JPH08183875A - High thermal conductive composite filler and high thermal conductive resin composition - Google Patents

Abstract

(57) [Summary] [Objective] To provide a resin composition having both high thermal conductivity and good electrical insulation, and to provide such a resin composition by simply kneading with the resin. Provide the material. [Structure] A high heat conductive composite filler in which a high heat conductive powder made of metal and / or carbon is coated with an electrically insulating coating, and a high heat conductive resin composition containing the same.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a high thermal conductive composite filler and a high thermal conductive resin composition. More specifically, it is possible to provide a resin composition which is useful as a sealing material for semiconductors, resistors, capacitors, etc., a material for electric / electronic parts such as substrates, housings, etc., as a component material for heat exchangers, bearings, etc. .

[0002]

2. Description of the Related Art With the recent advances in electronics technology toward miniaturization, weight reduction, and higher performance of electric and electronic devices, material conversion from metal materials to plastics is also progressing. Materials for electrical and electronic equipment such as semiconductors, resistors, sealing materials for heat-generating components such as capacitors, substrates, housings, heat exchangers, bearings, etc. There is a strong demand for materials with excellent heat dissipation as well as heat resistance. However, plastics generally have a problem that they are materials having low thermal conductivity. Therefore, various methods of adding a metal or an inorganic filler having a good thermal conductivity to plastics to obtain a good thermal conductor have been studied. For example, Japanese Patent Laid-Open No. 59-168042 discloses a method of adding a spherical filler made of a metal such as iron, copper or aluminum to a resin. Further, JP-A-60-49053 discloses a resin composition prepared by adding bronze short fibers to a fluororesin. However, these methods have a problem that, while metal has high thermal conductivity, it cannot obtain electrical insulation because it is a material having poor electrical insulation. Further, since metal easily reacts with oxygen, there is a problem that thermal conductivity is extremely lowered when an oxide film is formed on the surface. In addition, the resin may be decomposed due to heat generated by the oxidation of the metal during mechanical mixing with the resin. Further, as a method of adding an inorganic filler having electrical insulation and good heat conductivity in place of metal, for example, JP-A-61-1124
A method in which aluminum nitride is added to JP-A-3,
Japanese Patent Laid-Open No. 1-101513 discloses a material to which boron nitride is added. However, none of these have sufficiently satisfactory thermal conductivity as compared with the resin composition containing a metal.

[0003]

An object of the present invention is to provide a resin composition having both high thermal conductivity and good electric insulation, and to obtain such a resin composition only by kneading with the resin. It is to provide a composite filler that can be obtained.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a high heat conductive composite filler in which a high heat conductive powder made of metal and / or carbon is coated with an electrically insulating coating, and a high heat conductive resin composition containing the same. Related to things. As high thermal conductivity powder,
For example, metals corresponding to 4th to 6th periods of Groups 4 to 6 of the periodic table, metals corresponding to 4th to 6th periods of Groups 10 to 12 and 13th to 14th periods
Powders and carbon powders composed of a metal corresponding to the 2nd to 3rd periods of the group (1989 IUPAC classification method), one metal selected from the group of Mg, Fe and Pb, or an alloy of two or more selected from these be able to. Preferably, for example, Au, Ag, Pt, Ta, Cr, Al, Zn, Ni, Pb, W,
Examples of the powder include metals such as Zr, B, Mg, Si, Mo, Cu, Ti, and Fe, and powders composed of two or more kinds of alloys selected from these. Especially from the viewpoint of thermal conductivity, Ag, A
1, Zn, Ni, Mg, Cu and Ti are preferable, and Ag, Al and Z are preferable.
Particularly preferably n, Ni and Cu are used.

The carbon that can be used in the present invention preferably has a graphitization ratio of 30% or more, preferably 70% or more. For example, carbon obtained by growing a single crystal or obtained by thermally decomposing an organic substance. Examples thereof include graphite obtained by further heating these. Specific examples of carbon that can be used in the present invention include polyacrylonitrile (PAN) -based, pitch-based (petroleum-based, coal-based), rayon-based, mesophase-based carbon, carbon produced by a vapor phase pyrolysis method, and the like. Can be mentioned. Carbon (vapor grown carbon) obtained by the vapor phase pyrolysis method uses an iron-based catalyst to convert a hydrocarbon having a carbon number of 1 to 8 such as methane, ethane, propane, butane or benzene at a high temperature (for example, 100).
It can be produced by thermal decomposition at about 0 ° C. The carbon that can be used in the present invention is 3000 ° C.
Those treated at a high temperature before and after are high in graphitization rate and have high thermal conductivity, which is particularly preferable.

