JPWO2005111146A1 - Thermally conductive resin composition, method for producing the same, and housing - Google Patents

Abstract

The objective of this invention is providing the heat conductive resin composition which gives the molded article excellent in heat conductivity, electromagnetic shielding property, etc., its manufacturing method, and a housing. The thermally conductive resin composition of the present invention comprises: [A] 40 to 94% by volume of rubber-reinforced styrene resin, [B] 5 to 55% by volume of thermally conductive filler, and [C] an alloy having a melting point of 500 ° C. or less. And / or 1-20 volume% of metals are contained, and volume ratio [B] / [C] is 1 / 2-35 / 1. Moreover, it can also be set as the composition containing [D] metal deactivator, and the smoke generation etc. at the time of manufacture of a molded article etc. are reduced.

Description

  The present invention relates to a thermally conductive resin composition that provides a molded article having excellent molding processability and excellent thermal conductivity and electromagnetic shielding properties, a manufacturing method thereof, and a housing.

As the integration density of semiconductor elements such as LSIs increases, the operation speed increases, and electronic components are mounted with high density, heat radiation countermeasures for products equipped with heat generating components have become major issues. For example, metal and ceramics with high thermal conductivity have been conventionally used for housings of electronic components, but in recent years, resin compositions that have a high degree of freedom in shape selection and are easily reduced in weight and size have been used. (See Patent Documents 1, 2, and 3).
Patent Document 1 discloses a resin composition containing a thermoplastic resin such as PBT or PEEK, inorganic fibers such as aluminum nitride, and inorganic powder.
Patent Document 2 discloses a resin composition containing a specific block copolymer or hydrogenated block copolymer, a rubber softener, and a heat conductive material such as magnesium hydroxide.
In Patent Document 3, a filler made of sintered aluminum nitride powder or the like is dispersed in a matrix resin, and a metal network formed in a network by a low melting point metal or eutectic alloy having a melting point of 500 ° C. or lower is used. A high thermal conductive composite in which the filler is continuously welded to each other is disclosed.
Patent Document 4 discloses a resin composition containing polyphenylene sulfide, Sn—Cu alloy, etc., Cu—graphite and the like.

JP-A-8-283456 JP 2001-106865 A Japanese Patent Laid-Open No. 6-196684 International Publication No. 2003-29352

According to Patent Document 3, a mixed powder containing a resin, a low melting point alloy, and a filler is molded at room temperature, and then the resulting molded body is heated at a temperature at which the low melting point alloy is completely melted. A method for increasing the thermal conductivity of a compact by welding and cross-linking with a low melting point alloy is disclosed. However, when this form is obtained by melt kneading of the resin, there are the following problems. That is, when kneading is performed at a temperature at which the low melting point alloy is completely melted, the viscosity difference between the low melting point alloy and the resin at that temperature is large, and it is difficult to uniformly disperse the low melting point alloy in the resin. Moreover, since the fillers are cross-linked, if the content of the low-melting point alloy is increased, the resin content decreases, and there is a problem that the flexibility and molding processability of the resin decrease. Furthermore, since it is necessary to contain a large amount of a low melting point alloy having a smaller thermal conductivity than that of the filler, there is also a problem that it is difficult to greatly increase the thermal conductivity of the resin composition. These problems are partially solved by the technique disclosed in Patent Document 4, but may not be sufficient depending on the type of matrix resin.
The objective of this invention is providing the heat conductive resin composition which is excellent in moldability, and gives the molded article excellent in heat conductivity and electromagnetic shielding property, its manufacturing method, and a housing.

By the way, when the thermal conductivity of the resin composition is improved, there is a problem that the resin tends to generate heat when the raw material composition is kneaded or a molded product is produced, and smoke is emitted from the kneading apparatus or the molding apparatus. In the case of a heat conductive resin composition, smoke may continue from the resin lump taken out from the molding apparatus for a while, and the resin component may be oxidized, thereby causing deterioration of physical properties of the molded product.
Another object of the present invention is to reduce heat generation during production of pellets (composition) and molded products, and to provide molded products with excellent molding processability, excellent thermal conductivity, electromagnetic shielding properties, etc. It is providing a resin composition, its manufacturing method, and a housing.

  As a result of intensive studies to achieve the above object, the present inventors have used a specific resin component and an alloy and / or metal having a low melting point, and the alloy is semi-molten in which a solid phase portion and a liquid phase portion are mixed. The present invention has been completed by finding that the resin composition can be made less susceptible to the difference in viscosity between the resin component and the alloy, etc., and that the alloy and the like can be easily dispersed in the matrix containing the resin component. Is.

  In addition, as a result of intensive studies to achieve the above-described other objects, the present inventors speculated that smoke generation during the production of pellets (compositions) and molded products may be caused by alloys having a low melting point. . Then, by using a raw material composition further containing a metal atom constituting the alloy and / or a component capable of forming a complex with the ion (metal deactivator), heat generation during kneading of the raw material composition, etc. The present invention found that a resin composition excellent in thermal conductivity, electromagnetic shielding properties, etc. was obtained by maintaining good dispersibility in a matrix containing a resin component such as an alloy. It has been completed.

The present invention is shown below.
1. [A] rubber-reinforced styrene resin (hereinafter also referred to as “component [A]”) 40 to 94% by volume, and [B] heat conductive filler (hereinafter also referred to as “component [B]”) 5 to 5. 55% by volume and 1 to 20% by volume of an alloy and / or metal (hereinafter also referred to as “component [C]”) having a melting point of [C] of 500 ° C. or less (provided that component [A] and component The total of [B] and the component [C] is 100% by volume), and the volume ratio [B] / [C] of the component [B] and the component [C] is 1/2 to 35/1. The heat conductive resin composition characterized by the above-mentioned.
2. The component [A] is a rubber-reinforced styrene resin (A1) obtained by polymerizing a vinyl monomer (b) containing a styrene compound in the presence of the rubber polymer (a), or 2. The heat conductive resin composition according to 1 above, comprising a mixture of a rubber-reinforced styrene resin (A1) and a (co) polymer (A2) of a vinyl monomer.
3. 2. The heat conductive resin composition according to 1 above, wherein the component [B] is composed of at least one component selected from a carbon-based material, a ceramic-based material, and a metal-based material.
4). The component [C] is Sn—Cu—Bi, Sn—Cu—Zn, Sn—Bi, Sn—Cu, Sn—Al, Sn—Zn, Sn—Pt, Sn—Mn, Sn—Mg, Sn—Au. 2. The thermally conductive resin composition according to 1 above, which is at least one alloy selected from Bi-Cu, Al-Li, and Zn-Li.
5. Furthermore, [D] a metal deactivator (hereinafter also referred to as “component [D]”) is contained, and the content of the component [D] is the components [A], [B] and [C]. ] Is the heat conductive resin composition of said 1 which is 0.1-10 volume% when the sum total is 100 volume%.
6). 6. The thermally conductive resin composition according to 5 above, wherein the component [D] is an aromatic diacyl hydrazide compound and / or an azole compound.
7). Furthermore, the heat conductive resin composition of said 1 which contains polycarbonate resin and content of this polycarbonate resin is 1-150 mass parts with respect to 100 mass parts of said component [A].
8). Furthermore, the heat conductive resin composition of said 1 which contains a flame retardant and whose content of this flame retardant is 1-50 volume% with respect to a total of 100 volume% of all the polymers.
9. Furthermore, the heat conductive resin composition of the said 5 containing polycarbonate resin and content of this polycarbonate resin is 1-150 mass parts with respect to 100 mass parts of said component [A].
10. Furthermore, the heat conductive resin composition of said 5 which contains a flame retardant and whose content of this flame retardant is 1-50 volume% with respect to a total of 100 volume% of all the polymers.
11. A raw material composition containing [A] a rubber-reinforced styrene-based resin, [B] a thermally conductive filler, and [C] an alloy and / or a metal having a melting point of 500 ° C. or lower is heated to produce at least a component [C ] A process for kneading the raw material composition while making a part of the liquid phase a liquid phase, a method for producing a heat conductive resin composition.
12 12. The method for producing a thermally conductive resin composition as described in 11 above, wherein the raw material composition further contains [D] a metal deactivator.
13. The heat conductive resin composition according to 11 above, wherein the raw material composition further contains a polycarbonate resin, and the content of the polycarbonate resin is 1 to 150 parts by mass with respect to 100 parts by mass of the component [A]. Manufacturing method.
14 12. The method for producing a thermally conductive resin composition as described in 11 above, wherein the raw material composition further contains a flame retardant.
15. 13. The heat conductive resin composition according to 12 above, wherein the raw material composition further contains a polycarbonate resin, and the content of the polycarbonate resin is 1 to 150 parts by mass with respect to 100 parts by mass of the component [A]. Manufacturing method.
16. 13. The method for producing a thermally conductive resin composition as described in 12 above, wherein the raw material composition further contains a flame retardant.
17. [A] 40 to 94% by volume of a rubber-reinforced styrene resin, [B] 5 to 55% by volume of a thermally conductive filler, and [C] 1 to 20% by volume of an alloy and / or metal having a melting point of 500 ° C. or less. (However, the total of the component [A], the component [B] and the component [C] is 100% by volume.) The volume ratio [B] / [C] of the component [B] and the component [C] ] Is 1/2 to 35/1.
18. Furthermore, [D] contains a metal deactivator, and the content of the component [D] is 0 when the total of the component [A], the component [B] and the component [C] is 100% by volume. The housing according to 17 above, which is 1 to 10% by volume.
19. 18. The housing according to 17 above, further comprising a polycarbonate resin, wherein the content of the polycarbonate resin is 1-150 parts by mass with respect to 100 parts by mass of the component [A].
20. 18. The housing according to 17 above, further comprising a flame retardant, wherein the content of the flame retardant is 1 to 50% by volume with respect to 100% by volume of the total polymer.
21. 19. The housing according to 18 above, further comprising a polycarbonate resin, wherein the content of the polycarbonate resin is 1 to 150 parts by mass with respect to 100 parts by mass of the component [A].
22. 19. The housing according to 18 above, further comprising a flame retardant, wherein the content of the flame retardant is 1 to 50% by volume with respect to 100% by volume of the total polymer.

