TW200925200A - Insulating resin composition and application thereof - Google Patents

Abstract

The present invention provides a resin composition comprising: (A) a thermoplastic resin, (B) a granular material which has a number average particle diameter of 0.5 to 5 mm and is obtainable by granulating a fiber mainly having alumina with a number average fiber diameter of 1 to 50 μm, and (C) a filler composed of a material of which electric resistivity at 300 K is 10<SP>2</SP> Ωm or less. The resin composition can be molded into a molded article with electric insulation. The electric resistivity of the molded article has sufficient electric insulation in applications such as in electric and electronic parts.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating resin composition which can provide a molded article excellent in thermal conductivity for electrical insulation. [Prior Art] In recent years, in the field of electric power and electronic parts, the heat generated inside the parts has caused miniaturization and difficulties in advancement of the prior art. When equipment used to enhance heat management is not sufficient for this heat generation, the performance of electrical and electronic components may be reduced by the accumulation of heat. To handle this difficulty and to ensure the safety of heat generation, a component with high thermal conductivity is preferably used in power and electronic parts. Among the parts requiring high thermal conductivity, metal materials are mainly used at present, but metal materials have the disadvantages of retaining weight and being molded on miniaturized parts, and thus they are more and more often replaced by resin materials. © Many studies have been conducted on thermal conductive resin compositions including high thermal conductivity materials. Thermally conductive tantalum is used in molded articles in the form of fibers (fibrous thermally conductive tantalum) to provide a thermally conductive path in the article to provide excellent thermal conductivity. For example, a thermoplastic composition having a thermal conductive material has been proposed in which a carbon fiber having a specific fiber length is bundled (refer to Japanese Unexamined Patent Application No. (JP-A-) No. 9-157740 (paragraph [0023] 〕 to [0026]; equivalent to US 6, 120, 8 94; and a composition of a thermoplastic resin and a nitrided fiber and an inorganic powder having high thermal conductivity (refer to JP_A-8-28345 6 (Scope of Application)) 200925200 However, the molded articles obtained from the composition proposed in the foregoing are not all in accordance with the requirements of the actual use. For example, the molded article obtained from the composition disclosed in JP-A-9-157,403, wherein heat conduction The route is mainly made of carbon fiber, and since the heat conduction path made of carbon fiber is electrically conductive, it may not be suitable for electrically insulating electric or electronic parts. The heat conduction of the molded article obtained from the composition disclosed in JP-A-8-283456 Insufficiency. 0 SUMMARY OF THE INVENTION In such a case, one of the objects of the present invention is to provide an insulating resin composition which can provide an excellent guide for electric power and electronic parts. The present invention has been made in an effort to achieve the object and has completed the present invention. The present invention provides a resin composition comprising: (A) a thermoplastic resin; bismuth (B) particles. a material having a number average particle diameter of 0.5 to 5 mm and which can be obtained by granulating fibers mainly having alumina having a number average fiber diameter of 1 to 50 μm; and (C) a dip material, which is 300 K Further, the present invention provides a molded article obtainable by molding the foregoing resin composition. The resin composition of the present invention is an insulating resin composition, which can be Molded by, for example, molding into a molded article having electrical insulation by a known method. -6- 200925200 The resistivity of the molded article is substantially ίο12 ohm meters or more, and the molded article is in, for example, electric power. And electrical insulation of the application of the electronic component. From the insulating resin composition of the present invention, a molded article having excellent electronic insulation can be obtained and can be used as the main component and the electronic component. In particular, the molded article is suitable. It is an element related to parts and is very useful in industry. 实施 [Embodiment] The resin composition of the present invention comprises: (A) a thermoplastic resin; (B) a granular material having a number average particle diameter of 〇.5 3 It can be obtained by granulating a fiber having a number average fiber diameter of 1 to 50 μm, and (C) a material which is composed of a material having a resistivity of 300 K i 〇 2 ohm Q. The component (c) used is composed of a resistance of 300 Å or a lower material. Preferred examples of the material include materials such as Au (3x10., Ag (2x10_8 ohm meters), Cu (2xl ( T8 ohm meters) bismuth carbide (lxlO·6 ohm meters) and graphite (ΐχ10.5 ohm dimensions (3χ 1 0·6 ohm meters). In particular, the crucible made of carbonized sand, the crucible composed of graphite or the carbon i here, the one in the aforementioned brackets, represents a high measured at 3 〇〇 K and thus has a sufficiently high thermal conductivity. It is better to use a cut-off dip material for electric power and electrons of 5 5 mm and meters of alumina or a lower rate of 1 〇 2 ohms _ 8 ohm meters. Resistivity. 200925200 A crucible composed of niobium carbide is preferably a granular material having a number average particle diameter of 0.1 to 30 μm (preferably 0.5 to 20 μm, more preferably 1 to 1 μm). When the particle diameter is in the range of 0.1 to 30 μm, the surface of the resulting molded article is not significantly degraded. Therefore, this molded article having an excellent appearance is obtained, and the effect of improving the thermal conductivity becomes sufficient. Further, when the particle diameter is within this range, there is an advantage in that the moldability of the insulating resin composition becomes good. Examples of Q niobium carbide particles include the OY series (registered name:

Yakushima Denko Co., Ltd.). Preferred carbon fibers include resin-based carbon fibers. When measured at a temperature of 300K, the carbon fiber has a thermal conductivity of 1 watt/mK, a thermal conductivity of 120 watts/meter K or higher, and a thermal conductivity of 200 watts/meter K or higher. . The carbon fiber preferably has a fiber diameter of 1 to 20 μm and a fiber diameter of 5 to 15 μm. Examples of the carbon fiber include Dialead (manufactured by Mitsubishi Plastic Inc.) and Granock (manufactured by Nippon Graphite Fiber Corporation). This graphite may be natural graphite or may be artificial graphite. Natural graphite is preferred. The shape of the pigment (graphite crucible) composed of graphite can be scaly or spherical. The graphite crucible preferably has a number average particle diameter of 30 to 300 μm and a number average particle diameter of 30 to 1 μm. The number average particle diameter is preferably from 3 Å to 300 μm, because the high thermal conductivity and moldability of the resulting resin composition are balanced when the graphite mash is mixed into a thermoplastic resin (particularly a liquid crystal polyester described below). Excellent reason. The number average particle diameter can be easily measured by using the method of measuring the size distribution of the laser diffraction particles -8-200925200. The graphite crucible suitable for use in the present invention can be selected based on the number average particle diameter obtained by the laser diffraction particle size distribution method. Examples of readily available graphite crucibles include scaly graphite powder or granulated graphite powder (both from Nippon Graphite Industries Co., Ltd.) and scaly graphite (made from Nishimura Grpahite Inc., Ltd .). 〇 Among these exemplified graphites, scaly graphite is preferably used because the obtained resin composition has excellent moldability. The advantage of this scaly graphite is the cost, since it is cheaper than granular graphite. It is known that the thermal conductivity of a substance is inversely proportional to the electrical resistivity. When a material having a low resistivity (low resistivity material) (e.g., a metal material or a carbon fiber) is used as a highly thermally conductive material, the electrical insulation of the resulting molded article tends to decrease. Therefore, the use of low-resistivity materials is limited for power and electronic parts that generally require electrical insulation. On the other hand, the present invention provides a resin G composition which can be molded into a molded article by utilizing high thermal conductivity of a crucible composed of a low-conductivity material and maintaining sufficient electrical insulation. In the present invention, by using a dip material composed of a low-resistivity material and the following composition, the obtained molded article has an advantage that the electrical insulating property and the thermal conductivity are highly coordinated to the resin composition of the present invention. In the middle, the concentration of the material consisting of the low-resistivity material is preferably the same as or lower than the concentration (osmotic concentration) at which the conductive material is in contact with each other to form a conductive path, and the component (Β) is effectively located by A material consisting of low resistivity materials. Therefore, the 'thermal conduction pathway' consists of Group-9-200925200 parts (B) (materials that granulate mainly alumina fibers) and component (C) (low-resistivity materials) to have high thermal conductivity. And maintain the electrical insulation of the thermal path. Furthermore, even when the thermally conductive path is fabricated in such a way that the materials consisting of the low resistivity material are connected to each other with a suitable electrical insulator, it must be noted that the so-called tree dielectric disintegration occurs between the materials of low resistivity material, and The dielectric strength voltage of the obtained molded article was remarkably low. However, with respect to the molded article obtained from the insulating resin composition of the present invention, it is surprising that such dielectric collapse is sufficiently suppressed and the dielectric strength required for electric power and electronic parts is easily obtained. Excellent effect of potential (dielectric breakdown voltage: 1 kV/mm or higher). As the foregoing, the mixing amount of the component (C) is appropriately selected such that it is an osmotic concentration or lower in the obtained molded article, and based on the kind of the component (A), it is necessary to make the component ( The amount of mixing of C) is optimized to control the amount of mixing to be osmolality or less. The preferred mixing amount of the component (C) is based on the component (A), and is 1 to 50 parts by weight relative to 100 parts by weight of the thermoplastic resin component (C) of the component (A). Preferably, it is preferably from 1 to 40 parts by weight, more preferably from 5 to 40 parts by weight. When the compounding amount of the component (c) is in the foregoing range, the electrical insulation is sufficiently maintained, and a molded article having a high thermal conductivity can be obtained. The resin composition of the present invention comprises a particulate material (component (B)) having a number average particle diameter of 0.5 to 5 mm and which can be obtained by a fiber mainly having an alumina having a number average fiber diameter of 1 to 5 G It is obtained by granulation. Here, the particle size in the "granular material" means that the material is granular and the aspect ratio -10-200925200 (which is the ratio of the major axial length of the material to the minor axis length) is in the range of 1 to 2. The "number average particle diameter" is obtained by scanning electron microscopy or optical microscopy for the observation of the main axis and the minor axis of the granular material, and the arithmetic mean of 値 measured by 1 〇〇 or more of the granular material. Please