WO2006132185A1

WO2006132185A1 - Insulative and thermally conductive resin composition and formed article, and method for production thereof

Info

Publication number: WO2006132185A1
Application number: PCT/JP2006/311231
Authority: WO
Inventors: Yasuyuki Agari; Tsuneo Kamiyahata; Yoshikazu Inada
Original assignee: Nippon Kagaku Yakin Co., Ltd.
Priority date: 2005-06-06
Filing date: 2006-06-05
Publication date: 2006-12-14
Also published as: JP5340595B2; JPWO2006132185A1

Abstract

Provided is an insulative and thermally conductive composition comprising 15 vol % or more of a matrix resin, an electrically insulating filler, a metal powder having a melting point of 500˚C or higher and a low melting point alloy having a melting point of 500˚C or less. The resin composition is excellent in forming processability and can produce a formed article having high insulating property and thermal conductivity. Furthermore,a method for producing the resin composition and a method for producing the formed article are also provided.

Description

Specification

Insulating thermally conductive resin composition, molded article, and method for producing the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to an insulating heat conductive resin composition, a molded article, and a method for producing the same, and more specifically, has high electrical insulation and high thermal conductivity that can be used for a casing of an electronic device. The present invention relates to an insulating heat conductive resin composition excellent in moldability, a molded product, and a method for producing the same.

Background art

[0002] With increasing integration density of semiconductor elements such as LSIs, speeding up of operation, and high-density mounting of electronic components, heat dissipation countermeasures for electronic components serving as heat sources have become a major problem. For example, metal and ceramics with high thermal conductivity S have been used for the housing of electronic parts. However, in recent years, grease-based materials that have a high degree of freedom in shape selection and are easy to miniaturize have been used. . Conventionally, a resin composition in which a filler having a high thermal conductivity, for example, a metal, an alloy, or ceramics is dispersed in a matrix resin, is used as the resin material (for example, Patent Document 1). However, metals can give large thermal conductivity, while they have high electrical conductivity, so there is a problem that electrical insulation cannot be imparted to the resin-based material. On the other hand, a method of coating the surface of high thermal conductive powder with an electrically insulating coating has been proposed (for example, Patent Document 2).

Patent Document 1: JP-A-5-239321

Patent Document 2: JP-A-8-183875

Disclosure of the invention

Problems to be solved by the invention

However, in the method of Patent Document 2, CVD is adopted as a method of coating the surface of the high thermal conductive powder with an electrically insulating film. However, this method is inevitably expensive. A low-cost rosin-based material is desired. In addition, when using high thermal conductivity ceramics, it is necessary to make the filling high in order to ensure high thermal conductivity, and because of its high hardness, the kneading member of the molding apparatus is easily damaged! . [0004] Therefore, the present invention solves the above-mentioned problems, can obtain a molded product having high insulation and thermal conductivity, and has an insulating thermal conductive resin composition excellent in molding processability and The object was to provide a molded product as well as a manufacturing method thereof.

Means for solving the problem

[0005] In order to solve the above problems, the insulating heat conductive resin composition of the present invention comprises a matrix resin of 15 vol% or more, an electrically insulating filler, a metal powder having a melting point of 500 ° C or more, And a low melting point alloy having a melting point of 500 ° C. or lower.

The resin composition of the present invention is obtained by kneading a mixed powder composed of a low-melting-point alloy, a metal powder, an electrically insulating filler and a resin in a state where the low-melting-point alloy is heated to a temperature at which the low-melting-point alloy is in a semi-molten state. be able to. According to the present invention, by setting the low melting point alloy in a semi-molten state, the viscosity of the low melting point alloy is made higher than that in the case of complete melting so that the viscosity difference from the resin is reduced. It can be made easy to disperse by scab. Therefore, compared with the case where the low melting point alloy is kneaded in a completely melted state, a resin composition in which the low melting point alloy is more uniformly dispersed in the resin can be obtained. The low melting point alloy contacts or welds the electrically insulating fillers to connect the electrically insulating fillers together to form a three-dimensional heat transfer path. The low melting point alloy uniformly dispersed in the resin connects the electrically insulating fillers with a small volume content compared to the conventional one, and forms a heat transfer path uniformly distributed in three dimensions. The electric conduction path is interrupted by the electrically insulating filler, and becomes insulating. The low melting point metal also comes in contact with the metal powder, forms a three-dimensional heat transfer path and exhibits high thermal conductivity, but tends to exhibit conductivity. Therefore, it is possible to achieve both high thermal conductivity and high electrical insulation by optimizing the quantity ratio of the electrically insulating filler and the metal powder. As a result, it is possible to provide a resin composition having a high thermal conductivity and electrical insulation without reducing the molding processability by setting the volume content of the resin serving as the matrix to 15 vol% or more.