The thermally conductive resin composition of the present invention comprises [A] a rubber-reinforced styrene resin, [B] a thermally conductive filler, and [C] an alloy and / or a metal having a melting point of 500 ° C. or less, respectively. By containing a certain amount, a molded product having excellent molding processability (fluidity) and excellent thermal conductivity and electromagnetic shielding properties is obtained.
Other thermally conductive resin compositions of the present invention include [A] rubber-reinforced styrene-based resin, [B] thermally conductive filler, [C] an alloy and / or metal having a melting point of 500 ° C. or less, and [D ] By containing a predetermined amount of each of the metal deactivators, it is possible to reduce smoke generation during the production of a molded product, and to efficiently produce a molded product excellent in thermal conductivity, electromagnetic shielding properties, etc. it can.
When the said component [B] is disperse | distributing in the matrix containing the said component [A], it is excellent in especially heat conductivity and impact resistance.
When the said component [C] has connected the said component [B], it is excellent in heat conductivity especially.
When the said component [D] is an aromatic diacyl hydrazide compound and / or an azole compound, a molded article can be manufactured more efficiently.
Moreover, when a heat conductive resin composition contains a flame retardant, V-0 in UL94 specification can be achieved and it is excellent in a flame retardance.

  The manufacturing method of the heat conductive resin composition of this invention heats the raw material composition containing component [A], component [B], and component [C], and at least component [C], By providing the step of kneading the raw material composition while in the liquid phase, a composition in which the components [B], [C] and the like are uniformly dispersed in the resin component can be obtained. According to the method for producing another thermally conductive resin composition of the present invention, wherein the raw material composition further contains the component [D], the smoke generation time in the case of pellets, resin lumps, etc. is reduced, and the thermal conductivity In addition, it is possible to efficiently produce a heat conductive resin composition that gives a molded article excellent in electromagnetic shielding properties and the like.

In the molded article containing the heat conductive resin composition of the present invention, the components [B] and [C] are connected, preferably three-dimensionally, in the matrix mainly composed of the component [A]. Since it is contained with high dispersibility, it is structurally stable and has excellent thermal conductivity, electromagnetic shielding properties and heat dissipation properties. In addition, if the molded product is a peripheral member for releasing heat from the heat-generating component such as an electronic component to the outside, such as a housing, a substrate, a panel, a heat sink, etc., the heat-generating component malfunctions due to high temperature. Can be prevented, and the reliability of the device including the components can be improved.
In the housing of the present invention, the components [B], [C] and the like are uniformly dispersed in a matrix mainly composed of the component [A], and therefore, the housing is excellent in thermal conductivity, electromagnetic shielding properties and impact resistance. Furthermore, since the thermal emissivity is higher than that of metal or the like, heat dissipation is also excellent.

It is a schematic explanatory drawing which shows the measuring method of thermal conductivity using the test piece shape | molded in the Example.

Explanation of symbols

1; Test piece 2; Copper wire 3; Constantan wire 4; Thermocouple weld

The present invention will be described in detail below.
In the present invention, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acryl and methacryl.
The thermally conductive resin composition of the present invention comprises: [A] 40 to 94% by volume of a rubber-reinforced styrene resin, [B] 5 to 55% by volume of a thermally conductive filler, and [C] an alloy having a melting point of 500 ° C. or less. And / or 1 to 20% by volume of metal (provided that the total of the components [A], [B] and [C] is 100% by volume), and the components [B] and [C] above The volume ratio [B] / [C] is 1/2 to 35/1.
In the present invention, in addition to the above-mentioned components [A], [B] and [C], a heat conductive resin composition containing [D] a metal deactivator can also be used.

The rubber-reinforced styrene resin [A] preferably contains a copolymer resin obtained by polymerizing a styrene compound or the like in the presence of a rubbery polymer. As the copolymer resin, a rubber-reinforced styrene resin (A1) obtained by polymerizing a vinyl monomer (b) containing a styrene compound in the presence of the rubber polymer (a) may be used. it can.
Therefore, as the component [A], the rubber-reinforced styrene resin (A1) may be used alone, or a combination of the rubber-reinforced styrene resin (A1) and another thermoplastic polymer or resin. May be used. Examples of the latter case include those composed of a mixture of a rubber-reinforced styrene resin (A1) and a (co) polymer (A2) of a vinyl monomer.

  Examples of the rubbery polymer (a) include polybutadiene, styrene / butadiene copolymer, butadiene / acrylonitrile copolymer, styrene / butadiene / styrene block copolymer, and styrene / isoprene / styrene block copolymer. (Co) polymers and their hydrogenated products, ethylene / propylene copolymers, ethylene / propylene / nonconjugated diene copolymers, ethylene / butene-1 copolymers, ethylene / butene-1 / nonconjugated diene copolymers And non-diene (co) polymers such as ethylene / α-olefin copolymers such as isobutylene / isoprene copolymers, acrylic rubber, and silicone rubber. The hydrogenated product of the styrene / butadiene / styrene block copolymer includes a hydrogenated product of a styrene block and a styrene / butadiene random copolymer in addition to the hydrogenated product of the block copolymer. . The said rubbery polymer (a) can be used individually by 1 type or in combination of 2 or more types. In the present invention, when the rubber-reinforced styrene resin (A1) is obtained by emulsion polymerization, it is preferable to use a rubbery polymer made of latex.

  When the latex is used, the weight average particle diameter of the rubber-like polymer (a) in the latex is preferably 50 to 3,000 nm, more preferably 100 to 2,000 nm, and particularly preferably 120 to 800 nm. is there. When the weight average particle diameter is less than 50 nm, the impact resistance of the heat conductive resin composition of the present invention and a molded product containing the same tends to be inferior, and when it exceeds 3,000 nm, the surface appearance of the molded product tends to be inferior. It is in. The weight average particle diameter can be measured by a laser diffraction method, a light scattering method, or the like.

  As a method for producing the rubbery polymer (a), emulsion polymerization is preferable in consideration of adjustment of the average particle diameter and the like. In this case, the average particle size can be adjusted by selecting the production conditions such as the type of emulsifier and the amount used, the type and amount of initiator used, the polymerization time, the polymerization temperature, and the stirring conditions. Another method for adjusting the average particle size (particle size distribution) may be a method of blending two or more kinds of rubbery polymers (a) having different particle sizes.

  As the vinyl monomer (b) used for forming the rubber-reinforced styrene resin (A1), it is sufficient that a styrene compound is included. Otherwise, for example, a (meth) acrylic acid ester compound, cyanide is used. A vinyl compound, a maleimide compound, an acid anhydride, and the like can be used singly or in combination of two or more.

  Examples of the styrene compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, tert-butylstyrene, vinyltoluene, methyl-α-methylstyrene, divinylbenzene, brominated styrene, and the like. Of these, styrene, α-methylstyrene, and p-methylstyrene are preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of the (meth) acrylic acid ester compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, methyl acrylate, acrylic Examples include ethyl acid, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and the like. Of these, methyl methacrylate is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
Examples of the maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like. Can be mentioned. Of these, N-phenylmaleimide is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types. In addition, as another method for introducing a unit composed of a maleimide compound, for example, a method in which maleic anhydride is copolymerized and then imidized may be used.

Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used alone or in combination of two or more.
In addition to the above compounds, vinyl compounds having a functional group such as a hydroxyl group, an amino group, an epoxy group, an amide group, a carboxyl group, or an oxazoline group can be used as necessary. For example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N, N-dimethylaminomethyl methacrylate, N, N-dimethylaminomethyl acrylate, N, N-diethyl-p-aminomethylstyrene, methacrylic acid Glycidyl, glycidyl acrylate, 3,4-oxycyclohexyl methacrylate, 3,4-oxycyclohexyl acrylate, vinyl glycidyl ether, methallyl glycidyl ether, allyl glycidyl ether, methacrylamide, acrylamide, methacrylic acid, acrylic acid, vinyl oxazoline Etc. These can be used alone or in combination of two or more.