note that 1000 or more measurements of the fiber are photographed and binarized by the image processing device to obtain the number average fiber diameter of the fibrous material. The particulate material, component (B), is a material obtainable by granulating fibers mainly having alumina Φ (e.g., alumina fibers). Thereby, the synergistic effect of the granular material and the component (C), the electrical insulation and the thermal conductivity are highly coordinated. The "mainly alumina" fiber preferably contains about 50% by weight or more of alumina (i.e., alumina (ai2o3)). The aluminum oxide content in the fiber is preferably about 70% by weight or more, and preferably about 90% by weight or more. The fiber mainly having alumina has a component other than alumina, such as Q yttrium oxide (si〇2). The number average fiber diameter of the alumina fibers used in the particulate material is not limited and may be in the range of 1 to 50 μm, preferably 1 to 30 μm, more preferably 1 to 20 μm. When the number average fiber diameter is in the range of 1 to 50 μm, the granulation workability for obtaining a granular material is good, and there is an advantage that the fiber itself is difficult to cut in the granulation method. When the granular material of alumina having a too short diameter is used as the component (B), the effect of improving the thermal conductivity is impaired. The fiber strength of the molybdenum oxide fiber is not limited. Commercially available alumina fibers are useful in the present invention, and commercially available alumina has a fiber strength of from 100 μm to 100 η -11 to 200925200 m, preferably from 100 μm to 80 mm, and more preferably from 150 μm to 60 mm. When the fiber strength is in the range of from 1 μm to 1 mm, the resulting resin composition of the present invention is excellent in moldability, and thermal conductivity (which is one of the objects of the present invention) is further improved. Examples of commercially available oxidized Ming fibers include Altex (manufactured by Sumitomo Chemical Co., Ltd.), D enka A1 ceη (manufactured by D enki Kagaku kogyou), Maftec bulk fiber (manufactured by Mitsubishi Plastic ❹ Inc.), and Saffil alumina fiber (Saffil). Made by Japan Ltd.) Preferably, the alumina fiber is a fiber having an overall density of 0.2 to 1 g/cm 3 which can be measured according to Japanese Industrial Standards (JIS) K5 101-12. When this fiber is used, in addition to the ease of production of the granular material, it is advantageous in that the thermal conductivity of the molded article obtained from the resin composition obtained by the present invention is further improved. The overall density is preferably from 0.2 to 0.5 g/cm, more preferably from 0.2 to 0.4 g/cm, and most preferably from 0.2 to 0.35 g/cm. Although the alumina fibers having such an overall density are in the form of tufts, they can be made into a granular material in the granulation step of preparing the resin composition of the present invention described below, and have preferable workability. By granulating the alumina fibers, a particulate material of the component (Β) can be obtained. Examples of the granulation method include known methods such as agitating granulation, vibrating granulation, and honing granulation. Among them, stirring granulation is preferred. Examples of the agitator for agitating granulation include a rotary machine, a Nauta mixer, a ribbon blender, and a Henschel mixer. Among them, the Henschel mixer is preferred for the purpose of short-term processing. -12- 200925200 As the foregoing, the number average particle diameter of the granular material is in the range of 0.5 mm to 5 mm, preferably 1 mm to 2 mm, more preferably 1 mm to 1.5 mm. When the number average particle diameter is 0.5 mm or more, the workability (especially, the workability of the obtained resin composition) becomes good. When the number average particle diameter is 5 mm or less, the dispersibility of the particulate material in the molten resin becomes good to obtain a molded article by melting the resin composition, both of which provide good moldability. The conditions for obtaining granular φ material having such a number average particle diameter vary depending on the stirring machine, and basically, they can be controlled by the stirring rate and the stirring time, and the highest conditions can be attained by the prior experiment. Further, after the granulation treatment, the fine particles and the coarse particles are removed by a sorting operation to obtain a granular material having a number average particle diameter of 0.5 to 5 mm. Examples of classification operations include the use of a Dorco classifier, a siphon classifier, a tilting classifier, a spiral classifier, etc. as a wet sorting operation; and the use of a centrifugal sorter, inertial sorting, screen, etc. Dry sorting operation. This agitation granulation can be carried out by a known method, and the particles thereof include a method for powder granulation using the aforementioned mash mixer, a method of stirring and drying the alumina fibers after mixing in a suitable solvent, and stirring by a mixer or the like. Spray the appropriate solvent and then dry. Further, it may be a method of stirring by a mixer or the like while spraying a suitable solvent onto the pellet of alumina fiber. In this method, the usable solvent is, for example, water, an organic solvent or a mixture thereof. Preferably, water or a water/organic solvent mixture (wherein water is the main component) is suitably used as the solvent. Among the solvents, water is preferred. In the agitation granulation of the present invention, the astringent may be contained in a solvent. -13- 200925200 This astringent is not particularly limited and various types can be used. Examples of astringents include decane-based and titanate-based coupling agents. Examples of the decane-based coupling agent include, for example, γ-mercaptopropyltrimethoxydecane, 2-styrylethyltrimethoxydecane, Ν-ρ-(aminoethyl)-γ-aminopropyl Trimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, phenyltrimethoxydecane, methyldimethoxy Decane, which can be used alone or in combination with two or more. Examples of titanate-based coupling agents