink tablet according to any one of (1) to (4 ) above,
(6) The heat sink according to (5) above, wherein the heat sink is a heat sink that constitutes a chassis, a housing, or a part thereof.
(7) The heat sink according to the above (5) or (6) having a fin-like projection,
(8) A method of manufacturing a heat sink, wherein the heat sink tablet according to any one of (1) to (4) is injection-molded.

  As described above, the melt-molding tablet of the present invention and the heat sink obtained therefrom can obtain a heat sink highly filled with a heat conductive filler that has not been obtained conventionally, and can be melt-processed and fluidized. Molded products with excellent high thermal conductivity, weld endurance, and low burrs, so that electrical and electronic equipment, precision machinery equipment, etc. It is suitable for heat sink applications with various shapes such as automobile / vehicle-related parts and building materials. Moreover, compared with a metal thing, it is lightweight and has very high shape selectivity, and since it can be injection-molded, productivity is high.

  Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

  The polyarylene sulfide resin (A) used in the present invention includes polyphenylene sulfide (hereinafter sometimes abbreviated as PPS), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers, block copolymers, and mixtures thereof. Etc.

  Of these, polyphenylene sulfide is particularly preferably used. Such polyphenylene sulfide is a polymer containing a repeating unit represented by the following structural formula, preferably 70 mol% or more, more preferably 90 mol% or more. When the repeating unit is 70 mol% or more, the heat resistance is high. It is preferable at an excellent point.

  Further, such polyphenylene sulfide can be composed of 30 mol% or less of the repeating unit with a repeating unit having the following structural formula, and may be a random copolymer or a block copolymer. A mixture thereof may also be used.

  Such polyarylene sulfide resins are generally known methods, that is, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or JP-B-52-12240 and JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in the publication.

  In the present invention, the polyarylene sulfide resin obtained as described above is subjected to crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, an organic solvent, hot water, Of course, it is possible to use it after various treatments such as washing with an acid aqueous solution, activation with a functional group-containing compound such as an acid anhydride, amine, isocyanate, or a functional group-containing disulfide compound.

  Specific methods for crosslinking / high molecular weight polyarylene sulfide resin by heating include an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. Below, a method of heating until a desired melt viscosity is obtained at a predetermined temperature in a heating container can be exemplified. In this case, the heat treatment temperature is preferably 150 to 280 ° C., more preferably 200 to 270 ° C., and the treatment time is preferably 0.5 to 100 hours, more preferably 2 A range of ˜50 hours is selected, but by controlling both, a target viscosity level can be obtained. Such a heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade. However, in the case of efficient and more uniform treatment, a heating apparatus with a rotary or stirring blade is used. Is more preferable.

As a specific method for heat-treating polyarylene sulfide resin under an inert gas atmosphere such as nitrogen or under reduced pressure, an inert gas atmosphere such as nitrogen or under reduced pressure (preferably 7,000 Nm ⁻² or less), Examples of the heat treatment method include a heat treatment temperature of 150 to 280 ° C, preferably 200 to 270 ° C, and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours. Such a heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade. However, in the case of efficient and more uniform treatment, a heating apparatus with a rotary or stirring blade is used. Is more preferable.

  When the polyarylene sulfide resin is washed with an organic solvent, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing the polyarylene sulfide resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, sulfoxide sulfone solvents such as dimethyl sulfoxide, dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, dimethyl ether, dipropyl ether , Ether solvents such as tetrahydrofuran, halogen solvents such as chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, Alcohol / phenolic solvents such as cresol and polyethylene glycol, benzene and toluene Ene, and aromatic hydrocarbon solvents such as xylene may be used. Of these organic solvents, N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like are particularly preferably used. These organic solvents are used alone or in combination of two or more.

  As a specific method of washing with such an organic solvent, there is a method of immersing a polyarylene sulfide resin in an organic solvent, and it is possible to appropriately stir or heat as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning polyarylene sulfide resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. The polyarylene sulfide resin that has been washed with an organic solvent is preferably washed several times with water in order to remove the remaining organic solvent. The water washing temperature is preferably 50 to 90 ° C, more preferably 60 to 80 ° C.

  The following method can be illustrated as a specific method when the polyarylene sulfide resin is treated with hot water (preferably 100 to 220 ° C.). That is, in order to express a preferable chemical modification effect of the polyarylene sulfide resin by hot water washing, the water used is preferably distilled water or deionized water. The operation of the hot water treatment is usually performed by adding a predetermined amount of polyarylene sulfide resin to a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the polyarylene sulfide resin and water should be higher, and is preferably used at a bath ratio of 200 g or less of polyarylene sulfide resin per liter of water.

  The following method can be illustrated as a specific method in the case of acid-treating polyarylene sulfide resin. That is, there is a method of immersing the polyarylene sulfide resin in an acid or an aqueous solution of the acid, and it is possible to appropriately stir or heat as necessary. The acid used is not particularly limited as long as it does not have an action of decomposing polyarylene sulfide resin, and includes aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, chloroacetic acid, dichloroacetic acid and the like. Halo-substituted aliphatic saturated carboxylic acids, aliphatic unsaturated monocarboxylic acids such as acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid, etc. Dicarboxylic acid and inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid and silicic acid are used. Of these acids, acetic acid and hydrochloric acid are particularly preferably used. The polyarylene sulfide resin that has been subjected to acid treatment is preferably washed several times with water in order to remove the remaining acid or salt. The water washing temperature is preferably 50 to 90 ° C, particularly preferably 60 to 80 ° C. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the preferable chemical modification effect of the polyarylene sulfide resin by acid treatment.

  The melt viscosity of the polyarylene sulfide resin used in the present invention is preferably 80 Pa · s or less, more preferably 50 Pa · s or less, more preferably 20 Pa · s or less under conditions of 300 ° C. and a shear rate of 1000 / sec. More preferably. Although there is no restriction | limiting in particular about the minimum of melt viscosity, It is preferable that it is 5 Pa.s or more. Two or more polyarylene sulfide resins having different melt viscosities may be used in combination.

  When the melt viscosity of the polyarylene sulfide resin exceeds the above range, it tends to be disadvantageous in terms of melt fluidity.

  The melt viscosity of the polyarylene sulfide resin can be measured using a capillograph (manufactured by Toyo Seiki Co., Ltd.) apparatus under conditions of a die length of 10 mm and a die hole diameter of 0.5 to 1.0 mm.

  Examples of the heat conductive filler (B) used in the present invention include metal powder, metal flake, metal ribbon, metal fiber, beryllia, alumina, zinc oxide, magnesium oxide, titanium oxide and other metal oxides, aluminum nitride, Boron nitride, nitride such as silicon nitride, silicon carbide, aluminum borate whisker, zinc oxide whisker, barium titanate whisker, silicon nitride whisker, etc. whisker, ceramic fiber, zirconia fiber, alumina fiber, crystalline silica fiber, titanium oxide Examples thereof include fibers, fibers such as silicon carbide fibers, crystalline silica, inorganic fillers coated with a heat conductive material, carbon powder, graphite, PAN-based or pitch-based carbon fibers, carbon flakes, scaly carbon, and carbon nanotubes. .