  The vinyl monomer (b) contains a styrene compound, and in this case, the polymerization ratio (b1) / (b2) of the styrene compound (b1) and the other vinyl monomer (b2). ) Is preferably (2-95)% by mass / (98-5)% by mass, more preferably (10-90)% by mass / (90-10)% by mass, when the total of these is 100% by mass. It is. If the amount of the styrenic compound (b1) used is too small, the moldability tends to be inferior. If it is too large, the heat-conductive resin composition of the present invention and the molded product containing the chemical resistance, heat resistance, etc. May not be enough.

  As described above, the component [A] may be only the rubber-reinforced styrene resin (A1), and obtained by polymerization of the rubber-reinforced styrene resin (A1) and a vinyl monomer. It may be a mixture with the (co) polymer (A2). Examples of the vinyl monomer include compounds used for forming the rubber-reinforced styrene resin (A1), that is, styrene compounds, (meth) acrylic acid ester compounds, vinyl cyanide compounds, maleimide compounds, acid anhydrides. 1 or more types chosen from the compound which has a thing and a functional group can be used. Therefore, the (co) polymer (A2) is a polymer obtained by polymerizing components having exactly the same composition as the vinyl monomer (b) used for forming the rubber-reinforced styrene resin (A1). It may be a polymer obtained by polymerizing the same type of monomer with different compositions, or a polymer obtained by polymerizing different types of monomers with different compositions It may be. Two or more of these polymers may be contained.

  Examples of the (co) polymer (A2) include acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, styrene / methyl methacrylate copolymer, and acrylonitrile. -Styrene and N-phenylmaleimide copolymer etc. are mentioned. These can be used alone or in combination of two or more.

Next, a method for producing the rubber-reinforced styrene resin (A1) and the (co) polymer (A2) will be described.
The rubber-reinforced styrene resin (A1) is produced by preferably subjecting the vinyl monomer (b) to emulsion polymerization, solution polymerization, and bulk polymerization in the presence of the rubbery polymer (a). Can do.
In the production of the rubber-reinforced styrene resin (A1), the rubber polymer (a) and the vinyl monomer (b) are present in the reaction system in the presence of the total amount of the rubber polymer (a). In addition, the vinyl-based monomer (b) may be added all at once, or divided or continuously. Moreover, the method which combined these may be used. Furthermore, you may superpose | polymerize by adding the whole quantity or one part of rubber-like polymer (a) in the middle of superposition | polymerization.
When 100 parts by mass of the rubber-reinforced styrene resin (A1) is produced, the amount of the rubbery polymer (a) used is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and still more preferably 15 to 60 parts by mass.
Moreover, about each usage-amount of rubber-like polymer (a) and a vinyl-type monomer (b), the usage-amount of a vinyl-type monomer (b) with respect to 100 mass parts of rubber-like polymers (a), Usually, it is 25-1900 mass parts, More preferably, it is 60-560 mass parts.

When the rubber-reinforced styrene resin (A1) is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.
As the polymerization initiator, a redox in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, or the like and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation are combined. System initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used alone or in combination of two or more. Furthermore, the polymerization initiator can be added to the reaction system all at once or continuously. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b) whole quantity, Preferably it is 0.2-0.7 mass%.

  Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan, terpinolene, α -A dimer of methylstyrene or the like. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the vinyl monomer (b).

  As an emulsifier used in the case of emulsion polymerization, sulfate ester of higher alcohol, alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate, aliphatic sulfonate such as sodium lauryl sulfate, higher aliphatic carboxylate, phosphoric acid Anionic surfactants such as nonionic surfactants such as alkyl ester type and alkyl ether type of polyethylene glycol. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer (b) whole quantity.

The latex obtained by emulsion polymerization is usually purified by coagulation with a coagulant to make the polymer component into powder, and then washing and drying. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid.
A known method can be adopted as a production method by solution polymerization and bulk polymerization.

The graft ratio of the rubber-reinforced styrene resin (A1) is preferably 10 to 200% by mass, more preferably 15 to 150% by mass, and particularly preferably 20 to 100% by mass. When the graft ratio of the rubber-reinforced styrene resin (A1) is less than 10% by mass, the surface appearance and impact resistance of the thermally conductive resin composition of the present invention and a molded product containing the composition may be lowered. On the other hand, if it exceeds 200%, the moldability is inferior.
Here, the graft ratio refers to x grams of the rubber component in 1 gram of the rubber-reinforced styrene resin (A1) and 1 gram of the rubber-reinforced styrene resin (A1) in acetone (however, the rubbery polymer (a)). When A is an acrylic rubber, acetonitrile is used.) When the insoluble content when dissolved in y-gram is obtained, the value is obtained by the following formula.
Graft ratio (mass%) = {(y−x) / x} × 100

In addition, the intrinsic viscosity [η] (in methyl ethyl ketone) of the soluble component by acetone of the rubber-reinforced styrene resin (A1) (provided that acetonitrile is used when the rubbery polymer (a) is acrylic rubber). , Measured at 30 ° C.) is preferably 0.1 to 1.0 dl / g, more preferably 0.2 to 0.9 dl / g, and particularly preferably 0.3 to 0.7 dl / g. By setting it as this range, it is excellent in moldability, and the impact resistance of the heat conductive resin composition of this invention and a molded article containing the same is also excellent.
The graft ratio and intrinsic viscosity [η] are the types and amounts of polymerization initiators, chain transfer agents, emulsifiers, solvents, and the like when producing the rubber-reinforced styrene-based resin (A1). It can be easily controlled by changing the polymerization temperature or the like.

The (co) polymer (A2) can be produced by bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or the like.
The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the (co) polymer (A2) is preferably 0.1 to 1.0 dl / g, more preferably 0.15 to 0.7 dl / g. It is. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent. The intrinsic viscosity [η] of this (co) polymer (A2) can be controlled by adjusting the production conditions, as in the case of the rubber-reinforced styrene resin (A1).

  Intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the soluble component by acetone of the above component [A] (provided that acetonitrile is used when the rubbery polymer (a) is acrylic rubber) Is preferably 0.1 to 0.8 dl / g, more preferably 0.15 to 0.7 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent.

  Here, when the component [A] is a rubber-reinforced styrene resin (A1), and a (co) polymer obtained by polymerization of the rubber-reinforced styrene resin (A1) and a vinyl monomer. In any case of the mixture with (A2), the content of the rubber-like polymer (a) in the heat conductive resin composition of the present invention is preferably 1 to 50% by mass, more preferably 3 to 3%. It is 40 mass%, More preferably, it is 3-35 mass%, Most preferably, it is 5-35 mass%. If the content of the rubbery polymer (a) is too small, the impact resistance of the heat conductive resin composition of the present invention and the molded product containing the rubber polymer tends to be inferior. The surface appearance, rigidity, heat resistance, etc. tend to be inferior.

  Content of component [A] in the heat conductive resin composition of this invention is 40-94 volume% when the sum total of component [A], [B] and [C] is 100 volume%, Preferably it is 50-94 volume%, More preferably, it is 60-94 volume%. If the content of the component [A] is too large, the thermal conductivity of the heat conductive resin composition of the present invention and a molded product containing the composition tends to be inferior. And the impact resistance of the molded product tend to be inferior.

  The thermal conductive filler [B] is preferably made of a material having a thermal conductivity of 20 W / m · K or more at 25 ° C. Examples of this component [B] include carbon-based fillers, ceramic-based fillers, metal-based fillers, alloy fillers, etc. (excluding component [C]). These can be used alone or in combination of two or more. Of these, carbon fillers, ceramic fillers and metal fillers are preferred. In addition, although melting | fusing point, decomposition point, etc. of this component [B] are not specifically limited, It is preferable that both melting | fusing point and decomposition point exceed 500 degreeC, More preferably, it is 600 degreeC or more.

Moreover, the shape of the said component [B] is not specifically limited, Any of powder shape (a spherical shape, plate shape, indefinite shape, etc.) and fibrous shape (linear shape) can be used, and it can also be used in combination. .
As powder filler, graphite powder; metal powder such as iron, copper, nickel, aluminum, magnesium, titanium, chromium, gold, silver; aluminum oxide, magnesium oxide, zinc oxide, boron nitride, aluminum nitride, silicon nitride, etc. Ceramic powder etc. are mentioned. Also, composite powder made of metal and graphite such as copper-graphite can be used. Furthermore, composite particles formed by coating inorganic metals or organic particles made of a substance other than the above as a core and coating the above metal or the like to form a shell can also be used.
The average particle diameter of the powder filler is preferably 1 to 150 μm, more preferably 20 to 90 μm. By setting the average particle size within this range, a highly dispersible resin composition can be obtained.