The shape of the high thermal conductive powder can be selected according to the shape of the target high thermal conductive composite filler, but a preferable shape is an average diameter of 0.05 to 0.55.
A fibrous material having a diameter of 200 μm and an aspect ratio of 10 or more, or a particulate material having a particle diameter of about 0.05 to 300 μm can be mentioned. Also, the high thermal conductivity powder has a thermal conductivity of 60-
It is preferably in the range of 2000 W / (m · k). The electrically insulating coating is not particularly limited as long as it covers the base material and can electrically insulate the base material from each other so that the base materials do not come into contact with each other. A coating may be used, but a coating that does not melt off during kneading with a resin is preferable. Particularly preferred is electrical insulation and heat conductivity at 20 ° C. of 10 W /
Those having a high thermal conductivity of (m · k) or more, particularly 15 to 500 W / (m · k) can be mentioned, and specific examples thereof include aluminum nitride, boron nitride, silicon nitride, aluminum oxide, and magnesium oxide. , Silicon oxide, diamond and the like.

As a method for coating the surface of the high thermal conductive powder with an electrically insulating coating, a generally known chemical vapor deposition method (hereinafter abbreviated as CVD), for example, laser CVD, ion CVD, plasma CVD, thermal CVD, thermal Plasma CV
D, physical vapor deposition method (hereinafter abbreviated as PVD), for example, laser PVD, electron beam vapor deposition method, ion PVD, sol-gel method using a solution, and the like, but especially laser C
VD and thermal plasma CVD are preferred. In these ways
The obtained film is a film in which the surface of the powdery base material having high thermal conductivity is coated with the electrically insulating fine particles. The coating thickness of the electrically insulating coating that coats the surface of the high thermal conductive powder,
Although it is not particularly limited, it is desirable that the metal filler is coated to such an extent that the surface of the metal is not exposed in order to make the metal filler exhibit electric insulation and prevent oxidation. As such a coating material, one having a volume resistivity value of about 10 ¹³ Ω / cm or more is preferable. Among the shapes of the high thermal conductive composite filler thus obtained, preferred ones have an average diameter of 0.05 to 200 μm and an aspect ratio of 3 or more, more preferably an average diameter of 0.1 to 100 μm and an aspect ratio of 10 or more. A fibrous substance can be mentioned. Those having such a shape are preferable because they have a reinforcing effect in addition to imparting thermal conductivity. In addition, those having an average diameter of less than 5 μm have the effect of improving the surface smoothness. The average diameter is 0.0
A particle size of less than 5 μm is not preferable because it is difficult to mix a large amount with a resin. Further, as another preferable shape, a particulate material having an average particle diameter of 0.05 to 300 μm, and more preferably a particulate material having an average particle diameter of 0.1 to 200 μm can be mentioned. A large amount of particles having such a shape can be filled. In the present invention, one kind of the high thermal conductivity composite filler can be used alone or two or more kinds can be used at the same time.

By blending the highly heat-conductive composite filler of the present invention with a resin, it is possible to easily impart heat conductivity to the resin. For example, according to the method of the present invention, it becomes possible to impart a thermal conductivity of 5 W / m · k or more at room temperature while maintaining the electrical insulation of the resin. The compounding amount of the high thermal conductive composite filler of the present invention into the resin can be selected from a wide range according to the desired thermal conductivity, but is preferably 5 to 900 parts by weight with respect to 100 parts by weight of the resin. ,
More preferably, it is blended in the range of 10 to 230 parts by weight. If the blending amount is less than 5 parts by weight, the improvement of the thermal conductivity is poor, and filling exceeding 900 parts by weight is generally difficult. As a method for highly filling 200 parts by weight or more with respect to 100 parts by weight of the resin, a method of adding a plurality of powders having different particle sizes and shapes in combination may be used. The high thermal conductive composite filler of the present invention can be used by enhancing the affinity and bondability at the interface with the resin by surface-treating it with a coupling agent. The amount of such surface treatment is usually 0.01 to 5 parts by weight, preferably 0.5 to 2 parts by weight, of the surface of the high thermal conductive composite filler to be treated with 100 parts by weight of the coupling agent. What was processed can be used. If the amount is less than 0.01 parts by weight, the effect of improving the affinity and bondability of the interface between the resin and the filler cannot be expected, so there is little contribution to the improvement of the thermal conductivity. The effect of is not desirable and is not preferable because it may reduce the thermal conductivity.