Among them, in order to impart high heat radiation as a heat sink when filled in a resin, the thermal conductivity was measured by a laser flash method is Ru with 20W / mK or more thermally conductive filler (B). Specific examples of such heat conductive fillers include metal powder, metal flake, metal ribbon, metal fiber, beryllia, alumina, zinc oxide, magnesium oxide and other metal oxides, aluminum nitride, boron nitride, silicon nitride, etc. Examples thereof include nitrides, inorganic fillers coated with a thermally conductive substance, carbon powder, graphite, PAN-based or pitch-based carbon fibers, carbon flakes, scaly carbon, and carbon nanotubes.

  Among them, alumina, zinc oxide, aluminum nitride, boron nitride, silicon nitride, carbon powder, graphite, PAN-based or pitch-based carbon fibers, carbon flakes, scaly carbon, carbon nanotubes, etc. can be used in that the heat sink can be made lighter. preferable.

  Here, specific examples of the metal species of the metal powder, metal flake and metal ribbon include silver, nickel, copper, zinc, aluminum, magnesium, stainless steel, iron, brass, chromium and tin.

  Moreover, iron, copper, stainless steel, aluminum, brass, etc. can be illustrated as a specific example of the metal seed | species of the said metal fiber.

  Such metal powders, metal flakes, metal ribbons, and metal fibers may all be surface-treated with a surface treatment agent such as titanate, aluminate, and silane.

Specific examples of the metal oxide include SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope), ZnO (aluminum dope), and the like. These include titanate, aluminum and silane. The surface treatment may be performed with the surface treatment agent.

Specific examples of the nitride include AlN (aluminum nitride), BN (boron nitride), Si ₃ N ₄ (silicon nitride), etc., and these include titanate-based, aluminum-based and silane-based surfaces. Surface treatment may be performed with a treating agent.

Specific examples of the heat conductive material in the inorganic filler coated with the heat conductive material include aluminum, nickel, silver, carbon, SnO ₂ (antimony doped), and In ₂ O ₃ (antimony doped). Can do. Examples of the inorganic filler to be coated include mica, glass beads, glass fibers, carbon fibers, barium sulfate, zinc oxide, titanium oxide, and silicon carbide whiskers. Examples of the coating method include a vacuum deposition method, a sputtering method, an electroless plating method, and a baking method. The inorganic filler coated with these thermally conductive materials may also be subjected to surface treatment with a surface treatment agent such as titanate, aluminate and silane.

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, and the like based on the raw materials and the production method. The carbon powder that can be used in the present invention is not particularly limited in terms of its raw material and production method, and among them, acetylene black and furnace black are particularly preferably used. Further, as the carbon powder, various carbon powders having different characteristics such as particle diameter, surface area, DBP oil absorption amount and ash content are produced. The carbon powder that can be used in the present invention is not particularly limited in terms of these characteristics, but from the viewpoint of the balance between strength and thermal conductivity, the average particle size is 500 nm or less, particularly 5 to 100 nm, more preferably 10 to 70 nm. It is preferable to be in the range. The surface area (BET method) is preferably in the range of 10 m ² / g or more, more preferably 30 m ² / g or more. Furthermore, the DBP oil supply amount is preferably 50 ml / 100 g or more, particularly preferably 100 ml / 100 g or more. Furthermore, it is preferable that the ash content is 0.5% or less, particularly 0.3% or less.

  Such carbon powder may be surface-treated with a surface treatment agent such as titanate, aluminate, and silane. Moreover, it is also possible to use what was granulated in order to improve melt-kneading workability | operativity with resin.

  The shape of the heat conductive filler used in the present invention is not particularly limited, but in terms of being able to reduce the anisotropy of the effect of improving thermal conductivity, it is more powdery, granular, plate-like than fibrous filler. It is preferable to use non-fibrous fillers such as scales. As the powdery, granular, plate-like, and scale-like fillers referred to herein, alumina, zinc oxide, graphite, and carbon black are preferably used.

  In the present invention, the heat conductive filler may be used in combination of two or more, and the combination is not particularly limited, but in terms of reducing the anisotropy of the heat conductive effect, It is preferable to use a combination of a fibrous filler and a non-fibrous filler, or a combination of two or more of non-fibrous fillers, and the latter is more preferable. Moreover, when improving a strength, it is preferable to use two or more fillers containing carbon black, and when greatly improving the thermal conductivity, it is preferable to use two or more fillers containing graphite.

  The blending amount of the polyarylene sulfide resin and the heat conductive filler used in the present invention exhibits the characteristics of the filler used, and from the viewpoint of balance with melt processability, the polyarylene sulfide resin (A) and the heat The polyarylene sulfide resin (A) is usually 5 to 40% by volume and the heat conductive filler (B) is 95 to 60% by volume with respect to 100% by volume of the total amount of the conductive filler (B). Resin (A) 6-35% by volume, thermal conductive filler (B) 94-65% by volume is preferred, polyarylene sulfide resin (A) 7-25% by volume, thermal conductive filler (B) More preferably, it is 93 to 75% by volume.

  Furthermore, in the present invention, in order to achieve both the effect of giving the measurement stability by maintaining the shape as a tablet and the stable crushing of the tablet at the time of molding, the liquid is further removed from a mechanically solid state in a temperature range of 25 to 250 ° C. Or it is possible to add the substance (C) which changes to gas.

  The substance (C) used in the present invention is a substance that is dynamically changed from a solid state to a fluid or liquid state in a temperature range of 25 to 250 ° C. Examples of such substances include fatty acid monohydric alcohol esters, fatty acid metal salts, fatty acid esters of polybasic acids, fatty acid esters of polyhydric alcohols, and derivatives thereof, epoxy compounds, fatty acid esters of glycerin, silicone resins, phenolic compounds , Phosphate compounds, phosphite compounds, thioether compounds, benzophenone compounds, amide group-containing compounds, cyanurate compounds and salts thereof having a melting point or softening point of 40 to 250 ° C.