Examples of the fibrous filler include carbon fibers, carbon nanotubes, metal fibers made of the above metals, ceramic fibers such as alumina fibers, calcium titanate fibers, silicon nitride fibers, and glass fibers. Moreover, the composite fiber which coat | covers the inorganic fiber which consists of substances other than the above with the said metal etc. can also be used.
As the carbon fiber, a cellulose fiber, a PAN fiber, a pitch fiber or the like as a main raw material or a vapor phase growth method can be used. Note that some of the carbon fibers have higher thermal conductivity than inorganic fillers such as metal powders and ceramic powders. However, while showing favorable thermal conductivity with respect to the length direction, the thermal diffusibility and heat dissipation of the thermal conductive resin composition of the present invention and a molded article containing the thermal conductive resin composition may not be sufficient. Therefore, by using the carbon fiber and the inorganic filler in combination, the inorganic filler is connected to each other through the carbon fiber to form a three-dimensional heat conduction path. Can be improved. Of course, the carbon fibers are connected to each other via a component [C] to be described later, a three-dimensional heat conduction path is formed, and the heat diffusibility of the heat conductive resin composition of the present invention and a molded product including the same An effect of improving heat dissipation is also obtained.
The average diameter of the fibrous filler is preferably 1 to 35 μm, more preferably 5 to 20 μm. If the average diameter is too large, it may be crushed during kneading. The length is preferably 5 to 100 μm, more preferably 20 to 80 μm.
The powdery filler and the fibrous filler can be used singly or in combination of two or more.

In addition, as said component [B], what the surface modified | denatured with the coupling agent, the sizing agent, etc. can also be used. When the modified filler is used, the affinity with the resin component forming the matrix is improved, the dispersibility of the heat conductive filler [B], and further the heat conductive resin composition of the present invention and the same The thermal conductivity of the molded product containing can be further improved.
As the coupling agent, known coupling agents such as silane, titanium, and aluminum can be used. For example, isopropyl triisostearoyl titanate, acetoalkoxyaluminum diisopropylate, etc. can be used for the metal filler.
Examples of the sizing agent include epoxy resins, urethane-modified epoxy resins, polyurethane resins, and polyamide resins. These sizing agents are suitable for carbon fibers.
In the above modification, the component [B] is introduced into a solution in which a coupling agent or the like is dissolved in water or an organic solvent and immersed for a predetermined time, or a solution in which the coupling agent or the like is dissolved is sprayed on the component [B]. It can be done by such a method.

  Content of component [B] in the heat conductive resin composition of this invention is 5-55 volume% when the sum total of component [A], [B] and [C] is 100 volume%, Preferably it is 5-45 volume%, More preferably, it is 5-35 volume%. If the content of the component [B] is too large, the moldability, impact resistance and surface appearance of the resulting molded product tend to be reduced, while if too small, the thermal conductivity of the molded product is reduced. Tend to.

The component [C] is an alloy and / or metal having a melting point (liquidus temperature) derived from a phase diagram of 500 ° C. or less.
Examples of the component [C] include a Sn-based alloy, a Li-based alloy, and a Bi-based alloy. Examples of the Sn-based alloy include Sn-Cu-Bi, Sn-Cu-Zn, Sn-Al, Sn-Zn, Sn-Te, Sn-Pt, Sn-P, Sn-Mn, Sn-Ca, Sn-Mg, Sn-Cu, Sn-Ag, Sn-Au, Sn-Ba, Sn-Ge, Sn-Bi, etc. are mentioned. Examples of the Li-based alloy include Al—Li, Cu—Li, and Zn—Li. Moreover, Bi-Cu etc. are mentioned as a Bi type alloy. These can be used alone or in combination of two or more.

As said component [C], what becomes a semi-molten state in the melting temperature (for example, temperature of 200-300 degreeC) of the said component [A] is preferable, ie, lower temperature of melting | fusing point, for example, 400 degrees C or less More preferred is an alloy of
As an alloy having a melting point of 400 ° C. or less, Sn—Cu—Bi, Sn—Cu—Zn, Sn—Al, Sn—Zn, Sn—Mg, Sn—Cu, Sn—Ag, Sn—Au, Sn—Ba, Examples include Sn—Ge, Sn—Bi, Al—Li, Zn—Li, and Bi—Cu. Of these, Sn—Cu, Sn—Bi, and Sn—Cu—Bi are particularly preferable.

The content of the component [C] in the heat conductive resin composition of the present invention is 1 to 20% by volume when the total of the components [A], [B] and [C] is 100% by volume, Preferably it is 1-15 volume%, More preferably, it is 1-12 volume%. If the content of the component [C] is too large, the moldability, the surface appearance and the impact resistance of the resulting molded product tend to be reduced, while if too small, the thermal conductivity tends to be lowered. is there.
The volume ratio [B] / [C] of the above components [B] and [C] in the heat conductive resin composition of the present invention is 1/2 to 35/1, preferably 1/2. -30/1, more preferably 1 / 2-25 / 1. When the content of the component [B] is too small, the component [C] having a small thermal conductivity increases, and therefore the thermal conductivity of the thermal conductive resin composition of the present invention and a molded product containing the same tends to decrease. It is in. On the other hand, when there are too many said components [B], since the component [C] which connects components [B] will decrease, it exists in the tendency for thermal conductivity to fall.

  The metal deactivator [D] is a complex containing at least one atom of a metal atom constituting the component [B] and / or the component [C], preferably the thermally conductive resin composition of the present invention. It contains a substance capable of forming an inactive complex therein. By containing this component [D], it is possible to suppress alteration (oxidation, etc.) of the resin component due to the metal atoms and / or ions constituting the component [B] and / or the component [C]. it can. That is, even if the heat conductive resin composition of the present invention contains a trace amount of heavy metal ions such as copper ions derived from the above-mentioned component [B] or [C], this metal The activator [D] reacts with this ion or the like to form a complex, and the oxidation or the like of the resin component can be suppressed.

  As said component [D], an aromatic diacyl hydrazide compound, an azole compound, an azine compound, etc. are mentioned. These can be used alone or in combination of two or more.

（式中、Ｒ^１及びＲ^２は、同一であるか又は異なって、炭素数１〜４のアルキル基であり、ｓ及びｖは、それぞれ、１〜３の整数であり、ｔ及びｕは、それぞれ、２〜５の整数である。尚、ｓ及びｖが２又は３のとき、各Ｒ^１及び各Ｒ^２は、それぞれ、同一であっても、異なってもよい。）Examples of the aromatic diacyl hydrazide compound include compounds represented by the following general formula (1).

(In the formula, R ¹ and R ² are the same or different and each is an alkyl group having 1 to 4 carbon atoms, s and v are each an integer of 1 to 3, and t and u are respectively, an integer from 2 to 5. Note that when s and v is 2 or 3, each ^{R 1} and each ^{R 2,} respectively, may be the same or different.)

Examples of the compound represented by the general formula (1) include 2 ′, 3-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] propionohydrazide (the following formula (2) For example).

Examples of the azole compound include compounds such as imidazole, pyrazole, triazole, tetrazole, benzimidazole, and benzotriazole. These can be used alone or in combination of two or more.
In addition, these compounds may have a substituent. Examples of the substituent include alkyl groups having 1 to 12 carbon atoms, vinyl groups, phenyl groups, tolyl groups, xylyl groups, benzyl groups, naphthyl groups, alkoxyl groups having 1 to 4 carbon atoms, amino groups, phenylamino groups, mercapto groups. , A mercaptomethyl group, a mercaptoethyl group, —CH ₂ —N (R ³ ) ₂ (wherein R ³ is an alkyl group having 1 to 8 carbon atoms) and the like.

  Examples of imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, 2-pentylimidazole, 2-hexylimidazole, 2-cyclohexylimidazole, 2-phenylimidazole, and 2-nonyl. Imidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzylimidazole, 1-ethyl-2-methylbenzimidazole, 2-methyl-5,6-benzimidazole, 1 -Vinylimidazole, 1-allyl-2-methylimidazole, 2-cyanoimidazole, 2-chloroimidazole, 2-bromoimidazole, 1- (2-hydroxypropyl) -2-methylimidazole, -Phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-chloromethylbenzimidazole, 2-hydroxybenzimidazole, 2-ethyl-4-methylimidazole, 2-cyclohexyl -4-methylimidazole, 4-butyl-5-ethylimidazole, 2-butoxy-4-allylimidazole, 2-octyl-4-hexylimidazole, 2-methyl-5-ethylimidazole, 2-ethyl-4- (2 -Ethylamino) imidazole, 2-methyl-4-mercaptoethylimidazole, 2,5-chloro-4-ethylimidazole, 1-benzyl-2-methylimidazole, undecylimidazole and the like. These can be used alone or in combination of two or more.