In the present invention, the term “electrical insulation” means that the volume resistivity measured by a method according to JIS K6911 is at least ΩΩcm.

[0006] The resin composition according to one embodiment of the present invention comprises a thermoplastic resin of 30 vol% or more, an electric insulating filler of 5 to 40 vol%, a metal powder of 1 to: L0 vol%, and a low melting point. Alloy 1 ~: Contains LOvol%. [0007] Here, a metal filler having an oxide film on the surface can be used for the electrically insulating filter. The metal filler includes metal powder, metal flakes, and metal fibers. As the metal, a metal having a thermal conductivity of 80 WZm'K or more at 300K can be used, and examples thereof include copper, aluminum, tungsten, silicon, iridium, molybdenum, zinc, conoleto, nickel, and iron. be able to. Aluminum flakes are preferably used as the metal filler. Further, metal powder is contained separately from the above metal filler, but this metal powder has substantially no oxide film on the surface, and iron, copper, nickel, titanium, chromium, and at least of these metals. Those selected from the group consisting of alloys including one kind can be used. The low melting point alloy is selected from the group consisting of Sn-Cu, Sn-Al, Sn-Zn, Sn-Pt, Sn-Mn, Sn-Ag, Sn-Au, Al-Li, and Zn-U. At least one alloy can be used. As the matrix resin, a resin having a deflection temperature under load of 100 ° C or higher can be used. Moreover, it is preferable that the thermal conductivity of the resin composition is 2 WZm′K or more.

[0008] In addition, in the resin composition according to another aspect of the present invention, the matrix resin is a thermosetting resin, the electrically insulating filler is 5 to 65 vol%, and the metal powder is 1 to 10 vol%. , And low melting point alloy 1 to: LOvol%.

[0009] Here, in the electrically insulating filter, a metal filler having an acid film on the surface and Z or an inorganic filler can be used. Further, as the metal powder, any one selected from iron, copper, nickel, titanium, chromium, and a group force that is an alloy power including at least one of these metals can be used. Low melting point alloys include Bi-Sn, Bi-In, In-Zn, In-Sn, In-Ag, In-Na ゝ Na-Sn, Na-Au, Na-Ba ゝ Na-Li ゝ Li- A group force consisting of Ag, Li—Ca ゝ and Li—Ba can be used with at least one selected alloy. For thermosetting resin, a resin having a deflection temperature under load of 100 ° C or higher can be used. Moreover, it is preferable that the thermal conductivity of the resin composition is 2 WZm′K or more.

[0010] A molded article comprising the insulating thermally conductive resin composition of the present invention has a matrix resin of 15 vol% or more, an electrically insulating filler, a metal powder having a melting point of 500 ° C or more, and a melting point of 500 A mixed powder containing a low melting point alloy having a melting point of not higher than ° C is heated, the matrix resin is melted and kneaded, and the mixture is formed into a desired shape. As the molded product of the present invention, Examples of those that use thermosetting resin for matrix resin include printed circuit boards, LED module cases, and heat dissipation containers for electronic components.

[0011] The rosin composition of the present invention can be produced, for example, using the following method. That is, a mixed powder containing matrix resin, a metal filler having an oxide film on the surface, a metal powder having a melting point of 500 ° C or higher, and a low melting point alloy having a melting point of 500 ° C or lower is heated. The low melting point alloy is mixed in a semi-molten state in which the solid phase portion and the liquid phase portion are mixed, and the matrix resin is mixed in the molten state, and the mixture is formed into a desired shape.

The invention's effect

[0012] The resin composition of the present invention uses an electrically insulating filler, thereby reducing the filling rate of the filler, lowering the specific gravity compared to the conventional resin composition using a ceramic filler. It is possible to provide a resin composition which is excellent in formability and suitable for a molded article having high insulation and high thermal conductivity.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described.