  Specifically, stearic acid esters such as methyl stearate and stearic acid stearate, myristic acid esters such as myristyl myristate, montanic acid esters, monohydric alcohol esters of fatty acids such as methacrylic acid esters such as behenyl methacrylate, and the like Derivatives, sodium stearate, calcium stearate, magnesium stearate, potassium stearate, lithium stearate, zinc stearate, barium stearate, aluminum stearate, sodium montanate, calcium montanate, magnesium montanate, potassium montanate, montan Fatty acid metal salts such as lithium oxide, zinc montanate, barium montanate, aluminum montanate, distearyl phthalate, distemate trimellitic acid Fatty acid esters of polybasic acids such as ril, sorbitan tristearate, sorbitan monostearate, sorbitan monostearate, sorbitan distearate, sorbitan monopalmitate, sorbitan monostearate, polyethylene glycol monostearate, polyethylene glycol distearate Fatty acid esters of polyhydric alcohols such as poly (propylene glycol monostearate), pentaerythritol monostearate, stearic acid monoglyceride, palmitic acid / stearic acid monoglyceride, stearic acid mono / diglyceride, stearic acid / oleic acid / mono / diglyceride, behenine Fatty acid esters of glycerin such as acid monoglycerides, bisphenol type monofunctional and polyfunctional epoxy compounds, 2 2-methylenebis (4,6-di-t-butylphenyl) octyl phosphate, di (2,4-di-t-butylphenyl) pentaerythritol diphosphate, bis- (2,6-di-t-butyl-4) -Methylphenyl) phosphate compounds such as pentaerythritol diphosphate, bisphenol A pentaerythritol phosphite, tris (2,4-di-t-butylphenyl) phosphite, di (2,4-di-t-butylphenyl) penta Phosphite compounds such as erythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, triethylene glycol-bis (3- (3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate), 1,6-hexane Diol-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- t-butylanilino) -1,3,5-triazine, pentaerythryl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), 2,2-thio-diethylenebis (3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester Phenols such as 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, terpenephenol, 2-hydroxy-4-n-octyloxybenzophenone Compounds, amide group-containing compounds such as ethylene bisstearylamide, ethylenebisoleylamide, stearyl erucamide, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, triallyl cyanurate, Cyanurate compounds such as melamine / cyanurate salts and salts thereof, 2,5-bis (5′-t-butylbenzooxozalyl (2)) thiophene, epoxy group, methacryl group, amino group-containing or non-functional silicone resin Is mentioned. Moreover, the substance which is solid at 25 degrees C or less like a decomposition | disassembly foaming agent and changes to gas in the temperature range of 25-250 degreeC is mentioned. Specific examples of such substances include azodicarbonamide, azobisisobutyronitrile, N, N′-dinitrosopentamethylenetetramine, P, P′-dinitrosopentamethylenetetramine, P, P′-oxybis. Examples thereof include benzenesulfonylhydrazine, barium azodicarboxylate, trihydrazinotriazine, and 5-phenyltetrazole.

  In the present invention, the substance (C) may be any one of the above substances or a mixture of two or more kinds.

  The substance (C) used in the present invention changes from a solid to a liquid or gas in a temperature range of 25 to 250 ° C. from the viewpoint of handling properties and melt plasticization characteristics, preferably 40 to 230 ° C., more preferably Is preferably changed from solid to liquid or gas at 50 to 220 ° C, more preferably 60 to 200 ° C.

  In the present invention, the substance (C) is present as a solid during tablet production, and can be changed to liquid or gas when the tablet is melt-molded. In the present invention, by using such a substance (C), it is presumed that both the shape retention as a tablet and the measurement stability imparting effect by stable crushing of the tablet at the time of molding can be achieved.

  The amount of the substance (C) added is preferably 0.01 to 30 parts by weight, more preferably 100 parts by weight of the total amount of the polyarylene sulfide resin (A) and the heat conductive filler (B). Is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, and particularly preferably 1 to 10 parts by weight.

  When the amount of the substance (C) added is too larger than the range of the present invention, it bleeds out to the surface of the obtained molded product, thereby causing peeling of the interface between the thermoplastic resin and the filler, resulting in a decrease in mechanical properties. If the amount is too small, the measurement stability imparting effect due to crushing at the time of molding by addition tends to be small.

  Further, the present invention includes a viscosity at 25 ° C. as a technique for reducing the composition distribution during tablet production and making the tablet crushability uniform during melt molding so as to stabilize the measuring time during molding. It is possible to add a liquid organic compound (D) of 1 to 10000 mPa · s. A liquid organic compound having a viscosity of 1 to 10,000 mPa · s at 25 ° C. is an organic compound that is liquid and fluid at 25 ° C.

  Such substances include, for example, fatty acid monohydric alcohol esters, polybasic acid monohydric alcohol esters, polyhydric alcohol fatty acid esters, and derivatives thereof, glycerin fatty acid esters, silicone oils, phosphite compounds, and the like. The thing whose melting | fusing point is less than 25 degreeC is mentioned. Specifically, cetyl 2-ethylhexanoate, methyl coconut fatty acid, methyl laurate, isopropyl myristate, octyldodecyl myristate, butyl stearate, 2-ethylhexyl stearate, isotridecyl stearate, methyl caprate, methyl myristate , Monohydric alcohol esters of fatty acids such as methyl oleate, octyl oleate, lauryl oleate, oleyl oleate, 2-ethylhexyl oleate, decyl oleate, octidodecyl oleate, isobutyl oleate, dimethyl adipate, adipic acid Dioleyl, adipate, ditridecyl phthalate, diisobutyl adipate, diisodecyl adipate, dibutyl glycol adipate, 2-ethylhexyl phthalate, diisonophthalate Monohydric alcohol esters of polybasic acids such as didecyl phthalate, tridecyl phthalate, triisodecyl trimellitic acid, triisodecyl trimellitic acid, sorbitan monolaurate, sorbitan trioleate, sorbitan monooleate, sorbitan sesquioleate, sorbitan monolaurate , Polyoxymethylene sorbitan monolaurate, polyoxymethylene sorbitan monopalinate, polyoxymethylene sorbitan monostearate, polyoxymethylene sorbitan monooleate, polyoxymethylene sorbitan tetraoleate, polyethylene glycol, polyethylene glycol monolaurate, polyethylene glycol Monooleate, polyoxyethylene bisphenol A laurate, pentaerythritol, pentaerythritol Fatty acid esters of polyhydric alcohols such as lumonoolate and their derivatives, oleic acid monodiglyceride, oleic acid monoglyceride, oleic acid monoglyceride, 2-ethylhexanoic acid triglyceride, caprylic acid monodiglyceride, caprylic acid triglyceride, lauryl methacrylate, myristyl methacrylate , Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethylene glycolate, tri-2 -Ethylhexyl trimellitate, methyl acetyl ricinoleate, glyceryl triacetate, 2-ethylhexyl a Fatty acid ester of glycerin such as cetate, triphenyl phosphite, dibutyl hydrogen phosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxyl-5-t-butylphenyl) butane triphosphite, Phosphite compounds such as tetratridecyl-4,4′-butylidenebis- (3-methyl-6-tert-butylphenol) -di-phosphite, dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, alkyl Modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil And the like of the silicone oil.

  In the present invention, any one or a mixture of two or more liquid organic compounds (D) having a viscosity at 25 ° C. of 1 to 10,000 mPa · s may be used.

  The viscosity at 25 ° C. of the liquid organic compound (D) used in the present invention is 1 to 10,000 mPa from the viewpoint of the dispersibility of the liquid organic compound in the composition and the stabilization of the measuring time during molding, which is an effect of the present invention. S, preferably 2 to 9000 mPa · s, more preferably 100 to 9000 mPa · s, and still more preferably 200 to 9000 mPa · s.