  Examples of the pyrazole compound include pyrazole, 1-methylpyrazole, 3-methylpyrazole, 4-butylpyrazole, 1-methyl-3-propylpyrazole, 3-ethyl-5-methylpyrazole, 1- (3-hydroxypropyl) pyrazole, 5-phenylpyrazole, 5-benzylpyrazole, 1-phenyl-3-methylpyrazole, 1-cyanopyrazole, 3-chloropyrazole, 4-bromo-1-methylpyrazole, 1-phenyl-4,5,6,7- Tetrahydro-1H-indazole-3-carboxylic acid, 1- (2-chlorophenyl) -4,5,6,7-tetrahydro-1H-indazole-3-carboxylic acid, 1- (2,4-dichlorophenyl) -4, 5,6,7-tetrahydro-1H-indazole-3-carboxylate ethyl, 2-phenol 4,5,6,7-tetrahydro-2H-indazole-3-carboxylic acid, 7-methyl-2-phenyl-4,5,6,7-tetrahydro-2H-indazole-3-carboxylic acid, 1- (2-chlorophenyl) -cyclopenta-1H-pyrazole-3-carboxylic acid, 1-phenylcyclohepta-1H-pyrazole-3-carboxylic acid and the like. These can be used alone or in combination of two or more.

Examples of the triazole compound include 1,2,3-triazole, 1,2,4-triazole, 1-phenyl-1,2,3-triazole, 2-phenyl-1,2,3-triazole, 1-phenyl-1 2,4-triazole, 3- (N-salicyloyl) amino-1,2,4-triazole, and the like. These can be used alone or in combination of two or more.
Examples of tetrazole compounds include tetrazole, phenyltetrazole, mercaptotetrazole, [bis (2-ethylhexyl) aminomethylene] tetrazole, [bis (n-butyl) aminomethylene] tetrazole, [bis (n-hexyl) aminomethylene] tetrazole, [ Bis (n-octyl) aminomethylene] tetrazole and the like. These can be used alone or in combination of two or more.

Examples of the benzimidazole compound include 2-mercaptobenzimidazole and 2-mercaptomethylbenzimidazole. These can be used alone or in combination of two or more.
Examples of the benzotriazole compound include benzotriazole, tolyltriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α′- Dimethylbenzyl) phenyl) -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -benzotriazole, tolyltriazole potassium salt, benzotriazole, 2-methylimidazole adduct and the like. It is done. These can be used alone or in combination of two or more.

  The azine compound is preferably a triazine compound. For example, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 2,4,6-triaminotriazine, 1,3 , 5-triazine-2,4-dithiol monosodium, 6-dibutylamino-1,3,5-triazine-2,4-dithiol monosodium, 6-diethylamino-1,3,5-triazine-2, 4-dithiol, 6-dimethylamino-1,3,5-triazine-2,4-dithiol, 6-methoxy-1,3,5-triazine-2,4-dithiol, 6-phenylamino-1,3 Examples include 5-triazine-2,4-dithiol, 2-vinyl-4,6-diamino-1,3,5-triazine. These can be used alone or in combination of two or more.

  Other metal deactivators include ethylenediaminetetraacetic acid and its metal salts, decanedicarboxylic acid disalicyloyl hydrazide, N, N′-bis (2- (3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionyloxy) ethyl) oxamide, tris (2-tert-butyl-4- (3-tert-butyl-4-hydroxy-6-methylphenylthio) -5-methylphenyl) phosphite, oxalic acid Bisbenzylidenehydrazide, bis (2-phenoxypropionylhydrazide) isophthalate, 3,9-bis (2- (3,5-diamino-2,4,6-triazaphenyl) ethyl) -2,4,8,10 -Tetraoxaspiro [5.5] undecane etc. are mentioned. These can be used alone or in combination of two or more.

Since the heat conductive resin composition of the present invention is usually obtained by kneading the raw material composition at a temperature of 200 to 300 ° C. as described later, if the melting point of the component [D] is too low, Decomposition, vaporization, etc. occur inside, and a composition having a predetermined composition cannot be obtained. Therefore, the melting point of the component [D] is preferably 200 ° C. or higher, more preferably 210 ° C. or higher, still more preferably 220 ° C. or higher, and particularly preferably 250 ° C. or higher.
As said component [D], an aromatic diacyl hydrazide compound and an azole compound are preferable. A particularly preferable compound is a compound having a high melting point, 2 ′, 3-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] propionohydrazide (melting point: 226 to 228 ° C.), 3- (N-salicyloyl) amino-1,2,4-triazole (melting point 317 ° C.) and the like.

  Content of component [D] in the heat conductive resin composition of this invention is 0.1-10 volume% when the sum total of component [A], [B] and [C] is 100 volume%. Yes, preferably 0.2 to 5% by volume, more preferably 0.2 to 3% by volume. When there is too much content of the said component [D], the heat conductivity of the heat conductive resin composition of this invention and a molded article containing it may fall. On the other hand, if the content is too small, the smoke generation time in the production of pellets (composition) and molded articles becomes long, and the alteration (oxidation etc.) of the resin component may proceed.

Each content (volume ratio) of said component [A], [B], [C], [D] and an additive in the heat conductive resin composition of this invention is computed from the mass and specific gravity of each component. can do. In addition, specific gravity (20 degreeC) of said component [A], [B], [C], and [D] is respectively 0.99-1.09g / cm < ³ >, 1.9-20g / cm normally, respectively. ³ , 0.5 to 9.5 g / cm ³ , and 1.0 to 1.5 g / cm ³ .

  The thermally conductive resin composition of the present invention further includes other polymers; fillers, heat stabilizers, antioxidants, ultraviolet absorbers, flame retardants, anti-aging agents, plasticizers, antibacterial agents, colorants, and the like. It can also contain an additive.

  In this invention, it can be set as the heat conductive resin composition containing polycarbonate resin as another polymer. This polycarbonate resin can form a matrix with the said component [A]. By combining the component [A] and the polycarbonate resin, heat resistance, rigidity, flame retardancy and the like can be improved.

  The polycarbonate resin is not particularly limited, and may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, you may use combining an aromatic polycarbonate and an aliphatic polycarbonate. The polycarbonate resin may have a terminal modified with an R—CO— group or an R′—O—CO— group (R and R ′ each represents an organic group).

In the present invention, an aromatic polycarbonate is preferable, and those obtained by a reaction between a dihydroxyaryl compound and phosgene (phosgene method), those obtained by a transesterification reaction between a dihydroxyaryl compound and diphenyl carbonate (transesterification method), etc. Can be mentioned.
Here, as a dihydroxyaryl compound used as a raw material of the aromatic polycarbonate, bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) ) Propane (hereinafter also referred to as “bisphenol A”), 2,2′-bis (4-hydroxyphenyl) butane, 2,2′-bis (4-hydroxyphenyl) octane, 2,2′-bis (4 -Hydroxyphenyl) phenylmethane, 2,2'-bis (4-hydroxy-3-methylphenyl) propane, 2,2'-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2'- Bis (4-hydroxy-3-bromophenyl) propane, 2,2′-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclopentane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4,4 ′ -Dihydroxyphenyl sulfide, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxyphenyl sulfoxide, 4, Examples include 4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, hydroquinone, resorcin and the like. Of these, bisphenol A is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
A typical aromatic polycarbonate is obtained by reaction of bisphenol A and phosgene.
An aromatic polycarbonate and an aliphatic polycarbonate can be used individually by 1 type or in combination of 2 or more types, respectively.

The viscosity average molecular weight of the polycarbonate resin is preferably 8,000 to 50,000, more preferably 12,000 to 30,000, and still more preferably 15,000 to 26,000. This viscosity average molecular weight can be measured by a known method. If the viscosity average molecular weight is too small, the impact resistance of the molded product tends to be inferior. On the other hand, if the viscosity average molecular weight is too large, the moldability of the composition tends to be inferior. Two or more kinds of polycarbonate resins having different viscosity average molecular weights within the above range can also be used.
Moreover, the specific gravity at 20 ° C. of the polycarbonate resin is usually 1.18 to 1.22 g / cm ³ .

  The content of the polycarbonate resin is preferably 1 to 150 parts by mass, more preferably 10 to 150 parts by mass, and still more preferably 20 to 150 parts by mass with respect to 100 parts by mass of the component [A].

Examples of the filler include heavy calcium carbonate, light calcium carbonate, ultrafine activated calcium carbonate, special calcium carbonate, basic magnesium carbonate, kaolin clay, calcined clay, pyrophyllite clay, silane-treated clay, and synthetic silicic acid. Calcium, synthetic magnesium silicate, synthetic aluminum silicate, magnesium carbonate, magnesium hydroxide, kaolin, sericite, talc, fine powder talc, wollastonite, zeolite, zonotlite, asbestos, PMF (Processed Mineral Fiber), cucumber powder, sepiolite, titanium Potassium acid, elastadite, gypsum fiber, glass balun, silica balun, hydrotalcite, fly ash balun, shirasu balun, carbon balun, barium sulfate, aluminum sulfate, potassium sulfate Siumu, molybdenum disulfide, and the like. These can be used alone or in combination of two or more.
The content in the case of using the filler is preferably 1 to 30% by volume, more preferably 2 to 25% by volume, and still more preferably 2 to 2% with respect to 100% by volume in total of all the polymers in the composition. 20% by volume.