The insulating thermally conductive resin composition according to the present invention comprises a matrix resin of 15 vol% or more, an electrically insulating filler, a metal powder having a melting point of 500 ° C or higher, and a low melting point of 500 ° C or lower. Melting point alloy.

[0014] The matrix resin used in the present invention is a thermoplastic resin! / Is a thermosetting resin, and a heat-resistant resin having a deflection temperature under load specified in JIS K7191 of 100 ° C or higher is used. Can be used. Specifically, thermoplastic resins include polyphenylene sulfide (PPS), liquid crystal polymer, polyether ether ketone (PEEK), polyimide, polyether imide, polyacetal, polyether sulfone, polysulfone, polycarbonate, Polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, polyphthalamide, polyamide and the like PPS power is preferred. PPS has a low viscosity at the time of melting, and the filler can be easily dispersed. In addition, since PPS has high heat resistance, the degree of freedom in selecting a low melting point alloy to be used can be increased.

[0015] Thermosetting resins include phenol resin, polyimide resin, epoxy resin, isocyanate resin, furan resin, polyurethane resin, aryl resin, key resin, unsaturated poly Examples include ester resin, diallyl phthalate resin, melamine resin, and the like. Epoxy resin is preferable.

Here, the epoxy resin is not particularly limited, and a known epoxy resin can be used. Examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetrabromobisphenol A type epoxy resin, naphthalene type epoxy resin, biphenol type epoxy resin, tetramethylbiphenol type. Epoxy resin, bifunctional epoxy resin, bifunctional epoxy resin such as mixture of tetramethylbiphenol type epoxy resin, phenol novolac type epoxy resin, 0-cresol novolac type epoxy resin, phenol Polyfunctional epoxy resins such as aralkyl epoxy resin, naphthol aralkyl epoxy resin, and naphthol novolac epoxy resin can be used. Curing agents include amine curing agents such as aliphatic amines, aromatic amines, and aliphatic cyclic amines, phenol novolaks, xylene novolacs, biphenol novolacs, bisphenol A novolacs, dicyclopentadiene phenol novolacs, etc. A phenolic curing agent or a catalytic curing agent such as dicyanamide can be used. In order to accelerate the curing reaction, accelerators such as tertiary amines, imidazoles, and aromatic polyamines can be used.

[0017] The volume content of the matrix rosin is 15 vol% or more, more preferably 15 vol% to 65 vol%, in order to ensure molding processability.

[0018] Upon kneading with the filler, the temperature is equal to or higher than the melting point of the thermoplastic resin, preferably 250 ° C.

The mixture is heated and kneaded in a temperature range of ˜400 ° C., more preferably 300 ° C. to 350 ° C. In the case of a thermosetting resin, it can be kneaded at a temperature not higher than its decomposition temperature, preferably not higher than 300 ° C.

[0019] In the electrically insulating filler, a metal filler having an acid film on the surface and Z or an inorganic filler can be used. Metal fillers having an oxide film on the surface include metal powder, metal flakes, and metal fibers. As the metal, a metal having a thermal conductivity of 80 W / m ′ K or more at 300 K can be used, for example, copper, aluminum, tandastene, silicon, iridium, molybdenum, zinc, cobalt, nickel, iron, etc. I can list them. The metal filler forms an oxide film that preferably has an oxide film on the entire surface. To achieve this, dry oxidation such as air oxidation at room temperature or high temperature, wet oxidation using an acid such as nitric acid, and an acid oxidation method such as an electrolytic acid using an electrolytic solution can be used. . The metal filler having an acid film on the surface improves the insulation by the surface acid film, while the bulk portion other than the surface has a high thermal conductivity, so that it has a high thermal conductivity and a high electrical insulation. Both can be achieved.

[0020] Aluminum flakes are preferably used for the metal filler having an acid oxide film on the surface. It has high thermal conductivity, and has a highly insulating and strong oxide film formed of natural acid on the surface. It needs to be further oxidized to form an oxide film. It is not.

[0021] In addition, the inorganic filler includes magnesium oxide, acid aluminum, titanium oxide, acid oxide, zinc oxide, copper oxide, iron oxide, zirconium oxide, and other oxide fillers, aluminum nitride, nitride Nitride fillers such as boron, silicon nitride, titanium nitride, carbide fillers such as silicon carbide, titanium carbide, boron carbide, and hydrated metal compound fillers such as aluminum hydroxide, magnesium hydroxide, boehmite, etc. Can be mentioned. Preferably, the inorganic filler is one selected from the group force consisting of magnesium oxide, aluminum oxide, boron nitride, aluminum nitride, silicon carbide, and a combination thereof.