There are various types of coupling agents that can be used, but silane-based and titanate-based coupling agents are typical. As the silane coupling agent, for example, γ-mercapto-propyl-trimethoxysilane, 2-styryl-ethyl-trimethoxysilane, N-
β- (aminoethyl) γ-amino-propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl)
Examples thereof include ethyl-trimethoxysilane, γ-aminopropyl-trimethoxysilane, γ-glycidoxy-propyltrimethoxysilane, phenyltrimethoxysilane, and methyldimethoxysilane. These are used alone or in combination of two or more. can do. Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri (N, N-diaminoethyl titanate. ) Titanate, isopropyl tridodecylbenzene sulfonyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphate) titanate, tetraoctyl bis (ditridecyl phosphate) ) Titanate, tetra (2,2-diallyloxymethyl-1- Chill) bis (ditridecyl) phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, etc., which may be used alone or in admixture of two or more. You can It is also possible to use a silane coupling agent and a titanium coupling agent in combination.

The resin which can be used in the present invention is not particularly limited, but as the thermoplastic resin, the following resins or a mixture thereof can be exemplified. (1) Polyolefin, for example, polyethylene, polypropylene, polyisobutylene, polybutene, polymethylpentene, cyclic olefin, polybutadiene. (2) Atactic or syndiotactic polystyrene, poly (p-methylstyrene), poly (α-methylstyrene). (3) A copolymer of styrene or α-methylstyrene and a diene or an acrylic derivative and a mixture thereof, for example,
Copolymer blends known as ABS, MBS, ASA or AES polymers. (4) Polymers of vinyl halide compounds such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and their copolymers such as vinyl chloride / vinylidene chloride, vinyl chloride /
Vinyl acetate or vinylidene chloride / vinyl acetate copolymer. (5) Polymers obtained from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles. (6) Unsaturated alcohols and amines or acyl derivatives thereof or polymers obtained by acetalization thereof, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinyl polybenzoate, vinyl maleate,
Polyvinyl butyrate, polyvinyl formal, polyvinyl butyral resin. (7) Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycol, polyethylene oxide,
Polypropylene oxide, or its copolymers with bisglycidyl ether. (8) Polyacetals such as polyoxymethylene and polyoxymethylene containing ethylene oxide as a comonomer and polyacetals modified with thermoplastic polyurethanes, polyacrylates or MBS (methyl methacrylate-butadiene-styrene copolymer). (9) Polyphenylene oxide and modified polyphenylene oxide modified with impact-resistant polystyrene or the like. (10) Polyurethanes using a polyether or polyester as a soft segment and an aliphatic or aromatic polyisocyanate and precursors thereof.