  The viscosity at 25 ° C. is measured with a rotary viscometer (B-type viscometer).

  In the present invention, by using such a liquid organic compound (D), the tablet is uniformly dispersed when the tablet is manufactured, and when the tablet is melt-molded, the crushing at the time of measurement becomes uniform, and the measurement time of the molding is reduced. It is assumed that stability can be achieved.

  When the liquid organic compound (D) is added, the addition amount is 0.01 to 30 parts by weight with respect to 100 parts by weight of the total amount of the polyarylene sulfide resin (A) and the heat conductive filler (B). More preferably, it is 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, and most preferably 1 to 10 parts by weight.

  When the amount of the liquid organic compound (D) added is excessively larger than the range of the present invention, it bleeds out to the surface of the obtained molded product, thereby causing peeling of the interface between the thermoplastic resin and the filler, and on the contrary, mechanical properties. If the amount is too small, the effect of reducing the characteristic variation of the molded product due to the stabilization of the measuring time during molding obtained by addition tends to be small.

  In addition, in the present invention, when a phosphate ester is added in the substance (C) or the liquid organic compound (D), it is possible to improve easy crushability and fluidity at the time of tablet formation. The phosphoric acid ester used in the present invention is selected from monoesters, diesters, triesters and tetraesters of phosphoric acid, and preferred examples include those represented by the following formula (1).

  First, the structure of the phosphate ester represented by the formula (1) will be described. In the formula of the formula (1), n is an integer of 0 or more, preferably 0 to 10, particularly preferably 0 to 5. The upper limit is preferably 40 or less from the viewpoint of dispersibility.

  K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably k or m is an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1 respectively.

In the formula (1), R ^{1 to} R ⁸ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, neopentyl, and tert-pentyl. Group, etc. are mentioned, but hydrogen, methyl group and ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups or aromatic groups substituted with an organic residue containing no halogen. Examples of the aromatic group include aromatic groups having a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton, and among them, those having a benzene skeleton or a naphthalene skeleton are preferable. These may be substituted with a halogen-free organic residue (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include phenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, naphthyl groups, indenyl groups, anthryl groups and the like, but phenyl groups, tolyl groups, xylyl groups, cumenyl groups, A naphthyl group is preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, and Ph represents a phenyl group.

  Specific examples of such phosphate esters are selected from Daihachi Chemical Co., Ltd. PX-200, PX-201, PX-130, CR-733S, TPP, CR-741, CR-747, TCP, TXP, CDP. One or more selected from the group consisting of PX-200, TPP, CR-733S, CR-741, and CR-747, particularly preferably PX-200. , CR-733S and CR-741 can be used, but PX-200 is most preferable.

  In this invention, any 1 type of phosphate ester, or a mixture of 2 or more types may be sufficient.

  In the present invention, the phosphate ester not only has excellent plasticizing properties at the time of molding processing, but also because the familiarity of the polyarylene sulfide resin and the heat conductive filler is good, by using the phosphate ester, It is inferred that both the shape retention and the stability stability imparting effect due to the stable crushing of the tablet at the time of molding and the fluidity improving effect in the mold can be obtained.

  The addition amount in the case of adding the phosphoric acid ester is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the polyarylene sulfide resin (A) and the heat conductive filler (B). More preferably, it is 0.1-25 weight part, More preferably, it is 1-20 weight part, Especially preferably, it is 2-15 weight part. Especially, 3-10 weight part is preferable.

  If the amount of phosphate ester added is too much higher than the range of the present invention, it will bleed out on the surface of the resulting molded product, thereby causing peeling of the polyarylene sulfide resin and the thermally conductive filler interface, and mechanical properties. If the amount is too small, the effect of imparting metering stability and flow stability upon molding due to addition tends to be small.

  In the thermally conductive filler (B) used in the present invention, in order to improve the packing density between the fillers, and to further reduce the dimensional change rate at the time of temperature rise by filling more densely, to improve the dimensional stability, The particle size distribution preferably includes a considerable amount of particles having a larger particle size. In the cumulative particle size distribution curve measured by the laser diffraction method in terms of balancing the effects of improving dimensional stability and thermal conductivity at a high level, 25% by volume or more is based on 50% cumulative particle size (D50) × 1.5 Large particles are preferred, more preferably 30% by volume or more, and even more preferably 35% by volume or more. The upper limit is preferably 45% by volume or less.

  The measurement by the laser diffraction method uses a laser diffraction particle size distribution measurement device (for example, a laser diffraction particle size distribution measurement device SALD manufactured by Shimadzu Corporation) at a concentration of 100 ppm using a dispersible liquid such as water or a solvent as a dispersion medium. -3100). The “dispersible liquid” used above varies depending on the type of filler and cannot be generally described. However, the filler may be any liquid that can be uniformly dispersed with primary particles without secondary aggregation.

  In order to make the filler used in the present invention have such a particle size distribution as described above, for example, two or more fillers having different average particle sizes or particle size distributions are used in combination, or those obtained by fractionation by particle size by sieving or the like are desired. A method of mixing so as to obtain a particle size distribution can be employed.

  The particle size distribution is indicated by a curve in which the amount of particles (%) in each particle size interval measured by a laser diffraction particle size distribution measuring device is plotted. The cumulative particle size distribution curve is equal to or less than the particle size. It is a curve obtained by accumulating the amount of particles (%), and represents the percentage of the total amount of particles having a specific particle diameter or less.

  The heat sink tablet of the present invention can be further added with other fillers in order to impart mechanical strength and other characteristics, and use fillers such as fibers, plates, powders, and granules. be able to. Specifically, glass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, asbestos fibers, rock wool, etc., whisker-like fillers, mica, talc, kaolin, fused silica, calcium carbonate, glass Examples of the filler include powdery, granular, and plate-like fillers such as beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, and calcium polyphosphate. Among the fillers, glass fiber is particularly preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like. Further, the above fillers can be used in combination of two or more kinds, and are used, for example, for the purpose of achieving both mechanical strength and low warpage of a molded product. In addition, the surface of the filler used in the present invention has a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, etc.) or other surface treatment. It can also be used after being treated with an agent.

  Moreover, the glass fiber to be used may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

  The amount of the filler added is usually 0.5 to 150 parts by weight, preferably 5 to 100 parts by weight, and more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin (A). is there.

  The heat sink of the present invention has other components such as antioxidants and heat stabilizers (such as hindered phenols, hydroquinones, phosphites, and substitutes thereof) and weathering agents as long as the effects of the present invention are not impaired. (Resorcinol series, salicylate series, benzotriazole series, benzophenone series and hindered amine series, etc.), mold release agents and lubricants (montanic acid and its metal salt, its ester, its half ester, stearyl alcohol, stearamide, various bisamides, bisurea and Polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dyes (eg, nigrosine), crystal nucleating agents, plasticizers (eg, octyl p-oxybenzoate and N-butylbenzenesulfonamide), antistatic Agent Alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, and betaine amphoteric antistatic agents), flame retardants (for example, , Red phosphorus), melamine cyanurate, magnesium hydroxide, aluminum hydroxide and other hydroxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or their brominated flame retardants And a combination of antimony trioxide and the like) and other polymers.