[0022] When a metal filler having an oxide film on the surface is used as the electrically insulating filter, the volume content thereof is 5 to 40 vol%, more preferably 10 to 35 vol%. This is because if the volume content is less than 5 vol%, sufficient thermal conductivity cannot be obtained, and if it exceeds 40 vol%, the molding processability of the resin composition decreases. Further, when an inorganic filler is used in the electrically insulating filler, the volume content is 5 to 65 vol%, more preferably 15 to 65 vol%. If the volume content is less than 5 vol%, sufficient thermal conductivity cannot be obtained, and if it is greater than 65 vol%, the molding cacheability of the resin composition decreases.

[0023] The size of the electrically insulating filler is, in the case of a metal filler, a sieve passing rate of 150 m force S98% or more, more preferably a sieve passing rate of 100 / zm is 98% or more. In the case of an inorganic filler, the particle size is preferably 1 to 50 m.

[0024] It should be noted that the surface of the electrically insulating filler can be modified with a coupling agent! /, With a sizing agent, in order to impart affinity to the matrix resin. Matrix rosin Therefore, it is possible to improve the dispersibility of the electrically insulating filler and to further improve the thermal conductivity. As the coupling agent, known coupling agents such as silane, titanium, and aluminum can be used. For example, isopropyl triisostearoyl titanate or acetoalkoxyaluminum diisopropylate can be used. For the modification, the aluminum flake is immersed in a solution in which the coupling agent is water! /, Or a solution in an organic solvent for a predetermined time, or a solution in which the coupling agent is dissolved is sprayed on an aluminum-based filler. Can be used.

[0025] In addition, the surface of the electrically insulating filler can be modified by coating it with fluorine resin. The electrical insulation can be further improved, flame retardancy can be imparted to the electrically insulating filler, and scattering of the electrically insulating filler can also be suppressed. By suppressing scattering, workability can be improved. For the modification, the electrically insulating filler is immersed in a fluororesin dispersion or organosol for a predetermined time. / Or is sprayed with a fluororesin-containing dispersion or organosol on an aluminum filler and fired! The / can be dried.

[0026] In addition, the low melting point alloy is an alloy having a melting point (liquidus temperature) of 500 ° C or lower, which is preferably a semi-molten one at the melting temperature of the above heat-resistant resin. Can be used. As specific examples, a case where a thermoplastic resin is used for the matrix resin and a case where a thermosetting resin is used will be described. When thermoplastic resin is used, Sn-based alloys include Sn-Cu, Sn-Al, Sn-Zn, Sn-Te, Sn-Pt, Sn-P, Sn-Mn, Sn-Ag, Sn-Ca, Sn — Mg, Sn—Au, Sn—Ba, Sn—Ge, Li-based alloys include Al—Li, Cu—Li, and Zn—Li. More preferably, an alloy having a liquidus temperature of 400 ° C or lower, that is, Sn—Cu, Sn—Al, Sn—Zn, Sn—Pt, Sn—Mn, Sn—Ag, Sn—Au, Al—Li, At least one alloy selected from the group force selected from Zn-U force can be used. This is because the degree of freedom in selecting the kneaded oil to be kneaded can be increased. More preferably, at least one alloy selected from the group force consisting of Sn—Cu, Sn—Al, and Sn—Zn forces can be used. It is easy to obtain and low cost. More preferably, Sn—Cu can be used. This is because the selection range of the melting point is wide and the thermal conductivity is high. [0027] When thermosetting resin is used, Bi-Sn, Bi-In, In-Zn, In-Sn, In-Ag, In-Ag, In-Na-Na-Sn, Na-Au, Na-Ba ゝ Na-Li ゝ Li-Ag, Li-Ca ゝ Li-Ba and the like can be mentioned. More preferably, an alloy having a liquidus temperature of 400 ° C. or lower, that is, at least one alloy selected from the group consisting of Bi—Sn, Bi—In, In—Zn, and In—Sn is used. be able to. This is because the degree of freedom of selection of the kneaded oil to be kneaded can be increased. It is also easy to obtain and low cost. More preferably, BiSn can be used. This is because the selection range of the melting point is wide and the thermal conductivity is high.