(11) Diamine and dicarboxylic acid, and /
Alternatively polyamides and copolyamides obtained from aminocarboxylic acids or the corresponding lactams, eg polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6
/ 9, 6/12 and 4/6, polyamide 11, polyamide 12 and polyamide MXD6 obtained by condensation of m-xylenediamine and adipic acid, modified polyamide prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid 6T or even EPD
Polyamides or copolyamides modified with M or ABS, as well as polyamides which are condensed during processing (RIM polyamide system). (12) Polyetherimides, polyimides and polyamide-imides, and polybenzimidazoles. (13) Polyesters obtained from dicarboxylic acids and diols, and / or hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol, and polyesters further modified with polycarbonate or MBS. (14) Polycarbonates and polyester carbonates. (15) Polyallyl sulfone, polyallyl ketone, for example, polysulfone, polyether sulfone, polyether ether ketone, polyether ketone. (16) Polyphenylene sulfide or polyphenylene sulfide sulfone. (17) A melt-processable polyester capable of forming an optically anisotropic melt phase. (18) Fluorine resin, for example, polytetrafluoroethylene, ethylene / tetrafluoroethylene copolymer,
Tetrafluoroethylene / perfluorovinyl ether copolymer. (19) Natural polymers such as cellulose, rubber and gelatin, or homologous derivatives of chemically modified natural polymers thereof,
For example, cellulose acetate, cellulose propionate and cellulose acetate or cellulose ether, methyl cellulose, rosin, rosin ester or derivatives thereof. (20) Mixtures (polyblends) of the above polymers, eg PP / EPDM, PA6 / EPDM or ABS, P
VC / EVA, PVC / ABS, PVC / MBS, PC
/ ABS, PBT / ABS, PC / AS, PC / PB
T, PVC / CPE, PVC / acrylate, POM /
Thermoplastic PUR, PC / Thermoplastic PUR, POM / Acrylate, POM / MBS, PPE / HIPS, PPE
/ PA66 and copolymer, PA / HDPE, PA / P
P, PA / PPO. PA: Polyamide AS: Acrylonitrile Styrene CPE: Chlorinated Polyethylene POM: Polyoxymethylene PUR: Polyurethane Rubber

Examples of the polymer having a crosslinked structure (thermosetting resin) include the following polymers. (1) Aldehydes and crosslinked polymers obtained from phenol, urea or melamine, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins. (2) Drying and non-drying alkyd resins. (3) An unsaturated polyester obtained from a copolyester of a saturated and unsaturated dicarboxylic acid, a polyhydric alcohol and a vinyl compound as a crosslinking agent. (4) A crosslinkable acrylic resin obtained from a substituted acrylic ester, for example, an epoxy acrylic acid resin, a urethane acrylic acid resin or a polyester acrylic acid resin. (5) Alkyd resin, polyester resin or acrylate resin crosslinked with melamine resin, urea resin, polyisocyanate or epoxy resin. (6) Rubbers and silicone rubbers obtained from the crosslinking of polydienes based on butadiene or isoprene. (7) A cross-linked epoxy resin obtained from a polyepoxide, for example, bisglycidyl ether or an alicyclic diepoxide. Among these crosslinked polymers, a crosslinked epoxy resin obtained from a glycidyl compound having an average of two epoxy groups in the molecule as a polyepoxide is preferable. As the epoxy resin, glycidylated novolac, hydantoin, aminophenol, bisphenol, aromatic diamine or alicyclic epoxy compound is preferable.

Further, examples of the curing agent include the following. (1) Phenol novolac resin, for example, cresol novolac resin, bisphenol A novolac resin,
Naphthol novolac resin and phenol novolac resin. (2) Polyoxystyrene, for example, phenol aralkyl resin such as a condensation polymerization compound of 2,2-dimethoxy-p-xylene and phenols, polyparaoxystyrene. (3) Acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic anhydride. (4) Aliphatic, alicyclic or aromatic primary, secondary and tertiary amines. Further, a curing accelerator can be used for further curing. Examples of the curing accelerator include imidazole or its derivative, tertiary amine derivative, phosphine or its derivative, and the like. The curing accelerator is generally added in an amount of 0.1 to 10% by weight based on the epoxy resin. Curing agents for epoxy resins are generally used in equimolar amounts relative to the epoxy groups and the functional groups of the curing agent. Additives may be added to the novel composition within the range that does not impair the effects of the present invention in order to enhance the processing properties, mechanical, electrical and thermal properties, surface properties and photostability. Typical examples of such additives are finely divided fillers, reinforcing fillers, plasticizers, lubricants and mold release agents, adhesion promoters, antioxidants, heat and light stabilizers, flame retardants (eg antimony trioxide). Etc.), pigments and dyes.