include isopropyl triisostearate titanate, isopropyl trioctylide titanate, isopropyl tris(dioctyl pyrophosphate) titanate, Isopropyl tris(dimethylpropenyl)isostearyl decyl titanate, isopropyl tris(indene, fluorenyl-diaminoethyl) titanate, isopropyl tris(dodecylbenzene) Sulfonyl) titanate, isopropylisostearylnonyl propylene acrylate titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, Tetraisopropylbis(dioctylphosphonate)titanate φ ester, tetraoctylbis(di(dodecyl)phosphate) titanate, tetrakis(2,2-diallyloxymethyl) -1-butyl)bis(di(tridecyl)phosphate) titanate, bis(dioctylpyrophosphate)oxyacetate titanate and bis(dioctylpyrophosphate) titanate Ethylene glycol 'can be used alone or in combination with two or more. Further, a decane coupling agent and a titanate coupling agent can be used together. The coupling agent content may be 5 parts by weight or less with respect to 100 parts by weight of the total amount of alumina fibers, preferably 2 parts by weight or less. In the granular material of the present invention, it is difficult to observe the effect of improving the thermal conductivity-14-200925200 by an astringent (e.g., 'coupling agent), but when the amount of the coupling agent is too large, it will be molded by the obtained resin composition. The thermal conductivity and mechanical properties of the article are lower than preferred. However, in view of the affinity of the granular material for the resin to be mixed, and the improvement of the feeding property of the molded resin composition at the time of molding, the fibrous material obtained by treating a small amount of the coupling agent can be used. Shaped material. When the particulate material of the component (B) is thereby obtained, the component (?B) can have a preferred number of the present invention by the classification operation before the component (B) is used in the resin composition of the present invention. Particle diameter. The amount of the component (B) to be used in combination with the component (C) can be set within a range having high thermal conductivity and electrical insulation. The component (B) is preferably used in an amount of 10 to 400 parts by weight, more preferably 1 to 300 parts by weight, based on 100 parts by mass of the thermoplastic resin (component (A)). When the mixing amount of the component (C) is in the range of 10 to 400 parts by weight, the electrical insulating property and the thermal conductivity are still compatible. The thermoplastic resin of the component (A) used in the present invention may be a resin which can be molded at a molding temperature (melting temperature) of from 200 to 450 ° C and which can be used as an electrically insulating material. Examples of the thermoplastic resin as the component (A) include polyisolated hydrocarbons, polystyrene, polyamine, vinyl halide resin, polyacetal, saturated polyester 'polycarbonate, polyarylsulfonium, polyaryl ketone, Polyphenylene ether, polyphenylene sulfate, polyaryl ether ketone, polyether maple, polyphenylene sulfide mill, polyallyl ester, aromatic polyamine, liquid crystal polyester, and fluororesin. This thermoplastic resin may be used singly or may be used as a polymer mixture composed of two or more thermoplastic resins. Among the thermoplastic resins, preferred resins are liquid crystal polyester, polyether mill, polyene-15-200925200 propyl ester, polyphenylene sulfide, polyamine 4/6 or polyamine 6T, which are particularly excellent in heat resistance. Among them, polyphenylene sulfide and liquid crystal polyester are particularly preferable, and in addition, liquid crystal polyester is more preferable in terms of good thin-wall moldability. Liquid crystal polyesters having good thin-wall moldability are particularly suitable for the manufacture of components having complex shapes for use in electric power and electronic parts. Polyphenylene sulfide and liquid crystal polyester as suitable thermoplastic resins will be described in more detail below.

Basically, polyphenylene sulfide is a resin mainly comprising a structural unit represented by the following formula (10). As a method of producing the polyphenylene sulfide, examples of the method include a method of reacting a halogen-substituted aromatic compound with an alkali metal sulfide (for example, U.S. Patent No. 2,5,13,188 and Japanese Patent Application No. 44) -27671), a condensation reaction of thiophene in the presence of a basic catalyst, a copper salt or the like (as shown in U.S. Patent No. 3,274,165) or an aromatic compound and sulfur chloride in a Lewis acid The condensation reaction is carried out in the presence (as shown in Japanese Patent Application No. 46-27255). Further, commercially available polyphenylene sulfide (for example, polyphenylene sulfide obtained from Dainippon Ink and Chemicals Inc.) can also be used.

The liquid crystal polyester used in the present invention may be referred to as a thermotropic liquid crystal polymer which forms a melt at 450 ° C or lower. The liquid crystal polyester has a starting flow temperature of 28 (TC or higher. Note that the "starting flow temperature" is a heated melt of the liquid crystal polyester at a heating rate of 4 -16 to 200925200 ° C / min at 100 kg / At a square centimeter load, the melt has a melt viscosity of 48,000 poise when it is extruded. Examples of liquid crystal polyesters include: (1) by a combination of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and an aromatic diol Produced by polymerization, (2) by the polymerization of different types of aromatic hydroxycarboxylic acid, φ (3) by polymerization of aromatic dicarboxylic acid and aromatic diol, and (4) By the reaction of a crystalline polyester (e.g., polyethylene terephthalate) with an aromatic hydroxycarboxylic acid. These aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids are replaced by the use of their ester derivatives. The acid or aromatic diol, liquid crystal polyester is easy to produce, which is preferred. When the aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid used have an intramolecular carboxy Q group, the ester derivative Examples include conversion reactions in which a carboxylic acid group is converted into a highly reactive group (e.g., a hydrazine halide group and an acid anhydride). Derivatives, and esters of alcohols and ethylene glycols which can be converted to esterification to form polyesters. When the aromatic hydroxycarboxylic acids and aromatic diols used have intramolecular phenolic hydroxyl groups, the ester derivatives Examples include esters of a phenolic hydroxyl group and a lower carboxylic acid which can be esterified to form a polyester. The aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid and the aromatic diol may have a halogen atom on the aromatic ring. (e.g., chlorine and fluorine atoms), alkyl (e.g., methyl and ethyl), and aryl (e.g., phenyl), to the extent that they do not excessively dry. Examples of the structural unit in the liquid crystal polyester of the invention include the following: a structural unit derived from an aromatic hydroxycarboxylic acid:

(Αι) The aforementioned structural unit may have a halogen atom, an alkyl group or an aryl group as a substituent. Structural unit derived from an aromatic dicarboxylic acid: -18- 200925200

The aforementioned structural unit may have a halogen atom, an alkyl group or an aryl group as a substituent. Structural unit derived from aromatic diol: -19- 200925200

The aforementioned structural unit may have a halogen atom, an alkyl group or an aryl group as a substituent. An example of a combination of structural units selected from the preceding units constitutes a liquid crystal polyester comprising the following combinations (a) to (h). (a) : a combination of ( A, ), (Β,) and (C,), or a combination of (A!), (Βι), (B2) and (Ci); (b) : ( A2 ) , ( a combination of B3) and (C2), or a combination of (A2), (B!), (B3), and (C2); -20- 200925200 (c): a combination of (A,) and (A2); ) : Substituting some or all of (A!) of the structural unit combination (a) with (A2) for the resulting combination; (e): combining some or all of (B!) of the structural unit combination (a) with ( B3) replacing the resulting combination; (f): replacing some or all of (C!) of the structural unit combination (a) with (C3); φ (g): combining structural units (b) Part or all of (A2) replaces the obtained combination with (Ai); (h): adds (Bd and (C2) to the structural unit combination (the combination obtained by 〇. in terms of heat resistance, mechanical properties and processability) From the viewpoint of balance, a particularly preferred liquid crystal polyester has (the amount of the structural unit represented by Ad is at least 30 mol% based on the total structural unit of the liquid crystal polyacetate. The liquid crystal poly is equivalent to the combination of (a) and (b) Esters are disclosed in, for example, Japanese trials Patent application Nos. 47-47870 and 63-3888, and can be prepared by the method disclosed in, for example, Japanese Unexamined Patent Application No. 2002-146003. For example, the steps of the method for preparing the liquid crystal polyester A monomer (an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, an aromatic diol or a crude ester derivative thereof) is subjected to a melt polycondensation reaction to obtain an aromatic liquid crystal polyester having a relatively low molecular weight (hereinafter referred to as " Prepolymer ',), after which the prepolymer is powdered and the powder is heated to initiate solid phase polymerization. When this solid phase polymerization is carried out, it can be further polymerized to obtain a polymer having a higher molecular weight. By the combination of melt polymerization and solid phase polymerization - 21 - 200925200 The method for producing a liquid crystal polyester can improve the obtained liquid crystal polyester. In particular, it can be easily produced by appropriately solidifying a solid phase polymerization reaction. From the viewpoint of having a liquid crystal property at a desired starting temperature, preferably, the polyester of the present invention is a structural unit derived from p-hydroxybenzoic acid and a structural unit derived from 6-naphthoic acid. a structural unit of 80 mol%; a structural unit derived from argon-arsenic and a structural unit derived from 0-biphenyl are a total of 100% of the total structural unit of the liquid crystal polyester; and a structural unit derived from citric acid, a derivative unit, and The liquid crystal polyester of the present invention having a total structural unit derived from 2,6-naphthalenedicarboxylic acid of 10 to 35 mol% comprises the component (A), using the composition, An electrically insulating and high-conductive member can be obtained. The resin composition of the present invention may further comprise (E (component (D)) as a thermal conductive coating. This inclusion of the oxidized φ composition further improves the thermal conductivity. Further, when the thermoplastic resin of the liquid (A) is used, the resulting molded article is anisotropic. The anisotropy which is possessed by containing the component (D) as a heat-conductive crucible can be appropriately reduced as the component (D) to oxidize the ingot to be 96% by weight or more and the number average particle by oxidation. Fine particles composed of 01 α-alumina are preferred. The higher the content of the thermal conductivity, the more advantageous it is, and it is preferably 99% by weight or more, more preferably more. Further, the 'number average particle diameter is in the above range 丨 starting flow temperature: the conditions are optimal for liquid crystal polycondensation. The liquid crystal used in the crucible is derived from the 2-hydroxy-.30 to the 10,35 from the 4,4'-dihydroxy group. The isocyanate is formed by the liquid crystal polyester (Β) and C) Thermal moldings&gt;) Alumina fine-grained aluminum fine-grained resin crystalline polyester has a thermal conductivity as a group, and the thermal conductivity 〇(Α12〇3) content is 100 μm, and the alumina is 99.5% by weight. Or medium, moldability-22-200925200 The reason for the excellent is the same as in the component (B), such a number average particle diameter is preferably 0.1 to 70 μm, more preferably 0.1 to 50 μm, 0.1 to 20 μm. Especially good. Here, the number average particle diameter is an average enthalpy obtained by taking a photograph of the powdery fine particles using a scanning electron microscope