[0028] The particle size of the low melting point alloy is preferably 5 mm or less. This is because if the particle size is larger than 5 mm, it takes time to melt, and further, it is uniformly dispersed in the matrix resin. Further, the shape is not particularly limited, and any shape such as a spherical shape, a teardrop shape, a lump shape, or a dendritic shape can be used.

[0029] Further, the metal powder that is separate from the metal filler having the oxide film on the surface is substantially free of the oxide film on the surface, and is made of iron, copper, nickel, titanium, chromium, and these metals. Alloying force including at least one kind of group force which is selected Any force One kind of metal can be used Copper, iron or nickel is preferable.

[0030] The volume content of the low melting point alloy is 1 to: LOvol%, more preferably 1 to 7vol%. If it is smaller than lvol%, the amount of the low melting point alloy connecting the electrically insulating filler is reduced and the thermal conductivity is lowered. On the other hand, if it is larger than 10 vol%, the amount of low melting point alloy having a low thermal conductivity increases and the thermal conductivity decreases. The volume content of the metal powder is 1 to 10 vol%, more preferably 1 to 5 vol%. If it is less than lvol%, the effect of improving the thermal conductivity is not sufficient. If it is greater than 10 vol%, the electrical insulation is reduced. The volume content of the metal powder is preferably smaller than the volume content of the low melting point alloy. This is because if the volume content of the metal powder is larger than the volume content of the low-melting point alloy, the effect of decreasing the electrical insulation is greater than the effect of increasing the thermal conductivity.

[0031] In addition, the resin composition of the present invention, if necessary, improves the strength and elastic modulus of the molded article, or is made of metal fibers comprising the above metals, or glass fibers, alumina fibers, titanic acid. Ceramic fiber such as calcium fiber and silicon nitride fiber or calcium carbonate Can contain.

[0032] In addition, the resin composition of the present invention is prepared by dry blending a resin, an electrically insulating filler, etc. in advance, supplying it to a single-screw or twin-screw kneading extruder, etc., and kneading and then granulating. Thus, a pellet can be produced and molded into a desired shape using an injection molding machine, a compression molding machine, an extrusion molding machine or the like having a predetermined mold. When the low melting point alloy is added, the kneading temperature is preferably set to a temperature within the kneading temperature range of the resin, and further to a temperature at which the low melting point alloy is mixed in a solid phase and a liquid phase. For dry blending, a Henschel mixer, a super mixer, a tumbler, or the like can be used. If necessary, the metal powder having a high density can be dry blended separately from the resin, fed from the middle of extrusion (side feed), and kneaded. Further, the fibrous filler can also be kneaded by side feeding separately from the metal powder. The method of kneading the thermosetting resin composition is to melt and knead the resin, insulation filler, etc. using a roll, a mixer, a kneader, a kneader, a single-screw kneading extruder, a twin-screw kneading extruder, etc. went. The kneading temperature was set to a temperature at which the low melting point alloy was in a mixed state of liquid and solid layers. In the case of a thermosetting resin for molding material, it is kneaded, cooled and pulverized, and pelletized or tableted. The molding can be formed into a desired shape by transfer molding, compression molding, injection molding or the like.

[0033] Embodiment 1.

The resin composition according to the present embodiment includes a matrix resin of 30 vol% or more, an electrically insulating filler of 5 to 40 vol%, a metal powder of 1 to LOvol%, and a low melting point alloy of 1 to LOLO%. It is a waste. More preferably, a thermoplastic resin is used for the matrix resin, and a metal filler having an acid film on the surface is used for the electrically insulating filler. Furthermore, aluminum flakes are preferably used for the metal filler. The volume content of the aluminum flakes is 5 to 40 vol%, more preferably 10 to 35 vol%. When the volume content is less than 5 vol%, sufficient thermal conductivity cannot be obtained, and when the volume content exceeds 40 vol%, the moldability of the cocoon and resin composition decreases.