In producing the resin composition of the present invention,
Before the production of the filler together with the plastics material,
Granules or moldings can be conveniently obtained by mixing during or after, plasticizing the plastics material and mixing with the filler and calendering, extruding or injection molding. The powdered plastics material and the filler can be dry-blended, or the plastics material can be dissolved in a solvent, the filler can be suspended in the solution, and then the solvent can be removed to obtain a resin composition.
When a coupling agent is used in the present invention,
The filler may be directly added together with the above-mentioned filler, but the filler may be surface-treated with a coupling agent in advance and used. When a thermosetting resin and a polymer having a crosslinked structure are used, generally, the filler may be mixed in advance in one component, but by mixing the filler and the resin component together, molding and curing can be performed. Alternatively, it is convenient to add the filler before crosslinking. The powder mixture can be mixed in the plastics material in the form of a mixture, or the two components can be combined and then the third component added and mixed.

[0015]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. Although there are various methods for coating the metal with the electrically insulating high thermal conductive particles, the thermal plasma CVD method is used in this example. That is,
A composite filler is obtained by atomizing electrically insulating high thermal conductivity particles by thermal plasma and supplying a metal filler as a base material to an atmosphere containing the particles. The composite fillers in the examples below are all obtained using this method. The sources of the used materials are shown below. AIN: Tokuyama Co., Ltd. BN: Denki Kagaku Kogyo Co., Ltd. Al ₂ O ₃ : Sumitomo Chemical Co., Ltd. SiC: Tokai Carbon Co., Ltd. Toka Whisker Si ₃ N ₄ : Ube Industries Co., Ltd. UBE-SN-WA Cu: Japan Atomized Processing Co., Ltd. Ag: Fukuda Metal Foil & Powder Industry Co., Ltd. Al: Toyo Aluminum Industry Co., Ltd. Ni: Fukuda Metal Foil & Powder Industry Co., Ltd. Brass (copper / zinc 70/30): Fukuda Metal Foil & Powder Industry Co., Ltd.

Examples 1 to 12 As the resin to which the composite filler is added, cresol novolac epoxy resin / novolac phenol resin / antimony trioxide / brominated novolac epoxy resin / γ-glycidoxypropyltrimethoxysilane / carbon black / A mixture of carnauba wax / 2-phenylimidazole in a weight ratio of 85/40/15/10/3/3/2/1 was used. The resin and the composite filler shown in Table 1 below were mixed with a heating roll at 100 ° C. for 10 minutes, cooled, and coarsely pulverized to obtain a resin composition.

[0017]

[Table 1]

A plate having a size of 100 mm × 100 mm and a thickness of 3 mm was formed from the resin composition by a transfer molding method at a mold temperature of 175.
Molding was carried out under the molding conditions of a temperature of 80 ° C., an injection pressure of 100 kgf / m ² , a molding time of 3 minutes, and a preheating temperature of 80 ° C. Diameter 1 from this plate
0 mm, 1 mm thick disc for measuring thermal conductivity, diameter 100 mm,
A disk for measuring conductivity having a thickness of 2 mm was produced by cutting. For each of the above test pieces, by the following test method,
The thermal conductivity and the volume resistivity were measured. The thermal conductivity was measured by the laser flash method. (1) Volume resistivity: According to JIS K6911 (2) An electrode was painted on the sample surface with a conductive silver paste, and the volume resistivity was measured. The results are shown in Table 3.

Examples 13 to 21 Polyphenylene sulfide resin (hereinafter abbreviated as PPS) was used as the resin to which the filler was added. The composite filler and PPS shown in Table 2 below are mixed with a Henschel mixer (8
After mixing at 00 rpm) for 3 minutes, a resin composition was obtained with a twin-screw kneading extruder having a diameter of 30 mm (300 ° C., 60 rpm).

[0020]

[Table 2]

This resin composition is 100 mm × by injection molding.
Cylinder temperature 300 ℃, mold temperature 160 ℃, injection pressure (primary) 130 kgf / cm ² , injection pressure (secondary) 90 kgf / cm ² , holding time 10 seconds, cooling time 20 seconds It was molded under the molding conditions of. From this flat plate to Example 1
Samples similar to Nos. 12 to 12 were prepared by cutting and the thermal conductivity and volume resistivity were measured. The results are shown in Table 4.