  In the present invention, a tablet refers to a granular material obtained by compacting a raw material containing a powdery raw material in a solid phase. Such a tablet is obtained by compression molding a raw material containing a powdery raw material in a solid phase. be able to. In the above, the solid phase state means that the thermoplastic resin component contained in the raw material is not melted. For the compression molding, it is preferable to use a molding machine having a compression roll such as a tableting machine (rotary, single-shot, double, triple) or briquette machine. Examples of the powdery raw material include polyarylene sulfide resin powder (polyarylene sulfide resin powder), heat conductive filler, and the like that should be contained in the tablet. A powder of a composition obtained by melt-kneading a material can also be used, and one or more of these can be appropriately selected and used so as to have a desired composition.

  The heat sink tablet manufacturing method of the present invention comprises, for example, polyarylene sulfide resin powder and a thermally conductive filler, which are uniformly blended in a solid phase using a Banbury mixer, kneader, roll, uniaxial or biaxial extruder, etc. It can be obtained by tableting with a tableting machine or a molding machine having a compression roll. Also, polyarylene sulfide resin and thermally conductive filler are dry blended in advance using a Banbury mixer, kneader, or roll, or once melt-kneaded using a single or twin screw extruder, etc. without dry blending. Then, after cooling and pulverizing to form a powder, it is possible to form a tablet by using a tableting machine or a molding machine having a compression roll. In this case, the polyarylene sulfide resin used for melt kneading is not particularly limited in powder form or pellet form as long as melt kneading is possible, but it reduces the variation in characteristics due to poor dispersion of the heat conductive filler. It is preferably in the form of powder or pulverized product. Also, when using a single-screw or twin-screw extruder to make a pre-melted and kneaded composition in powder form, if the amount of heat conductive filler used is large, the fluidity deteriorates, so extrusion from the die is difficult. In some cases, however, pelletization may be difficult. In such a case, as described in JP-A-8-1663, kneading and extrusion may be performed with the head portion of the extruder open. When the amount of the heat conductive filler is large, a flaky composition may be obtained. In the present invention, if necessary, a pellet or flake composition obtained by melt-kneading in advance by these methods is cooled and pulverized to form a powder and then tableted. In addition, these methods can be combined into tablets. That is, the composition powder obtained by melt-kneading the polyarylene sulfide resin and the heat conductive filler, and the thermoplastic polyarylene sulfide resin powder and / or the heat conductive filler have a desired content. It can be adjusted and tableted. Among the above methods, the process is simple, and the mixture obtained by uniformly blending polyarylene sulfide resin powder and heat conductive filler in a solid phase is converted into tablets using a tableting machine or a molding machine having a compression roll. Is preferred.

  The polyarylene sulfide resin powder can be obtained by subjecting the pellets to normal temperature or freeze pulverization, in addition to the polyarylene sulfide resin usually available in powder form. Freezing and pulverization can be performed by using a generally known hammer type (atomizer) pulverizer, cutter type pulverizer, grinder type, or mortar type pulverizer after being frozen with dry ice or liquid nitrogen. it can. As the polyarylene sulfide resin powder used in the present invention, particles obtained by measurement based on a laser diffraction particle size distribution measurement method from the viewpoint of uniform composition between the obtained tablets and good handling properties of the obtained tablets The number average particle diameter of the maximum major axis is preferably 1000 μm or less, more preferably 800 μm or less, and even more preferably 500 μm or less. Moreover, it is preferable from a viewpoint of handleability that the sieve corresponding to 5 micrometers is what does not pass substantially. In order to obtain a powder having such a particle size, the powder obtained by pulverization or the like may be appropriately sieved using a sieve having a desired size.

  In addition, considering the melt processability and the surface appearance of the resulting molded product for the heat conductive filler, the size of the heat conductive filler is 1000 μm when measured based on the sieving test method based on JIS-K0069. It is preferable that it passes through a sieve corresponding to No. 1, more preferably that passes through a sieve corresponding to 800 μm, particularly preferably that passes through a sieve corresponding to 500 μm. Moreover, it is preferable that the sieve corresponding to 0.1 μm does not substantially pass. Here, “substantially does not pass” means that 95% by weight or more does not pass.

  Such a heat conductive filler may be selected from commercially available ones, or classified by using a sieve, and those having a required size can be taken out and used. In addition, as for the shape of the heat conductive filler to be used, fiber shape, plate shape, scale shape and crushed product are preferably used from the availability of pellets of the composition, and further the strength of the molded product obtained in production, etc. From the point of view, a fiber shape, a plate shape or a scale shape is preferable.

  Furthermore, two or more types having different particle sizes may be used in combination depending on the required characteristics.

  In the present invention, when blending other components that can be blended as necessary, the blending method is not particularly limited, and the polyarylene sulfide resin composition powder previously melt-kneaded with the polyarylene sulfide resin is polyarylene sulfide resin. When the polyarylene sulfide resin powder and the heat conductive filler are uniformly blended in the solid phase, they may be added and blended together. Moreover, when using the powder of the composition which melt-kneaded polyarylene sulfide resin and the heat conductive filler previously, you may add and blend another component together in the case of the melt-kneading. Further, it may be added by adhering around the tablet.

  As the shape of the tablet of the present invention, when considering shape retention during transportation and easy crushability during molding, for example, columnar, elliptical columnar, truncated cone shape, spherical, elliptical spherical, egg-shaped, Macek type , Disk-shaped, cubic-shaped, and prismatic-shaped. Among these, a cylindrical shape, an elliptical column shape, a spherical shape, an elliptical spherical shape, a truncated cone shape, an egg shape, and a Macek shape are preferable from the viewpoint of measurement stability during processing.

  Further, the tablet size of the tablet is preferably a bottom surface of 15 mm diameter or less × length of 20 mm or less, in particular, the maximum value of the bottom surface diameter or length (height) is preferably less than 15 mm, and the minimum value is 1 mm or more. It is preferable that As for the method for defining the maximum diameter and the minimum diameter with respect to those having a non-circular bottom surface, when the maximum diameter and the minimum diameter of the circumscribed circle are specified, the maximum diameter is preferably less than 15 mm and the minimum diameter is 1 mm or more. More preferably, the maximum diameter is 12 mm or less and the minimum diameter is 1.5 mm or more.