[0034] The resin composition according to the present embodiment can reduce the filling rate of the filler as compared with the conventional resin composition using a ceramic filler, so that it has a low specific gravity and a moldability. In addition, it is possible to provide a resin composition having excellent insulation properties and high thermal conductivity. this Therefore, it can be applied to a housing of an electronic component and a heat sink or a fan for releasing heat from the electronic component to the outside. For example, it can be suitably used for a heat sink material of a semiconductor element, a casing of a fan motor, a housing for a motor core, a case for a secondary battery, a case of a notebook computer or a mobile phone, and the like.

Embodiment 2.

In the resin composition according to the present embodiment, the matrix resin is a thermosetting resin, the thermosetting resin is 15 vol% or more, the electrically insulating filler is 5 to 65 vol%, and the metal powder is 1 ~: LOvol% and low melting point alloy 1 ~: L0vol%. Preferably, a metal filler having an oxide film on the surface and Z or an inorganic filler are used for the electrically insulating filler. The volume content of the thermosetting resin is at least 15 vol%, more preferably at least 25 vol%, in order to ensure moldability.

[0036] The resin composition according to the present embodiment has the same effects and uses as the resin composition according to Embodiment 1. It can also be used for adhesives, printed circuit boards, LED module cases, and heat dissipation containers for electronic components. Adhesives are used to bond electronic components such as IC chips, resistors, capacitors, etc. mounted on substrates in semiconductor elements, high-density substrates and module components, adhesion between circuit boards and heat sinks, and LED chip substrates. It can be used for bonding. It can also be used to bond ceramic parts and metal parts in in-vehicle engines. In addition, the printed circuit board can be used as a new printed circuit board that replaces the conventional glass epoxy board in order to prevent the temperature rise of the printed circuit board on which electronic components are mounted at high density. Furthermore, in order to improve heat dissipation, it is also possible to provide a structure in which a metal heat dissipation plate is provided on one side of a substrate made of the resin composition of the present invention, and wiring is provided on another side. In addition, the LED module case is a combination of an insulating substrate made of the resin composition of the present invention and a heat sink as a countermeasure against heat in LED devices for lighting and backlights in which a large number of LEDs are arranged on the substrate. It can be set as a trick. In addition, it can be used as a heat dissipation container for electronic components in semiconductor packages and LED packages in order to improve heat dissipation.

Example

[0037] Hereinafter, the present invention will be described in detail by way of examples. (Sample preparation)

Polyphenol-sulfide (PPS) for rosin, aluminum flakes made of Toyo Aluminum (screen passage particle size 45 m 98%), copper powder for metal powder (Nikko Materials, particle size 20-25 μm) Sn-Cu alloy powder (average particle size 25 μm) was used as the low melting point alloy. The alloy used was a 4-30% Cu-Sn composition so that it was in a semi-molten state when kneaded with rosin.

[0038] The raw material mixed powder blended in the composition shown in Table 1 was put into a kneading extruder, kneaded at a temperature of 290 to 310 ° C, and extruded to produce a molding pellet. The molding pellets were molded by hot pressing to obtain a sample having a diameter of 50 mm and a thickness of 5 mm for measuring thermal conductivity and measuring electrical insulation.

For comparison, a sample using alumina (manufactured by Micron, average particle size of 35 m) and boron nitride (manufactured by Mitsui Chemicals, average particle size of 0.85 m) as a heat conductive filler was also prepared. Table 2 shows the composition.

Epoxy resin (biphenol type epoxy resin and tetramethylbiphenol type epoxy resin), phenolic curing agent (phenol novolak) as curing agent, 2-ethylimidazole as curing accelerator, inorganic filler As acid 匕 magnesium (Kyowa Chemical Industry, average particle size 30 μm) or acid 匕 aluminum (Kinsei Matec), metal powder is copper powder (Nikko Materials, particle size 20-25 μm), Bi-Sn alloy powder (average particle size 25 m) was used as the low melting point alloy. The alloy used was a composition of 15 to 98% Bi—Sn so as to be in a semi-molten state when kneaded with rosin.

For comparison, a sample consisting only of an epoxy resin, a curing agent, and a curing accelerator was also prepared. Table 3 shows the composition.