Comparative Example 1 A resin composition was prepared and thermal conductivity and volume resistivity were measured by the same method and proportion as in Example 1 except that Cu powder having an average particle diameter of 11 μm was used as a filler. . Comparative Example 2 A resin composition was prepared and thermal conductivity and volume resistivity were measured by the same method and ratio as in Example 1 except that AlN powder having an average particle diameter of 2 μm was used as a filler. Comparative Example 3 A resin composition was prepared and the thermal conductivity and volume resistivity were measured in the same manner and in the same proportions as in Example 13, except that Cu powder having an average particle diameter of 11 μm was used as the filler. Comparative Example 4 A resin composition was prepared and the thermal conductivity and volume resistivity were measured by the same method and proportion as in Example 13, except that AlN powder having an average particle diameter of 2 μm was used as the filler. The results are shown in Table 3.
And shown in Table 4.

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

EFFECTS OF THE INVENTION According to the present invention, the electric conductivity which is not obtained by the resin composition containing a metal filler having a high thermal conductivity due to the presence of the metal composite filler coated with the electrically insulating high thermal conductive particles. It is possible to provide a resin composition that also has an insulating property, and more specifically, a sealing material for semiconductors, resistors, capacitors, etc., materials for electric / electronic parts such as substrates, housings, heat exchangers, bearings, etc. A resin composition useful as a device constituent material can be provided.

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[Procedure amendment]

[Submission date] February 2, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 10

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

As a method for coating the surface of the high thermal conductive powder with an electrically insulating coating, a generally known chemical vapor deposition method (hereinafter abbreviated as CVD), for example, laser CVD, ion CVD, plasma CVD, thermal CVD, thermal Plasma CV
D, physical vapor deposition method (hereinafter abbreviated as PVD), for example, laser PVD, electron beam vapor deposition method, ion PVD, sol-gel method using a solution, and the like, but especially laser C
VD and thermal plasma CVD are preferred. In these ways
The obtained film is a film in which the surface of the powdery base material having high thermal conductivity is coated with the electrically insulating fine particles. The coating thickness of the electrically insulating coating that coats the surface of the high thermal conductive powder,
Although it is not particularly limited, it is desirable that the metal filler is coated to such an extent that the surface of the metal is not exposed in order to make the metal filler exhibit electric insulation and prevent oxidation. As such a coating material, one having a volume resistivity of about 10 ¹³ Ω · cm or more is preferable. Among the shapes of the high thermal conductive composite filler thus obtained, preferred ones have an average diameter of 0.05 to 200 μm and an aspect ratio of 3 or more, more preferably an average diameter of 0.1 to 100 μm and an aspect ratio of 10 or more. A fibrous substance can be mentioned. Those having such a shape are preferable because they have a reinforcing effect in addition to imparting thermal conductivity. In addition, those having an average diameter of less than 5 μm have the effect of improving the surface smoothness. The average diameter is 0.05 μm
If it is less than 1, it is not preferable because it is difficult to mix a large amount with the resin. Further, as another preferable shape, a particulate material having an average particle diameter of 0.05 to 300 μm, more preferably,
Examples thereof include particles having an average particle size of 0.1 to 200 μm. A large amount of particles having such a shape can be filled. In the present invention, one kind of the high thermal conductivity composite filler can be used alone or two or more kinds can be used at the same time.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