  In addition, in order to keep the shape stable during transportation, the compression fracture strength value (crush strength value) when pressure is applied perpendicularly to the side of the tableting surface of the tablet or the compression surface of the compression roll, Preferably it is 5-100N, More preferably, it is 15-80N. As a method for obtaining a preferable crushing strength value, for example, it is most dependent on the raw material composition, and by adding the substance (C), liquid organic compound (D) or phosphate ester, or in the tableting process, A method of supplying the raw material so that the raw material is uniformly filled in the raw material supply pocket (rotary when the tableting machine is a rotary type, compression roll in the case of a molding machine having a compression roll) The raw material filling speed is adjusted by adjusting the rotational speed of the material and the feed rate of the raw material), a method of reducing the rotational speed of the compression roll and extending the pressurization time of the material on the compression roll, using a feed screw in the hopper High tablet density and high crushing strength are achieved by the effective degassing and pre-compression method before roll compression with the screw. It is obtained. The crushing strength value is measured by placing a tablet on a strain gauge such as a load cell, and lowering the indenter at a low speed (preferably 0.1 to 2.0 mm / sec), and straining the tablet at the time of compressive fracture. It can be performed using a method of measuring the pressure indicated by the gauge.

  By using such a method, it is possible to obtain a heat sink tablet that could not be achieved conventionally.

  By using such a method, it is possible to obtain a composition in which a thermally conductive filler that cannot be conventionally achieved is highly filled.

  The tablets thus obtained are melt-molded such as injection, extrusion or press, especially injection molding methods (general injection molding, injection compression molding, two-color molding, sandwich molding, etc. Among them, general injection molding and injection compression molding are preferred. ) Can be processed into a three-dimensional molded product, a sheet, a container or the like.

  In the present invention, the molded product obtained by the above-described molding method can impart characteristics such as high heat dissipation, weld part durability, low burr property, and the like.

Moreover, the heat sink thus obtained has high heat dissipation. Oite this onset Ming can heat conductivity to obtain a heat sink having high heat dissipation property as above 5W / mK. In a more preferred embodiment, a heat sink of 10 W / mK or more can be obtained, and in a more preferred embodiment, a heat sink of 20 W / mK or more can be obtained. Although there is no particular limitation on the design of the material, a heat conductive filler having a higher thermal conductivity is used, and molding is performed at low speed and high pressure during molding, and the filler is oriented and aligned. By forming a conduction path, it is possible to obtain about 100 W / mK.

  In addition, the measuring method of thermal conductivity is measured with a laser flash method constant measuring apparatus.

  The heat sink tablet of the present invention can be melt-molded, and can provide a heat sink that achieves high heat dissipation, weld part durability and low burr that cannot be obtained conventionally. Taking advantage of the excellent characteristics of the CPU, heat sinks and heat sinks for CPUs of computers such as personal computers and home-use game machines, heat sinks for disk drives of DVD players and DVD recorders, heat sinks for HDD recorders, home TVs, IC covers (housings) used for recreational purposes such as heat-radiating parts such as power supply units for displays such as plasma displays and liquid crystal televisions, control parts for OA equipment such as printers and fax machines, transfer device peripheral parts, toys and pachinko machines Heat dissipation fan, mobile phone, various computers, various AV machines , Heat sinks used for housings and chassis of OA equipment, etc., heat sinks, car stereos, ABS (anti-lock brake system), inverters, lighting, heat sinks for automobile electrical components and housings, etc. Heat sinks for various applications that require heat storage prevention or heat dissipation, such as applications that require high thermal conductivity, automotive parts, thermal equipment such as power generation systems such as internal combustion engines, electrical / electronic parts, medical equipment, In particular, it is effective as a heat sink, a chassis, a housing having fin-like projections, or a heat sink constituting a part thereof.

  Hereinafter, although an example is given and the present invention is explained in detail, the gist of the present invention is not limited only to the following examples.

Reference Example 1 Thermoplastic resin PPS-1 (polyphenylene sulfide): M3910 (manufactured by Toray Industries, Inc .: linear type) (310 ° C., melt viscosity at a shear rate of 1000 sec ⁻¹ is 15 Pa · s), a sample mill (Kyoritsu Riko) SK-M type) and classified with a sieve at 80 mesh pass and 150 mesh on to obtain a number average particle size of 150 μm.
PPS-2 (polyphenylene sulfide): M2588 (manufactured by Toray Industries, linear type) (310 ° C., melt viscosity at shear rate of 1000 sec ⁻¹ is 84 Pa · s), sample mill (SK-M type manufactured by Kyoritsu Riko Co., Ltd.) ) And classified with a sieve at 60 mesh pass and 150 mesh on to obtain a number average particle size of 200 μm.

PA6 (nylon 6): CM1001 (manufactured by Toray Industries, Inc.) is immersed in liquid nitrogen, pulverized with a sample mill (SK-M type, manufactured by Kyoritsu Riko Co., Ltd.), and classified with a sieve at 42 mesh pass and 80 mesh on. A number average particle diameter of 300 μm was obtained.
In the above, the number average particle diameter was measured using a laser diffraction particle size distribution measuring apparatus manufactured by Shimadzu Corporation.

Reference Example 2 Thermally conductive filler graphite (GP): # 2922 (scale-like filler, average particle size 83 μm, manufactured by SUPERIOR GRAPHITE CO.) Thermal conductivity 150 W / mK.
Alumina (Al): AL-17-H (standard grain low soda alumina, average particle size 60 μm, Showa Denko) thermal conductivity 27 W / mK.
Zinc oxide (Zn): PZ (Large particle zinc oxide, average particle size 5 μm, manufactured by Hux Itec Corp.) Thermal conductivity 54 W / mK.
Alumina (Ala): AL-32B (low soda alumina, average particle size 2.9 μm, manufactured by Sumitomo Chemical Co., Ltd.) Thermal conductivity 27 W / mK.
Alumina (Alb): AL-33 (low soda alumina, average particle size 11.7 μm, manufactured by Sumitomo Chemical Co., Ltd.) thermal conductivity 27 W / mK.

Reference Example 3 Filler silica (Si): FB-40S (spherical fused silica, average particle size 42 μm, manufactured by Denki Kagaku Kogyo Co., Ltd.) Thermal conductivity 2 W / mK
The thermal conductivity is measured by using a sample obtained by compacting various heat conductive fillers or fillers into a disk shape of 10 mm diameter × 2 mm thickness using a table press at a pressure of 20 MPa, and using a laser flash method constant manufactured by Rigaku Corporation. It was measured with a measuring device.
The filler size in the table below indicates that when a sample of 500 g was taken and classified using a sieve having a roughness corresponding to the size, it did not remain on the sieve.

Reference Example 4 Substance (C) that changes from a solid to a liquid or gas in a temperature range of 25 to 250 ° C. (uses 42 mesh pass through sieve)
HWE: Montanate ester wax “Lico Wax” E (manufactured by Clariant Japan) Melting point 78 ° C.
PX-200: “PX-200” (powdered aromatic condensed phosphate ester, CAS No. 139189-30-3, manufactured by Daihachi Chemical Industry Co., Ltd.) having a melting point of 95 ° C. and 42 mesh passed through a sieve was used.