and selecting 50 to 100 particles from the photograph for image analysis. Further, preferably, when the cumulative particle size distribution is measured, the alumina fine particles have a narrow particle size distribution, D90/1() (10% cumulative particle diameter from the fine particle side and 90% cumulative particle U) The sub diameters are defined as D1G and D9G, respectively, being 7 or less. Dlfl and D90 are measured, for example, by a laser diffraction particle size distribution measurement method using a Mastersizer (manufactured by Malvern Instruments Ltd.). The alumina fine particles are not particularly limited in shape as long as they satisfy the aforementioned alumina content and the number average particle diameter, but are preferably spherical, about spherical or polyhedral. Further, preferably, the major axis length of the alumina fine particles is regarded as L (micrometer) and the minor axis length is regarded as S (micrometer), and the L/S ratio is 1.0 to 3.0. φ This alumina fine particle may be a commercially available alumina fine particle. Examples of commercially available alumina fine particles include Sumikorandom manufactured by Sumitomo Chemical Co., Ltd. Further, a commercially available product (e.g., oxidized fine granules produced by Showa Denko K.K. or alumina fine granules produced by Nippon Light Metal Co., Ltd.) can be used as the component (D). When the resin composition of the present invention contains the component (D) in addition to the components (A) to (C), the component (D) is used in an amount of 5 to 250 based on 100 parts by weight of the component (A). The parts by weight are preferably from 1 to 200 parts by weight, more preferably from 20 to 150 parts by weight. -23- 200925200 When the amount of the component (D) is 5 to 250 parts by weight, the advantage is that the heat conductivity is excellent, and the moldability is not significantly impaired. As described above, the resin composition of the present invention contains components (B) and (C), or components (B), (C) and (D), and component (A), and provides good thermal conductivity. Molded items. Molded articles can be made by a variety of known methods. Examples of the method include extrusion molding, injection molding, pressure molding, and blow molding. Further, in the molding composition of the present invention, one type or a plurality of conventional additives may be added and used in the range of not impairing the desired effects of the present invention, including "including a pigment (for example, glass fiber), a fluororesin, and a detachment. Molding agents (eg, metal soaps), colorants (eg, dyes and pigments), antioxidants, thermal stabilizers, UV absorbers, antistatic agents, surfactants, and the like. In addition, one type or more substances with external lubrication can be added, such as high carbon fatty acids, high carbon fatty acid esters, high carbon fatty acid metal salts, and fluorinated carbon based surfactants. © The method for producing the insulating resin composition of the present invention is not particularly limited, and examples thereof include a method of combining the components (A) to (C), or using a Henschel mixer, a rotary machine or the like to mix the components (A) to (D), followed by melt kneading using an extruder. Further, 'examples include a method of melt-kneading by an extruder, component (A) is charged from the first charge, and after the other components are mixed using a Henschel mixer, a pusher or the like, they are fed from the side feed, And melted and kneaded. The resin composition thus obtained can be appropriately molded depending on the shape of the target part, but it is preferably injection molding. As for the molded article obtained by injection molding -24-200925200, a molded article having a complicated shape such as a thin-walled member can be obtained. The molded article obtained in the foregoing manner may be a molded article having a dielectric constant of 1 〇 12 ohm meters or higher and a dielectric breakdown voltage of 1 mm thick of 2 kV/mm or higher. The molded article has a high thermal conductivity, and even if it is a low resistivity material represented by the component (C), it has excellent electrical insulation and sufficient dielectric disintegration as power and electronic parts. Voltage, so it is very useful in applications related to this part. Further, after a molded article having a size of 64 mm x 64 mm χ 3 mm thick was obtained from the insulating resin composition of the present invention, the resistivity of the molded article was measured in accordance with ASTM D257. Further, after a molded article having a size of 64 mm χ 64 mm x 1 mm thick was obtained from the insulating resin composition of the present invention, the disintegration voltage of the molded article was measured in accordance with the short-term disintegration test described in JIS C2110. As for the preferred φ of the molded article obtained from the resin composition of the present invention, the following applications can be exemplified. With regard to the application of molded articles obtained from the insulating resin composition of the present invention, suitable applications include housings for electric power and electronic devices, and electric equipment (eg, generators, motors, transformers, alternators, Parts of voltage regulators, rectifiers, inverters, repeaters, power interfaces, switches, circuit breakers, blade switches, poles, power boxes, sockets, relay boxes. In addition, it is suitable for electronic components that generate heat during operation, such as detectors, LED lamps, lamp holders, lamp reflector lamps, lampshades, connectors, small-sized switches, coil shafts, capacitors, oscillators, and various terminals - 25- 200925200, transformers, plugs, printed circuit boards, small-sized motors, head mounts, power modules, hard disk drive parts (hard disk drive hubs, actuators, hard disk substrates, etc.), DVD parts (eg, Optical heads, etc.) and computer related parts. In addition, it can be used for encapsulating resins for semiconductor elements, coils, etc., optical parts for optical devices (such as cameras), parts for generating high friction heat (such as roller bearings), and for vehicles and