By blending the highly heat-conductive composite filler of the present invention with a resin, it is possible to easily impart heat conductivity to the resin. For example, according to the method of the present invention, it becomes possible to impart a thermal conductivity of 5 W / m · k or more at room temperature while maintaining the electrical insulation of the resin. The compounding amount of the high thermal conductive composite filler of the present invention in the resin can be selected from a wide range according to the desired thermal conductivity, but is preferably 5 to 900 parts by volume with respect to 100 parts by volume of the resin. ,
More preferably, it is mixed in the range of 10 to 230 parts by volume . Amount is less than 5 parts by volume and poor improvement in thermal conductivity, also filled exceeding 900 parts by volume is generally difficult. As a method of highly filling 200 parts by volume or more with respect to 100 parts by volume of resin, a plurality of particles having different particle sizes or
May be used by adding fillers having different shapes in combination. The high thermal conductive composite filler of the present invention can be used by enhancing the affinity and bondability at the interface with the resin by surface-treating it with a coupling agent. The treatment of such surface treatment typically 0.01 to 5 parts by volume relative to the high thermal conductivity composite filler 100 parts by volume to be treated, preferably, the surface with a coupling agent 0.5 to 2 parts by volume What was processed can be used. If the amount is less than 0.01 part by volume, the effect of improving the affinity and bondability of the interface between the resin and the filler cannot be expected, so there are few places that contribute to the improvement of thermal conductivity.
Further, even if it exceeds 5 parts by volume , not only further effect can be expected but also the thermal conductivity may be lowered, which is not preferable.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The resin which can be used in the present invention is not particularly limited, but as the thermoplastic resin, the following resins or a mixture thereof can be exemplified. (1) Polyolefin, for example, polyethylene, polypropylene, polyisobutylene, polybutene, polymethylpentene, cyclic olefin, polybutadiene. (2) Atactic or syndiotactic polystyrene, poly (p-methylstyrene), poly (α-methylstyrene). (3) A copolymer of styrene or α-methylstyrene and a diene or an acrylic derivative and a mixture thereof, for example,
ABS, MBS (methyl methacrylate-butadiene-su
Chi copolymers), ASA or known copolymer mixtures as AES polymers. (4) Polymers of vinyl halide compounds such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and their copolymers such as vinyl chloride / vinylidene chloride, vinyl chloride /
Vinyl acetate or vinylidene chloride / vinyl acetate copolymer. (5) Polymers obtained from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles. (6) Unsaturated alcohols and amines or acyl derivatives thereof or polymers obtained by acetalization thereof, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinyl polybenzoate, vinyl maleate,
Polyvinyl butyrate, polyvinyl formal, polyvinyl butyral resin. (7) Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycol, polyethylene oxide,
Polypropylene oxide, or its copolymers with bisglycidyl ether. (8) Polyacetals such as polyoxymethylene and polyoxymethylene containing ethylene oxide as a comonomer and polyacetals modified with thermoplastic polyurethanes, polyacrylates or MBS (methyl methacrylate-butadiene-styrene copolymer). (9) Polyphenylene oxide and modified polyphenylene oxide modified with impact-resistant polystyrene or the like. (10) Polyurethanes using a polyether or polyester as a soft segment and an aliphatic or aromatic polyisocyanate and precursors thereof.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

[0015]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. Coating the surface of high thermal conductivity powder with an electrical insulation coating
Although there are various methods described above, the thermal plasma CVD method is used in this embodiment. That is, the electrically insulating particles are atomized by thermal plasma,
A composite filler is obtained by supplying a highly heat-conductive powder as a base material to an atmosphere containing these fine particles. The composite fillers in the examples below are all obtained using this method. The sources of the used materials are shown below. AIN: Tokuyama Co., Ltd. BN: Denki Kagaku Kogyo Co., Ltd. Al ₂ O ₃ : Sumitomo Chemical Co., Ltd. SiC: Tokai Carbon Co., Ltd. Toka Whisker Si ₃ N ₄ : Ube Industries Co., Ltd. UBE-SN-WA Cu: Japan Atomized Processing Co., Ltd. Ag: Fukuda Metal Foil & Powder Industry Co., Ltd. Al: Toyo Aluminum Industry Co., Ltd. Ni: Fukuda Metal Foil & Powder Industry Co., Ltd. Brass (copper / zinc 70/30): Fukuda Metal Foil & Powder Industry Co., Ltd.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

A plate having a size of 100 mm × 100 mm and a thickness of 3 mm was formed from the resin composition by a transfer molding method at a mold temperature of 175.
Molding was carried out under the molding conditions of a temperature of 80 ° C., an injection pressure of 100 kgf / m ² , a molding time of 3 minutes, and a preheating temperature of 80 ° C. Diameter 1 from this plate
0 mm, 1 mm thick disc for measuring thermal conductivity, diameter 100 mm,
A disk for measuring conductivity having a thickness of 2 mm was produced by cutting. For each of the above test pieces, by the following test method,
The thermal conductivity and the volume resistivity were measured. (1) The thermal conductivity is measured by the laser flash method.
It was (2) Volume resistivity: According to JIS K6911 , an electrode was painted on the surface of the sample with a conductive silver paste, and the volume resistivity was measured. The results are shown in Table 3.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0019

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Examples 13 to 21 Polyphenylene sulfide resin (hereinafter abbreviated as PPS) was used as the resin to which the composite filler was added. The composite filler shown in Table 2 below and PPS were mixed for 3 minutes with a Henschel mixer (800 rpm), and then a resin composition was obtained with a twin-screw extruder with a diameter of 30 mm (300 ° C., 60 rpm).