Reference Example 5 Liquid organic compound (D)
PN411: “PN-411” (polyglyceric acid ester manufactured by Ajinomoto Fine Techno Co.) Viscosity at 8000 mPa · s at 25 ° C.

  BPD: “Exepal BP-DL” (polyoxyethylene bisphenol A lauric acid ester manufactured by Kao Corporation) Viscosity of 280 mPa · s at 25 ° C.

  The viscosity is measured at 25 ° C. using a rotary viscometer (B-type viscometer).

Examples 1-6
A rotary tableting machine manufactured by Tsukishima Machine, equipped with a thermoplastic resin of Reference Example 1 and a predetermined amount of the thermally conductive filler shown in Reference Example 2 in an amount shown in Table 1 using a Henschel mixer and equipped with an automatic raw material supply feeder. By using the tablet at room temperature, a cylindrical tablet (tablet) 7 mm in diameter and 3 mm long (maximum value 7 mm, minimum value 3 mm) was obtained. Subsequently, the following evaluation was performed using each obtained tablet.

Comparative Examples 1-3
The thermoplastic resin of Reference Example 1, the heat conductive filler shown in Reference Example 2, and the predetermined amount of filler shown in Reference Example 3 were blended in the amount shown in Table 1 with a Henschel mixer in the same formulation as in Example. Melting and kneading were carried out at the resin temperatures shown in Table 1 with a PCM30 (biaxial extruder; manufactured by Ikegai Co., Ltd.) with the head part removed, to obtain an indefinitely shaped composition. Subsequently, after drying with a hot air dryer at 140 ° C. for 3 hours, the following evaluation was performed.

  These results are shown in Table 1.

Examples 7-12
Table 2 shows the thermoplastic resin of Reference Example 1, the thermally conductive filler shown in Reference Example 2, and the substance (C) that changes from solid to liquid or gas in the temperature range of 25 to 250 ° C. shown in Reference Example 4. A 7 mm diameter x 3 mm long cylindrical tablet by blending in a predetermined amount shown in Table 2 and the amount shown in Table 2 with a Henschel mixer, and using a rotary tableting machine made by Tsukishima Machine equipped with an automatic raw material supply feeder. A maximum value of 7 mm and a minimum value of 3 mm). Subsequently, the following evaluation was performed using each obtained tablet.

  These results are shown in Table 2.

Examples 13-17
A predetermined amount of the thermoplastic resin of Reference Example 1, the thermally conductive filler shown in Reference Example 2, and the liquid organic compound (D) shown in Reference Example 5 are blended in the amounts shown in Table 3 using a Henschel mixer, and automatic raw materials A 7 mm diameter × 3 mm long cylindrical tablet (maximum value 7 mm, minimum value 3 mm) was obtained by normal temperature tableting using a rotary tableting machine manufactured by Tsukishima Machine equipped with a feeder. Subsequently, the following evaluation was performed using each obtained tablet.

  These results are shown in Table 3.

Examples 18-20
The thermoplastic resin of Reference Example 1, the thermally conductive filler shown in Reference Example 2, and the substance (C) that changes from solid to liquid or gas in the temperature range of 25 to 250 ° C. shown in Reference Example 4, or Reference Example A predetermined amount of the liquid organic compound (D) shown in Fig. 5 was blended in the amount shown in Table 4 using a Henschel mixer, and a 7 mm diameter was obtained by tableting at room temperature using a rotary tableting machine manufactured by Tsukishima Machine equipped with an automatic raw material supply feeder. A columnar tablet (maximum value 7 mm, minimum value 3 mm) with a length of 3 mm was obtained. Subsequently, the following evaluation was performed using each obtained tablet.

  These results are shown in Table 4.

(1) Thermal conductivity Using a UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), a square-shaped product of 50 mm × 50 mm × thickness 3 mm under the temperature conditions of the resin temperature and mold temperature shown in Tables 1 to 4 (Film gate) was molded, and the thermal conductivity of this molded product was measured by a laser flash method constant measuring device (LF / TCM-FA8510B manufactured by Rigaku Corporation).

(2) Durability of weld part Using UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), resin temperature in Tables 1 to 4, temperature conditions of mold temperature, molding lower limit pressure +5 MPa, center part is resin association 100 ASTM No. 1 tensile test molded products having gates formed at both ends of the molded product so as to form a (weld) portion were formed. About 100 molded products, a TSA-70L thermal shock tester (manufactured by Tabay Espec) Then, the molded product was placed on an iron plate, and the crack occurrence state in the weld part after 5 cycles was observed with 1 hour of 140 ° C. exposure time, no room temperature exposure time, and −20 ° C. exposure time of 1 hour as one cycle. The case where the weld part was not cracked at all was rated as ◎, the case where 1-9 pieces were broken, the case where it was broken, and the case where 10 pieces or more were broken were marked as × (if ◎ and ○, it was excellent in practicality).

(3) Fluidity Using a UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), a square shaped product (film gate) of 50 mm × 50 mm × thickness 3 mm under the temperature conditions of the resin temperature and mold temperature shown in Table 2 ) And the molding lower limit pressure at that time was measured (the lower the molding lower limit pressure, the better the fluidity). In addition, when the tablet of Example 1 was similarly evaluated for fluidity, it was 220 MPa.

(4) Tablet meltability Using a hot plate, place 10 tablets on the hot plate under the resin temperature conditions shown in Table 3, place a preparation on the tablet, and place a 50 g weight on the tablet. The melt time was measured with a stopwatch (the shorter the melt time, the better the meltability and the shorter the time required for molding). In addition, when the tablet meltability of the tablet of Example 2 was similarly evaluated, it was 45 seconds.

(5) Burr length Using a PS20E2ASE injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), (a) width 4 mm × length 20 mm × thickness 500 μm, (b) width 4 mm × length 20 mm × thickness 20 μm on the circumference. Using an 80 mm diameter x 2 mm thick disk-shaped mold having two protrusions, injection molding is performed under the resin temperature and mold temperature conditions shown in Tables 1 to 4, and the thick (a) protrusion reaches the tip. The filling length of the protrusion (b) having a small thickness when filling was measured to obtain a burr length. The gate position was the center of the disk (if the burr length is short, the low burr property is good).

(6) Crushing strength A tablet was placed on the load cell, and an indenter whose compression surface was a flat surface of 16 mmφ was lowered at a low speed of 0.4 mm / sec, and the pressure indicated by the load cell at the time of tablet compression fracture was measured. In addition, it shows about the used crushing strength measuring device.
Pressure application part: Linear motion (made by Oriental Motor), 6RK60RGK-AM, 60W (motor part), 6LF13-1A (linear head part), MAX140kgf (1373N)
Display: ASG-156A-42-17-1 (manufactured by Asahi Keiki Co., Ltd.), 0.1-300 kgf (0.98-2942N), resolution 1/3000.