loads. Irradiation components and power component insulation boards for use with related zero φ pieces. The invention has been described herein, and it will be apparent that it can be varied in many ways. Such variations are intended to be included within the spirit and scope of the present invention, and all such modifications as may be apparent to those skilled in the art are included in the scope of the following claims. Japanese Patent Application No. 2007-236374, filed on Sep. 12, 2007, and the Japanese Patent Application No. 2008-122025, filed on May 8, 2008 The scope and details are fully incorporated herein by reference. EXAMPLES The present invention is illustrated by the following examples, which are not intended to limit the scope of the invention. Use the following as component (C). Carbonized sand 1 : OY-3 » Yakushima Denko Co., Ltd. Carbon fiber 1 : D i al e ad K 2 2 3 H G, M i t s u b i s hi P1 a s t i c In c . -26- 200925200 Graphite 1 : CB-150, produced by Nippon Graphite Fiber Corporation. Use the following as component (D). Oxidized ingots 1. Advanced alumina AA-18, manufactured by Sumitomo Chemical Co., Ltd., having a number average particle diameter of 18 μm and an alumina content of 99.6% by weight. Alumina fine particles 2 : Advanced alumina AA-1.5, Sumitomo 0 Chemical Co., Ltd. produced 'number average particle diameter of 1.5 μm, and alumina content of 99.6% by weight. Alumina fine particle 3: L ow-soda alumina ALM-41, Sumitomo Chemical Co., Ltd. produced 'number average particle diameter of 1.5 μm and alumina content of 99.9% by weight. Oxidized ingot 4: Advanced alumina AA-03, Sumitomo Chemical Co., Ltd. produced a number average particle diameter of 0.3 μm and an alumina content of 99.6% by weight.产 Production Example 1 [Method of Preparation of Particulate Material 1] Oxidized Ming Fiber (Denka Alcen, manufactured by Denki Kagaku Kogyo KK, alumina content 100% by weight, number average fiber diameter 3 · 2 μm) overall density 〇 28 g / cm ^ 3 It was put into a Henschel mixer (Super mixer G1 00, Kaw at a MGFC ο., manufactured by L td.), and stirred and granulated to obtain a particulate material 1. The number average particle diameter of the particulate material 1 was measured by an optical microscope to be 1.0 mm. -27- 200925200 Production Example 2 [Production of Liquid Crystal Polyester] In a reactor equipped with a stirring device, a torque meter, a nitrogen-passing tube, a thermometer, and a reflux condenser, 994.5 g (7.2 m) of a pair was placed. Hydroxybenzoic acid, 446.9 g (2.4 mol) of 4,4,-dihydroxybiphenyl, 299.0 g (1.8 mol) of p-nonanoic acid, 99.7 g (0.6 mol) of isophthalic acid and @1347.86 Acetic acid anhydride (13.2 mol) was replaced with nitrogen in the inside of the reactor, and then increased to 150 under a nitrogen stream. (: up to 30 minutes, and re-distilled for 1 hour while maintaining this temperature. Thereafter, increase to 320 ° C for 2 hours and 50 minutes while distilling off the distilled by-product acetic acid and unreacted acetic anhydride, thereby obtaining a pre- Polymer, at which time an increase in torque was observed and this was considered complete. The resulting prepolymer was cooled to room temperature, honed with a coarse honing machine, and then increased from room temperature to 250 ° C for one hour under nitrogen. Then, it was raised to 5 hours from 250 ° C to 285 ° C and maintained at 285 ° C for 3 hours to carry out solid state polymerization. The starting liquid temperature of the obtained liquid crystal polyester was 327 t. The ester is represented by LCP 1. Examples 1 to 7 and Comparative Examples 1 to 4 The particulate material obtained in Production Example 1, the liquid crystal polyester obtained in Production Example 2, and one selected from alumina fine particles 1 to 4 , tantalum nitride 1, carbon fiber 1 or graphite 1 by the composition shown in Table 1, using the same direction of the twin screw extruder (PCM-30, manufactured by Ikegai Iron Works, Ltd.) at -28-200925200 340 ° C kneading and granulation. Using an injection machine (PS40E5ASE, manufactured by Nissei Plastic Industrial Co., Ltd.) The obtained granules were injection-molded at a cylinder temperature of 3 50 ° C and a mold temperature of 130 ° C to obtain a molded article 1: 126 mm x 12 mm x 6 mm, molded article 2: 64 mm X 64 mm X 3 mm thick, mold Plastic article 3: 64 mm χ 64 mm x 1 mm thick. A plate (MD) having a thickness of 1 mm was cut in a direction perpendicular to the major axis of the molded article 1 as a sample for thermal conductivity evaluation. This sample was used for laser irradiation. The thermal constant measurement device (TC-7000, manufactured by Ulvac-Riko Inc.) of the flash U-ray method was used to measure the thermal diffusivity of these samples, and the specific heat was measured by DSC (DSC7, PERKINELMER Japan C 〇·, Lt d · manufactured). The specific gravity was measured by an automatic specific gravity measuring device (ASG-320K, Kanto-measure Co., Ltd.) The thermal conductivity of the sample was obtained by thermal diffusivity x specific gravity of heat X. Using molded article 2, determined according to ASTM D257 Resistivity of 300 K. Using dielectric article 3, the dielectric breakdown voltage was measured according to the short-term collapse test described in JIS C2110. @ The results are shown in Table 1. -29- 200925200 ο £ ο Comparative Example 4 § ^ (N 3_0χ109 ο Comparative Example 3 § δ 23.9 m τ·^ 1 Comparative Example 2 1 2 ^ rH rn 3.0x10 ° 00 (NL Comparative Example 1I 〇m O - (N 1 - Η (Ν 11.ΟχΙΟ10) oo o Μ O _4. 22 - Ο ν〇1 3.0χ10131 o ri Instance 6 ι&gt;σ&lt; 1 6.0x1 ο12 1 o Example 5 §2 s ^ 〇〇σν 11.0x10° 1 v〇ro Example 4 §g ^ ^ ο 00 9.0χ1012 1 m IK inch ΟΝ 1 9·0χ1012 o inch · Example 2 §2 ^ Ο ν〇1 3.0χ10131 o cn Example 1 i 2jqS 00 ΙΟ 1 4.0χ10131 〇o /—N y—N /—V ^ Φ Φ Φ Φ φ A ^ _ oiW^^^WiiliilW φβΙιΐιίΙΦ^^^^ S^^^SlISi _] —粗墨墨墨拍 ft 起翠蘧an An and An and 2藜磐 屯 嘁囍 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热 导热M) -30- 200925200 It is clear from the insulating resin compositions of Examples 1 to 7 that the obtained molded article has a thermal conductivity in the MD direction of 5 W/mK or higher and has excellent thermal conductivity. In addition, the resistivity is 1 〇 2 ohm meters or higher, and is not sufficient as the resistance 値 ' of the insulating components used in power and electronic parts and the dielectric breakdown voltage is 2 kV / mm or higher. This is excellent. In the resin compositions of Comparative Examples 1 and 2 using carbonized tantalum or carbon fibers, the heat conductivity of the obtained molded article was insufficient, and in Comparative Examples 3 and 4 in which a large amount of carbon fiber or graphite was mixed, the obtained molded article was obtained. The resistivity becomes small and the electrical insulation is insufficient. Example 8