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EFFECTS OF THE INVENTION According to the present invention, a powder having high thermal conductivity is electrically isolated.
Provided is a resin composition having high thermal conductivity due to the presence of a high thermal conductive composite filler coated with an edging film , and also having electrical insulation properties not obtained by a resin composition containing a metal filler. More specifically, a resin composition useful as a sealing material for semiconductors, resistors, capacitors, etc., a material for electric / electronic parts such as substrates, housings, etc., as a component material for heat exchangers, bearings, etc. Can be provided.

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Claims (17)

[Claims] 1. A high thermal conductivity composite filler obtained by coating a high thermal conductivity powder made of metal and / or carbon with an electrically insulating coating. 2. The high thermal conductive composite filler according to claim 1, wherein the coating film is composed of electrically insulating particles. 3. The high thermal conductive composite filler according to claim 1, wherein the thermal conductivity of the electrically insulating coating measured at 20 ° C. is 10 W / (m · k) or more. 4. The high thermal conductive powder has a thermal conductivity of 60 to 20.
The range having a range of 00 W / (m · k).
High thermal conductivity composite filler. 5. The high thermal conductive powder corresponds to a metal corresponding to 4th to 6th periods of Groups 4 to 6 of the periodic table, a metal corresponding to 4th to 6th periods of Groups 10 to 12 and a second to third period of 13th to 14th groups. The high thermal conductive composite filler according to claim 1, which comprises one metal selected from the group of metals (IUPAC classification method in 1989), Mg, Fe, and Pb, or two or more alloys selected from these, or carbon. 6. The high thermal conductive powder is Au, Ag, Pt, T.
a, Cr, Al, Zn, Ni, Pb, W, Zr, B, Mg, S
The high thermal conductive composite filler according to claim 5, which is made of one kind of metal or two or more kinds of alloy selected from the group of i, Mo, Cu, Ti, and Fe. 7. The high thermal conductive powder is Ag, Al, Zn, N.
The high thermal conductive composite filler according to claim 6, which is composed of one kind of metal or two or more kinds of alloy selected from the group consisting of i, Mg, Cu and Ti. 8. The high thermal conductive powder is Ag, Al, Zn, N.
The high thermal conductive composite filler according to claim 7, which is made of one kind of metal or two or more kinds of alloy selected from the group of i and Cu. 9. The electrically insulating coating is selected from the group consisting of aluminum nitride, boron nitride, silicon nitride, aluminum oxide, magnesium oxide, silicon oxide and diamond.
The high thermal conductive composite filler according to claim 1, which is one kind or two or more kinds. 10. The high thermal conductive powder has a particle size of 0.05 to 2
The highly heat-conductive composite filler according to claim 1, which is a fibrous material having a diameter of 00 μm and an average aspect ratio of 5 or more. 11. The high thermal conductive powder has a particle size of 0.05 to 3
The highly heat-conductive composite filler according to claim 1, which is a particulate material having a diameter of 00 μm. 12. The high thermal conductive composite filler according to claim 1, which is surface-treated with a coupling agent. 13. The filler has a mean diameter of 0.05 to 20.
The highly heat-conductive composite filler according to claim 1, which is a fibrous material having a thickness of 0 μm and an average aspect ratio of 3 or more. 14. The filler has a mean diameter of 0.1 to 100.
The highly heat-conductive composite filler according to claim 13, which is a fibrous material having a micrometer and an average aspect ratio of 10 or more. 15. The shape of the filler has an average particle size of 0.05 to 3
The highly heat-conductive composite filler according to claim 1, which is a particulate material having a diameter of 00 μm. 16. The shape of the filler has an average particle size of 0.1 to 20.
The high thermal conductive composite filler according to claim 15, which is a particle having a size of 0 μm. 17. A high thermal conductive resin composition obtained by mixing the resin with the high thermal conductive composite filler according to claim 1.