Examples of the heat stabilizer include phosphites, hindered phenols, thioethers, and the like. These can be used alone or in combination of two or more.
The content in the case of using the heat stabilizer is preferably 0.01 to 5% by volume with respect to 100% by volume in total of all the polymers in the composition.

Examples of the antioxidant include hindered amines, hydroquinones, hindered phenols, and sulfur-containing compounds. These can be used alone or in combination of two or more.
The content in the case of using the antioxidant is preferably 0.01 to 5% by volume with respect to 100% by volume in total of all the polymers in the composition.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more.
The content when using the ultraviolet absorber is preferably 0.01 to 10% by volume, more preferably 0.05 to 5% by volume, with respect to 100% by volume in total of all the polymers in the composition. More preferably, it is 0.1-5 volume%.

Examples of the flame retardant include organic flame retardants, inorganic flame retardants, and reactive flame retardants. These can be used alone or in combination of two or more.
Organic flame retardants include brominated epoxy compounds, brominated alkyltriazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene resins Halogenated flame retardants such as brominated bisphenol cyanurate resin, brominated polyphenylene ether, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, toki Hexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate Phosphate esters such as phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, compounds modified with these substituents, various condensed types Phosphorus ester compounds, phosphorus-based flame retardants such as phosphazene derivatives containing phosphorus element and nitrogen element, and the like can be mentioned. These can be used alone or in combination of two or more.

Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium-based, molybdenum-based, zinc stannate, guanidine salt, silicone-based, and phosphazene-based compounds. These can be used alone or in combination of two or more.
Reactive flame retardants include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl polyacrylate) , Chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether and the like. These can be used alone or in combination of two or more.

When the flame retardant is used, the content thereof is preferably 1 to 50% by volume, more preferably 2 to 40% by volume, and still more preferably 5 to 100% by volume of the total polymer in the composition. 40% by volume.
In addition, when making the heat conductive resin composition of this invention contain a flame retardant, it is preferable to use a flame retardant adjuvant together. As this flame retardant aid, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony tartrate and other antimony compounds, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, Examples thereof include ammonium polyphosphate, tin oxide, and iron oxide. These can be used alone or in combination of two or more.

Examples of the antiaging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds. Thiobisphenol compound, hindered phenol compound, phosphite compound, imidazole compound, nickel dithiocarbamate salt compound, phosphate compound and the like. These can be used alone or in combination of two or more.
The content in the case of using the anti-aging agent is preferably 0.01 to 10% by volume, more preferably 0.05 to 5% by volume, with respect to 100% by volume in total of all the polymers in the composition. More preferably, it is 0.1-5 volume%.

Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, and diisodecyl phthalate; dimethyl adipate , Diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di- Fatty acid esters such as (2-ethylhexyl) sebacate, diisooctyl sebacate; trimellitic acid isodecyl ester, trimellitic acid octy Esters, trimellitic acid esters such as trimellitic acid n-octyl ester, trimellitic acid isononyl ester; di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinolate, trilauryl phosphate, tristearyl phosphate , Tri- (2-ethylhexyl) phosphate, epoxidized soybean oil, polyether ester and the like. These can be used alone or in combination of two or more.
When the plasticizer is used, the content thereof is preferably 0.5 to 20% by volume, more preferably 1 to 15% by volume, and still more preferably with respect to 100% by volume of the total polymer in the composition. 1 to 10% by volume.

Examples of the antibacterial agents include zeolite antibacterial agents such as silver zeolite and silver-zinc zeolite, silica gel antibacterial agents such as complexed silver-silica gel, glass antibacterial agents, calcium phosphate antibacterial agents, and zirconium phosphate antibacterial agents. Silicate antibacterial agents such as silver-magnesium aluminate, titanium oxide antibacterial agents, ceramic antibacterial agents, whisker antibacterial agents, etc .; formaldehyde releasing agents, halogenated aromatic compounds, road Organic antibacterial agents such as propargyl derivatives, thiocyanate compounds, isothiazolinone derivatives, trihalomethylthio compounds, quaternary ammonium salts, biguanide compounds, aldehydes, phenols, pyridine oxide, carbanilide, diphenyl ether, carboxylic acid, organometallic compounds; inorganic and organic Hybrid antibacterial agent; natural anti Agent, and the like. These can be used alone or in combination of two or more.
When using the antibacterial agent, the content thereof is preferably 0.01 to 10% by volume, more preferably 0.05 to 5% by volume, more preferably 100% by volume of the total polymer in the composition. Preferably it is 0.1-5 volume%.

  Examples of the colorant include organic dyes, inorganic pigments, and organic pigments. These can be used alone or in combination of two or more.

The heat conductive resin composition of the present invention is preferably prepared by kneading the raw material composition containing the above components [A], [B], [C], etc., so that the component [A] is in a molten state. It can be produced by kneading [C] in a semi-molten state in which a solid phase portion and a liquid phase portion are mixed.
In the method for producing a heat conductive resin composition of the present invention, the raw material composition containing the above components [A], [B] and [C] is heated, and at least a part of the component [C] is made into a liquid phase. However, a step of kneading the raw material composition is provided. In addition, the said raw material composition may contain additives, such as said polymer [D]; other polymers, such as polycarbonate resin, and a flame retardant.

The amount of the above components [A], [B] and [C] used is 40 to 94% by volume, 5 to 55% by volume and 1 to 20% by volume, respectively, when the total amount is 100% by volume. Preferably, they are 50-94 volume%, 5-45 volume%, and 1-15 volume%, More preferably, they are 60-94 volume%, 5-35 volume%, and 1-12 volume%. The volume ratio [B] / [C] of the above components [B] and [C] is 1/2 to 35/1, preferably 1/2 to 30/1, more preferably 1/2. ~ 25/1.
Moreover, the usage-amount in the case of using the said component [D] is 0.1-10 volume% when the sum total of said component [A], [B] and [C] is 100 volume%, Preferably it is 0.2-5 volume%, More preferably, it is 0.2-3 volume%.

The raw material composition is an aggregate of raw material components, and when kneading, each component may be used alone, or may be used as a mixture prepared by arbitrarily combining in advance. As an example of the latter, a pellet composed of the components [A] and [B] can be used as one of the raw material components.
Moreover, as said component [C], it is preferable to use the lump with an average particle diameter of 5 mm or less. If this average particle size is too large, it takes time to knead, and it may be difficult to uniformly disperse in the resulting composition.

  The raw material composition is kneaded with a Banbury mixer, a roll mixer, a kneader, an extruder, or the like, usually while heating at a temperature of 200 to 300 ° C., preferably 200 to 250 ° C. At this time, in order to bring the component [C] into a semi-molten state in which the solid phase portion and the liquid phase portion are mixed, it is preferable to heat while adjusting the kneading conditions in consideration of the melting point. Specific examples of the kneading conditions for the raw material composition include a method of kneading with an extruder set at a cylinder temperature of 240 ° C .; kneading using a Banbury mixer until the internal temperature reaches 220 ° C., and further kneading for about 2 minutes. Methods and the like.

  In addition, after the said kneading | mixing process, the shaping | molding process which makes a pellet etc. predetermined shape can also be provided. In this molding step, various known molding machines can be used. When a composition containing no component [D] is used and pellets, resin masses, and the like are formed by this molding step, smoke may be emitted from the surface. However, by using the composition containing component [D], the smoke is usually extinguished within 10 minutes. Therefore, by the production method of the present invention, the composition containing the component [D] has a reduced smoke generation time in the case of pellets or the like, and provides a heat conduction that gives a molded product excellent in thermal conductivity, electromagnetic shielding properties, etc. The functional resin composition can be produced efficiently.

  In the heat conductive resin composition of this invention, said component [B], [C], and [D] are disperse | distributing in the matrix containing the said component [A]. Moreover, it is preferable that the said component [C] has connected the said component [B]. Further, in the composition containing the above component [D], a part or all of the above component [D] is included by forming a complex with the metal atom and / or its ions constituting the above component [C]. There may be.

The heat conductive resin composition of the present invention is excellent in fluidity and easy to mold under normal injection molding conditions.
Moreover, the heat conductive resin composition of this invention is excellent in heat conductivity, The heat conductivity measured by the method as described in the following Example, Preferably it is 1-7 W / m * K, More preferably, it is 1 6 W / m · K, more preferably 1.5 to 5 W / m · K.