Polyphenylene sulfate PPS1 (T-3G, manufactured by Dainippon Ink and Chemicals Inc.), particulate material 1 obtained in Production Example 1, carbon fiber 1 and oxidized mineral particles 2 are represented by the composition shown in Table 2, using the same direction of the double A screw extruder (PCM-30, manufactured by Ikegai Iron Works, Ltd.) was kneaded and granulated at 300 °C. Using an injection machine (PS40E5 ASE, manufactured by Nissei Plastic Industrial Co., Ltd.), the obtained granules were injection-molded at a cylinder temperature of 305 ° C and a mold temperature of 130 ° C to obtain a molded article 1 : 1 26 mm χ 12 mm χ 6 mm, molded object 2: 64 mm χ 64 mm x 3 mm thick, molded article 3: 64 mm X 64 mm x 1 mm thick. A plate (MD) having a thickness of 1 mm was cut in a direction perpendicular to the major axis of the molded article 1 as a sample for thermal conductivity evaluation. Using this sample, the thermal diffusivity of these samples was measured by a thermal constant measuring apparatus (TC-7000, manufactured by Ulvac-Riko Inc.) of a laser flash method. And by DSC (DSC7, PERKINELMER -31 - 200925200

Japan Co., Ltd. manufactured by measuring the specific heat, and measuring the specific gravity by an automatic specific weight measuring device (ASG-320K, Kanto-measure Co., Ltd.). The thermal conductivity of the sample is obtained by the thermal diffusivity X being greater than the thermal X specific gravity. Using a molded article 2, a resistivity of 300 K was measured in accordance with ASTM D257. Using the molded article 3, the dielectric collapse voltage was measured in accordance with the short-term collapse test described in JIS C21 10. The results are shown in Table 2. 〇 Table 2 Example 8 PPS1 (parts by weight) 100 Particulate material 1 (parts by weight) 190 Carbon fiber 1 (parts by weight) 17 Alumina fine particles 2 (parts by weight) 27 Thermal conductivity (MD) (Watts per meter K) 6.2 Resistance Rate (ohm meters) Ι.ΟχΙΟ13 Dielectric breakdown voltage (kV/mm) 2.0 〇

It is clear from the insulating resin composition of Example 8 using polyphenylene sulfide as the component (A) that the obtained molded article has a thermal conductivity of 5 W/mK or higher and has excellent thermal conductivity, and It also has good resistivity and dielectric breakdown voltage results. -32-

Claims (1)

200925200 X. Patent Application No. 1 · A resin composition comprising: (A) a thermoplastic resin; (B) a granular material having a number average particle diameter of 〇.5 to 5 mm and which may have a number average fiber diameter It is obtained by granulating fibers of alumina of 1 to 5 micrometers; and (C) pigment, which is composed of a material having a resistivity of 1 〇 2 ohm meters or lower D of 3 Å. 2. The resin composition of claim 1, wherein the component (C) is contained in the composition in an amount of from 1 to 5 parts by weight based on 1 part by weight of the component (A). 3. The resin composition of claim 1, wherein the component (C) is a material selected from the group consisting of tantalum carbide, tantalum or carbon fiber pigment. 4. The resin composition of claim 1, wherein the component Ο (B) is granulated by granulating fibers mainly having an overall density of 0.2 to 1 g/cm 3 of alumina. material. 5. The resin composition of claim 1, wherein the component (B) is a granular material obtained by granulating a fiber mainly having alumina while stirring. 6. The resin composition of claim 1, wherein the component (b) is contained in the composition in an amount of from 10 to 40 parts by weight based on 100 parts by weight of the component (A). 7 · The resin composition of claim 1 of the patent scope, wherein component -33- 200925200 (A) comprises polyphenylene sulfide. 8. The resin composition of claim 1, wherein component (A) comprises a liquid crystal polyester. 9. The resin composition of claim 8, wherein the liquid crystal polyester is a liquid crystal polyester having a starting temperature of 2 80 ° C or higher. 10. The resin composition of claim 8 or 9, wherein the liquid crystal polyester is the following liquid crystal polyester: φ is derived from the total structural unit of the liquid crystal polyester, derived from a structural unit of p-hydroxybenzoic acid and derived from The sum of the structural units of 2-hydroxy-6-naphthoic acid is from 3 8 to 80% by mole; based on the total structural unit of the liquid crystal polyester, the structural unit derived from hydroquinone and derived from 4,4,-dihydroxyl The sum of the structural units of biphenyl is 10 to 35 mol%; and the structural unit derived from citric acid, the structural unit derived from isodecanoic acid, and the derived from 2,6-, based on the total structural unit of the liquid crystal polyester. The sum of the knotted units of the naphthalene diacid is from 10 to 35 mol%. 1 1. A resin composition as claimed in claim 1 which further comprises (D) alumina fine particles having a number average particle diameter of from 1 to 100 μm. 12. The resin composition of claim 1 or 1 wherein the content of component (D) is from 5 to 250 parts by weight based on 100 parts by weight of component (A). A molded article obtained by molding the composition of claim 1 of the patent application. -34- 200925200 1 4. The molded article of claim 13 wherein the molded article has a resistivity of 1012 ohm meters or higher and a dielectric fracture voltage of 1 millivolt is 1 kilovolt. /mm or higher. -35- 200925200 七明说单单单为符图表表代定图指表:案代图本本表' '代代} } 定一指/IV /|\ 无无0 八, this case if there is a chemical formula When revealing the chemical formula that best shows the characteristics of the invention: no ❹ -4-