(7) Filler cumulative ratio (evaluated in Examples 12 and 18 to 20)
From the cumulative particle size distribution curve of the thermally conductive filler of Reference Example 2, the volume ratio of particles having a cumulative degree of 50% particles (D50) × 1.5 or greater was calculated.

  The cumulative particle size distribution curve is obtained by blending the heat conductive filler (B) of Reference Example 2 with a Henschel mixer in the same composition as in the example, and about 0.05 g of the obtained heat conductive filler (B). Add 50ml of water, stir, and add a few drops of surfactant solution (a level that does not cause bubbles) in a few drops of "Mypet" (manufactured by Kao) to 100cc in advance. After dispersing with a washing machine, the particle amount (%) in each particle diameter section was plotted using a laser diffraction particle size distribution analyzer SALD-3100 manufactured by Shimadzu Corporation. From the accumulated distribution curve, D50 (average particle size) Diameter), the particle diameter of D50 × 1.5 and the volume ratio thereof were determined.

(8) Dimensional stability (linear expansion coefficient, evaluated in Examples 12 and 18 to 20)
Using a UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), a test piece having a thickness of 80 mm × 80 mm × 2 mm (film gate) was prepared at the resin temperature and mold temperature shown in Table 4, and the center part of the molded product A prismatic molded product having a length of 10 mm, a width of 1 mm and a thickness of 2 mm was cut out in a direction perpendicular to the flow direction of the resin and measured at 30 ° C. to 150 ° C. (5 ° C./min) using TMA (manufactured by Seiko Denshi). .

Comparative Example 4
A mixture of 45.5% by weight (70.2% by volume) of polyphenylene sulfide resin (T-3AG, manufactured by Toprene) and 45.5% by weight (23.6% by volume) of the alumina of Reference Example 2 using a Henschel mixer. Is supplied to the twin-screw extruder, 9% by weight (6.2% by volume) of aluminum borate whisker (manufactured by Shikoku Kasei Kogyo Co., Ltd.) is melt-kneaded from the side of the extruder, and pelletized resin A composition was obtained. Using this pellet, a UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), a square-shaped product (film gate) of 50 mm × 50 mm × thickness 3 mm under a temperature condition of a resin temperature of 320 ° C. and a mold temperature of 150 ° C. ), And the thermal conductivity of this molded product was measured with Rigaku Corporation LF / TCM-FA8510B, a laser flash method constant measuring apparatus. The thermal conductivity was 1.5 W / mK. In addition, using a UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), a resin temperature of 340 ° C., a mold temperature of 150 ° C., a molding lower limit pressure + 5 MPa, and the central portion becomes a resin association (weld) portion. In this way, 100 ASTM No. 1 tensile test molded products with gates formed on both ends of the molded product are molded, and 100 molded products are molded using a TSA-70L thermal shock tester (manufactured by Tabay Espec). It was placed on an iron plate, and the crack occurrence state in the weld part after 5 cycles was observed with 1 cycle of 140 ° C exposure time, no exposure time at normal temperature, and 1 hour exposure time of -20 ° C. The welds of 95 molded products were cracked. Using a PS20E2ASE injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), two protrusions of (a) width 4 mm × length 20 mm × thickness 500 μm, (b) width 4 mm × length 20 mm × thickness 20 μm on the circumference. When an 80 mm diameter x 2 mm thick disk-shaped mold is used and injection molding is performed at a resin temperature of 340 ° C. and a mold temperature of 150 ° C., and the thick (a) protrusion is filled to the tip The filling length of the protrusion (b) having a small thickness was measured. The burr length was 250 μm or more.

Example 21
Using the tablet of Example 10, on the side of a box-shaped molded product having a length of 40 mm, a width of 40 mm, a height of 4 mm, and a thickness of 2 mm, a square fin-shaped projection 4 having a width of 40 mm, a height of 5 mm, and a thickness of 2 mm. Using a UH1000 (80t) injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd.), a molded product with a single casing is injection molded under the same resin temperature and mold temperature conditions as in Example 10. As a result of installing a car audio DSP processor and operating the car audio and measuring the internal temperature of the housing after 5 hours, the temperature rise was reduced and the operation was good without any reading error. Therefore, it can actually be used as a heat sink.

  As is apparent from the results of Tables 1 to 4, according to the melt-molding tablet of the present invention and the heat sink obtained therefrom, the heat conductive filler can be highly filled, and the heat conductivity and weld portion that have not been obtained in the past can be obtained. It can be seen that durability and low burr are obtained. From Table 4, it can be seen that by setting the filler cumulative ratio within a preferable range, in addition to the above effects, dimensional stability and thermal conductivity can be balanced at a high level. Further, since melt processing excellent in moldability (fluidity, tablet meltability) is possible, it is possible to develop the heat sink used for obtaining high heat dissipation.

Claims (8)

A heat sink tablet comprising a polyarylene sulfide resin (A) and a thermally conductive filler (B) having a thermal conductivity of 20 W / mK or more measured by a laser flash method, wherein (A) and (B) (A) 5 to 40% by volume and (B) 95 to 60% by volume are uniformly blended in a solid phase and tableted by a tableting machine or a molding machine having a compression roll. A tablet for heat sink, wherein a heat sink having a thermal conductivity of 5 W / mK or more measured by a laser flash method is obtained by melt-molding the tablet. Furthermore , monohydric alcohol esters, phosphate esters, aliphatic metal salts, polybasic acid monohydric alcohol esters, polyhydric alcohol fatty acid esters of fatty acids that change from solid to liquid or gas in the temperature range of 25-250 ° C. , and At least one substance (C) selected from derivatives thereof, fatty acid esters of glycerin, silicone resins, phenolic compounds, benzophenone compounds, amide group-containing compounds, cyanurate compounds and salts thereof is used as component (A) and (B ) 100 parts by weight of the total of components, comprising 0.01 to 30 parts by claim 1 tablet sink according. Further , monohydric alcohol esters of fatty acids having a viscosity of 1 to 10,000 mPa · s at 25 ° C. , monohydric alcohol esters of polybasic acids, fatty acid esters of polyhydric alcohols, and derivatives thereof, fatty acid esters of glycerin, silicone oils, phosphites for at least one liquid organic compound (D) to component (a) and (B) total 100 parts by weight of components selected from the system compounds and the like, according to claim 1, wherein comprising 0.01-30 parts by weight Tablet for heat sink. Claim 1-3 thermally conductive filler (B) is characterized in that more than 25 vol% in the cumulative particle size distribution curve is cumulative of 50% particle diameter (D50) × 1.5 larger particles The heat sink tablet as described. Claim 1-4 heatsink formed by melting a tablet sink according to any one. 6. The heat sink according to claim 5 , wherein the heat sink is a chassis, a housing, or a heat sink constituting a part thereof. The heat sink of Claim 5 or 6 which has a fin-like protrusion. A method for producing a heat sink, wherein the heat sink tablet according to any one of claims 1 to 4 is injection-molded.