  As mentioned above, since the heat conductive resin composition of this invention is excellent in fluidity | liquidity, it is excellent also in the workability of a molded article. Therefore, a molded product having high thermal conductivity can be easily obtained by a known molding method such as injection molding, extrusion molding, hollow molding, compression molding, vacuum molding, foam molding, blow molding or the like. The molding temperature is usually 210 to 250 ° C, preferably 220 to 250 ° C. In addition, when it uses as a molded article using the composition which does not contain a component [D], smoke may continue from the surface for a while, a resin component may oxidize, and shape maintenance property etc. may fall. However, by using a composition containing component [D], complete smoke suppression is usually achieved within 10 minutes, preferably within 8 minutes, more preferably within 6 minutes.

  Furthermore, the heat conductive resin composition of this invention is excellent also in electromagnetic shielding property. In recent years, electronic devices using computers such as personal computers, word processors, and video games have become familiar. Since these electronic devices use high-speed signals, they are easily affected by electromagnetic waves, and these devices themselves generate electromagnetic waves. As the range of use of radio waves expands, the electromagnetic environment deteriorates, and electromagnetic waves interfere with each other, and what is effective for one device becomes an obstacle to the other device. Furthermore, it is said that unnecessary electromagnetic waves generated for various reasons also pollute the electromagnetic environment. The heat conductive resin composition of the present invention can be formed into a molded product that blocks the passage of electromagnetic waves from the outside in order to ensure a good environment against the contamination of the electromagnetic environment as described above.

  The molded product is particularly suitable for peripheral members (housing, substrate, panel, heat sink, heat radiating fin, fan, packing, etc.) for releasing heat from the heat-generating component to the outside. In addition, it is also suitable for audio back panels, liquid crystal plate fixing members for liquid crystal televisions, motor peripheral members for digital video cameras, and the like. The surface of the molded product may be subjected to secondary processing such as painting, sputtering, welding, etc., depending on the application.

  The housing of the present invention includes the above-described thermally conductive resin composition of the present invention. That is, said component [A], [B], and [C] are each contained in a predetermined ratio. Furthermore, it is possible to contain components [D], other polymers such as a polycarbonate resin, and additives such as a flame retardant in a predetermined ratio. Each amount is as described above.

The housing of the present invention can be manufactured using the above-described heat conductive resin composition of the present invention. Examples of the molding method include injection molding, extrusion molding, hollow molding, compression molding, vacuum molding, foam molding, blow molding and the like.
The housing of the present invention includes electronic components (circuit boards, chips, thermal heads, etc.), electrical products (TVs (including liquid crystal types and portable types)), personal computer displays (including liquid crystal types), radios (including portable types). ), A camera (digital camera or the like), a video camera, an audio (CD or the like), a video (DVD or the like) player, a recorder, a recorder, an illumination, or the like.

  Hereinafter, the present invention will be described more specifically with reference to examples. “Part” and “%” are based on volume unless otherwise specified.

1. The raw material component of a heat conductive resin composition The raw material component used for manufacture of a heat conductive resin composition is shown below.
1-1. Ingredient [A]
(1) Rubber reinforced styrene resin (ABS-1)
Styrene and acrylonitrile are emulsion-polymerized in the presence of a latex containing polybutadiene rubber particles having a weight average particle size of 280 nm and toluene-insoluble content of 80% by mass, resulting in 41.5% by mass of polybutadiene rubber, 42.7% by mass of styrene unit and acrylonitrile. A rubber-reinforced styrene-based resin (hereinafter also referred to as “ABS-1”) having a unit amount of 15.8% by mass was obtained.
The graft ratio of this resin is 55% by mass, the intrinsic viscosity [η] of the acetone-soluble component (measured in methyl ethyl ketone at 30 ° C.) is 0.45 dl / g, and the specific gravity at 20 ° C. is 1.01 g / cm ³ .
(2) Rubber reinforced styrene resin (ABS-2)
Styrene and acrylonitrile are emulsion-polymerized in the presence of a latex containing polybutadiene rubber particles having a weight average particle size of 280 nm and toluene-insoluble content of 80% by mass, so that polybutadiene rubber is 60% by mass, styrene unit amount is 11.3% by mass, and acrylonitrile unit amount. A rubber-reinforced styrene-based resin (hereinafter also referred to as “ABS-2”) composed of 28.7% by mass was obtained.
The graft ratio of this resin is 50% by mass, the intrinsic viscosity [η] of the acetone-soluble component (measured in methyl ethyl ketone at 30 ° C.) is 0.4 dl / g, and the specific gravity at 20 ° C. is 0.98 g / cm ³ .
(3) Acrylonitrile styrene resin (AS)
A copolymer composed of 74.5% by mass of styrene units and 25.5% by mass of acrylonitrile units (hereinafter also referred to as “AS”) was used. The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) is 0.50 dl / g, and the specific gravity at 20 ° C. is 1.08 g / cm ³ .

1-2. Other polymers (polycarbonate resin)
Viscosity average molecular weight converted from solution viscosity measured at a temperature of 20 ° C. using a product name “NOVAREX 7022PJ” (hereinafter also referred to as “PC”) manufactured by Mitsubishi Engineering Plastics Co., Ltd., and using methylene chloride as a solvent. The specific gravity at 1,000, 20 ° C. is 1.2 g / cm ³ .

1-3. Ingredient [B]
(1) Graphite powder Product name “10099M” manufactured by Nishimura Graphite Co., Ltd., having an average particle size of 40 μm, thermal conductivity at 25 ° C. of about 120 W / m · K, and specific gravity at 20 ° C. of 2.3 g / cm ³ is there.
(2) Ceramic filler Aluminum oxide ceramics (trade name “AC2500-SI” manufactured by Admatechs) with an average particle size of 35 μm, thermal conductivity at 25 ° C. of 35 W / m · K, specific gravity at 20 ° C. Is 3.7 g / cm ³ .

1-4. Ingredient [C]
(1) Sn—Bi alloy An alloy having an average particle diameter of 25 μm and a melting point of 139 ° C.
(2) Sn—Cu alloy An alloy having an average particle diameter of 25 μm and a melting point of 227 ° C.

（２）金属不活性化剤（Ｄ２）
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1-5. Ingredient [D]
(1) Metal deactivator (D1)
3- (N-salicyloyl) amino-1,2,4-triazole (trade name “ADK STAB CDA-1” manufactured by Asahi Denka Co., Ltd.) represented by the following formula (3). The specific gravity at 20 ° C. is 1.04 g / cm ³ .

(2) Metal deactivator (D2)
2 ′, 3-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] propionohydrazide represented by the following formula (4) (trade name “Adekastab, manufactured by Asahi Denka Co., Ltd.) CDA-10 "). The specific gravity at 20 ° C. is 1.05 g / cm ³ .

1-6. Flame retardant (1) Brominated epoxy flame retardant: Bromochem First, trade name “F3020”. The specific gravity at 20 ° C. is 2.5 g / cm ³ .
(2) Aromatic condensed phosphate ester flame retardant 1,3-phenylenebisdixylenyl phosphate (manufactured by Daihachi Chemical Co., Ltd., trade name “PX-200”). The specific gravity at 20 ° C. is 1.22 g / cm ³ .
(3) Polytetrafluoroethylene The specific gravity at 20 ° C. is 2.2 g / cm ³ .
(4) Antimony trioxide (flame retardant aid)
The product name “PATOX-M” manufactured by Nippon Seiko Co., Ltd. was used. The specific gravity at 20 ° C. is 5.7 g / cm ³ .

2. Manufacture and evaluation of a heat conductive resin composition Manufacture and evaluation were performed about both the composition containing a metal deactivator and the composition which does not contain.

2-1. Production and Evaluation of Composition not Containing Component [D] Examples 1-1 to 1-9 and Comparative Example 1-1
Extruder in which each of the above raw material components was mixed for 5 minutes with a mixer at the blending ratio (volume conversion) shown in Table 1, and then the temperature from the raw material charging side to the die was set in the order of 190 ° C., 220 ° C. and 240 ° C. (Nippon Placon Co., Ltd., model “DMG”) was added and kneaded to obtain pellets (resin composition). Then, the test piece for evaluation of the predetermined shape and magnitude | size according to the evaluation item was obtained for this pellet using the injection molding machine (Nippon Steel Co., Ltd. make, model "J100-5C"). The molding conditions are a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C.
In addition, although Example 1-4 and 1-5 are the examples which mix | blended PC as another polymer, the compounding quantity of this PC is 117 mass parts with respect to 100 mass parts of component [A], respectively. And 132 parts by mass.

Each evaluation item and its measuring method are as follows. The evaluation results are also shown in Table 1.
(1) Molding processability The molding processability was determined according to the following criteria from the kneading situation by the extruder.
○: Melt kneading was possible and pellets could be obtained.
X: Kneading was impossible and no pellet was obtained.
(2) Thermal conductivity Thermal conductivity at 60 ° C. was measured using a steady heat flow meter (model “TCHM-DV”) manufactured by DYNATECH R & D. The test piece is a cylindrical body having an inner diameter of 50 mm. In the measurement, in order to accurately measure the temperature difference between the upper and lower surfaces of the test piece, as shown in FIG. 1, CC (copper-constantan) thermocouples were embedded in the upper and lower surfaces of the test piece center by hot pressing. By using a hot press, the flatness of the test piece can be improved, and the adhesion between the test piece and the thermocouple can be improved. The measurement of thermal conductivity was performed after maintaining the predetermined temperature for 1 hour in order to stabilize the heat flow rate.

(3) Volume resistivity (Rv)
Measurement was performed using a high resistance meter manufactured by Agilent Technologies. The test piece is a disc having an inner diameter of 100 mm and a thickness of 2 mm. The unit of volume resistivity is Ω · cm.
(4) Electromagnetic shielding properties Using TR17301 spectrum analyzer TR472 manufactured by Advantest Corporation, electromagnetic wave reflectivity was measured, and electromagnetic shielding properties in a frequency range of 0 to 1,000 MHz were evaluated. The test piece is a flat plate having a length of 150 mm, a width of 150 mm, and a thickness of 3 mm. If it is 50 dB or more, the electromagnetic shielding property is “present”.

(5) Smoke extinction test Using an injection molding machine (model name “EC60” manufactured by Toshiba Machine Co., Ltd.) with a cylinder temperature of 240 ° C., five 150 to 200 g resin masses were placed in the atmosphere at 20 ° C. Then, it was placed on an iron plate and the time until smoke disappeared was measured.
(6) Flammability A vertical combustion test was conducted in accordance with UL94 standard. The test piece is a flat plate having a length of 127 mm, a width of 13 mm, and a thickness of 2.0 mm.

From Table 1, the following is clear. Comparative example 1-1 is an example which does not contain component [B] and [C], and was inferior to heat conductivity and electromagnetic shielding property.
On the other hand, Examples 1-1, 1-2, 1-3, 1-6, 1-7, 1-8, and 1-9 depend on the types of components [B] and [C] and the presence or absence of flame retardants. It was excellent in thermal conductivity and electromagnetic shielding properties. Moreover, Examples 1-4 and 1-5 which contain polycarbonate resin (PC) as another polymer were also excellent in thermal conductivity and electromagnetic shielding properties. Furthermore, Examples 1-3, 1-5 and 1-6 containing a flame retardant exhibited V-0 or V-1 in the UL94 standard.

2-2. Production and Evaluation of Composition Containing Component [D] Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-2
Each raw material component described above was used in the blending ratios shown in Tables 2 and 3, and pellets were obtained in the same manner as in Example 1-1 to obtain evaluation test pieces. Using this test piece, various evaluations were performed in the same manner as in Example 1-1. The evaluation results are shown in Tables 2 and 3.

From Tables 2 and 3, the following is clear. Comparative Example 2-1 is an example containing a large amount of a metal deactivator, and since the metal deactivator became non-uniformly dispersed, the time until smoke extinguishes became long.
On the other hand, Examples 2-1 to 2-11 are examples in which a rubber-reinforced styrene resin, a thermally conductive filler, an alloy, and a metal deactivator are respectively contained in preferable ratios, and the time until smoke extinction is short. It was excellent in thermal conductivity and electromagnetic shielding properties. Comparing Example 1-8 and Example 2-1, in which the types and content ratios of the components [A], [B], and [C] are common, Example 2-1 is specific to thermal conductivity and volume. The time to extinguishment was halved without decreasing the resistance. The same applies to Example 1-9 and Example 2-8.
Moreover, Example 2-5 is an example which further contains a flame retardant, and showed V-0 in the UL94 standard.

  Since the heat conductive resin composition of the present invention is excellent in molding processability, it can be formed into a molded product having excellent heat conductivity and electromagnetic wave shielding properties. Housing, substrate, panel, heat sink, heat radiation fin, fan, packing Etc. can be used. These members are suitable for electronic components such as circuit boards, chips, thermal heads, motors, etc .; electrical devices such as televisions, radios, cameras, video cameras, audios, videos, lighting fixtures, etc. It is suitable for a housing, a heat sink and a fan for releasing the heat of the outside, an audio back panel, a liquid crystal plate fixing member of a liquid crystal television, and the like.

Claims (22)

  [A] 40 to 94% by volume of a rubber-reinforced styrene resin, [B] 5 to 55% by volume of a thermally conductive filler, and [C] 1 to 20% by volume of an alloy and / or metal having a melting point of 500 ° C. or less. (However, the total of the component [A], the component [B] and the component [C] is 100% by volume.) The volume ratio [B] / [C] of the component [B] and the component [C] ] Is 1 / 2-35 / 1. The heat conductive resin composition characterized by the above-mentioned.   The component [A] is a rubber-reinforced styrene resin (A1) obtained by polymerizing a vinyl monomer (b) containing a styrene compound in the presence of the rubber polymer (a), or The heat conductive resin composition of Claim 1 containing the mixture of the rubber reinforcement | strengthening styrene resin (A1) and the (co) polymer (A2) of a vinyl monomer.   The thermally conductive resin composition according to claim 1, wherein the component [B] is composed of at least one component selected from a carbon-based material, a ceramic-based material, and a metal-based material.   The component [C] is Sn—Cu—Bi, Sn—Cu—Zn, Sn—Bi, Sn—Cu, Sn—Al, Sn—Zn, Sn—Pt, Sn—Mn, Sn—Mg, Sn—Au. The thermally conductive resin composition according to claim 1, which is at least one selected from Bi—Cu, Al—Li, and Zn—Li.   Further, [D] contains a metal deactivator, and the content of the component [D] is 0 when the total of the components [A], [B] and [C] is 100% by volume. The heat conductive resin composition according to claim 1, wherein the heat conductive resin composition is 1 to 10% by volume.   The thermally conductive resin composition according to claim 5, wherein the component [D] is an aromatic diacyl hydrazide compound and / or an azole compound.   Furthermore, the heat conductive resin composition of Claim 1 which contains polycarbonate resin and content of this polycarbonate resin is 1-150 mass parts with respect to 100 mass parts of said component [A].   Furthermore, the heat conductive resin composition of Claim 1 which contains a flame retardant and whose content of this flame retardant is 1-50 volume% with respect to a total of 100 volume% of all the polymers.   Furthermore, polycarbonate resin is contained, The content of this polycarbonate resin is 1-150 mass parts with respect to 100 mass parts of said component [A], The heat conductive resin composition of Claim 5.   Furthermore, the heat conductive resin composition of Claim 5 which contains a flame retardant and whose content of this flame retardant is 1-50 volume% with respect to a total of 100 volume% of all the polymers.   A raw material composition containing [A] a rubber-reinforced styrene-based resin, [B] a thermally conductive filler, and [C] an alloy and / or a metal having a melting point of 500 ° C. or lower is heated to produce at least a component [C ] A process for kneading the raw material composition while making a part of the liquid phase a liquid phase, a method for producing a heat conductive resin composition. The method for producing a thermally conductive resin composition according to claim 11, wherein the raw material composition further contains [D] a metal deactivator.
  The thermally conductive resin according to claim 11, wherein the raw material composition further contains a polycarbonate resin, and the content of the polycarbonate resin is 1 to 150 parts by mass with respect to 100 parts by mass of the component [A]. A method for producing the composition.   The manufacturing method of the heat conductive resin composition of Claim 11 in which the said raw material composition contains a flame retardant further.   The thermally conductive resin according to claim 12, wherein the raw material composition further contains a polycarbonate resin, and the content of the polycarbonate resin is 1-150 parts by mass with respect to 100 parts by mass of the component [A]. A method for producing the composition.   The manufacturing method of the heat conductive resin composition of Claim 12 in which the said raw material composition contains a flame retardant further.   [A] 40 to 94% by volume of a rubber-reinforced styrene resin, [B] 5 to 55% by volume of a thermally conductive filler, and [C] 1 to 20% by volume of an alloy and / or metal having a melting point of 500 ° C. or less. (However, the total of the component [A], the component [B] and the component [C] is 100% by volume.) The volume ratio [B] / [C] of the component [B] and the component [C] ] Is 1/2 to 35/1.   Furthermore, [D] contains a metal deactivator, and the content of the component [D] is 0 when the total of the component [A], the component [B] and the component [C] is 100% by volume. The housing according to claim 17, wherein the housing is 1 to 10% by volume.   The housing according to claim 17, further comprising a polycarbonate resin, wherein the content of the polycarbonate resin is 1-150 parts by mass with respect to 100 parts by mass of the component [A].   The housing according to claim 17, further comprising a flame retardant, wherein the content of the flame retardant is 1 to 50% by volume based on 100% by volume of the total polymer.   Furthermore, polycarbonate resin is contained, The content of this polycarbonate resin is 1-150 mass parts with respect to 100 mass parts of said component [A], The housing of Claim 18.   The housing according to claim 18, further comprising a flame retardant, wherein the content of the flame retardant is 1 to 50% by volume with respect to 100% by volume of the total polymer.

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