[0042] (Measurement of thermal conductivity)

In the case of thermoplastic thermally conductive resin composition, manufactured by DYNATECH R & D (model TCHM DV) steady state heat flow meter was used. During the measurement, CC (copper-constantan) thermocouples were embedded in the upper and lower surfaces of the sample by hot pressing in order to accurately measure the temperature difference between the upper and lower surfaces of the sample. By using a hot press, the flatness of the sample can be improved, and the adhesion between the sample and the thermocouple can be increased. In addition, in order to stabilize the heat flow, the measurement was performed after maintaining the temperature at a predetermined temperature for 1 hour. Tables 1 and 2 show the results of thermal conductivity measurements. In the case of a thermosetting heat conductive resin composition, it is not necessary to embed a thermocouple in the sample!熱 Laser The thermal conductivity was calculated using one flash method. The thermal diffusivity was measured according to JIS R1611 by laser flash method using a thermal constant measuring device (model number TC7000) manufactured by ULVAC-RIKO, and the specific heat was measured by a heat flux differential scanning heat flow meter (model number) DSC—50) was measured according to JIS K7123, the density was measured according to the JIS K7 112A method by the underwater substitution method, and these were multiplied to calculate the thermal conductivity. Table 3 shows the measurement results of thermal conductivity.

[0043] (Electrical insulation measurement)

The volume resistivity and applied voltage were measured according to JIS K6911. For measuring the volume resistivity, an HP16008B measurement cell and an HP4339A high resistance meter were used. In order to reduce contact resistance, conductive rubber was placed on the top and bottom surfaces of the sample. The results are shown in Tables 1 to 3.

[0044] (Adhesive strength measurement)

The tensile shear adhesive strength of a composition using a thermosetting resin as a matrix resin was measured according to JIS K6850.

[0045] [Table 1]

[0046] [Table 2]

[0047] [Table 3-1] Example 4 Example 5 Example 6 Epoxy resin 4 0 3 8 3 2

MgO 6 0 6 0 6 0

Cu 0 1 3

Bi-Sn 0 1 5

Thermal conductivity (WAi · K) 4. 0 4. 4 5. 2

Insulation characteristics

Applied voltage (V) 1 0 00 1 0 00 1 00 0 Volume resistivity (Ω-cm) 1 0 ¹⁵ 1 0 ¹ 1 0 ^{1 5} Adhesive strength (MPa) 1 4 1 4 1 4

[Table 3-2] Example 7 Example 8 Example 9 Comparative Example 4 Epoxy resin 5 0 48 4 2 1 0 0 Aluminum oxide 5 0 50 50 0

Cu 0 1 3 0

Bi-Sn 0 1 5 0 Thermal conductivity (W / m · Κ) 3. 6 4. 0 4. 5 0. 2 Insulation characteristics

Applied voltage (V) 1 0 0 0 1 00 0 1 00 0 1 0 00 Volume resistivity (Ω · cm) 1 0 "1 0 ^{1 4} 1 0 ^{1 4} 1 0 ¹⁵ Adhesive strength (MPa) 1 4 1 4 1 4 1 5 [0048] (Result)

In Examples 1 to 3, by using aluminum flakes, volume resistivity 10 ^{1 (>} Ω 'cm or more, good insulation with applied voltage of 100 V or more, and good thermal conductivity with thermal conductivity of 2 WZm'K or more. In Comparative Example 2, the thermal conductivity of 2 WZm'K can also be obtained, but it has to be filled with 50 vol%, and the molding processability is reduced.Comparative Example 3 has a thermal conductivity of Force using boron nitride, which is said to be good, With a filling amount almost the same as in Example 1, it was impossible to obtain a thermal conductivity of 2 W Zm'K.

[0049] In Examples 4 to 9 using a thermosetting resin, a volume resistivity of 10 ¹ Ω Ω 'cm or higher, an applied voltage of 100 V or higher, and a thermal conductivity of 2 WZm'K or higher. Good thermal conductivity could be secured. Moreover, even when a filler such as an insulating filler was included, the same high adhesive strength as in the case of a single resin could be obtained.

Claims

The scope of the claims

[I] Matrix resin 15 vol% or more, an electrically insulating filler, an insulating thermally conductive resin composition containing a metal powder having a melting point of 500 ° C. or higher and a low melting point alloy having a melting point of 500 ° C. or lower object.

[2] The matrix resin according to claim 1, comprising 30% by volume or more of the matrix resin, 5 to 40% by volume of the electrically insulating filler, 1 to 10% by volume of the above metal powder, and 1 to 10% by volume of the low melting point alloy. A rosin composition.

[3] The resin composition according to claim 2, wherein the electrically insulating filler is a metal filler having an acid film on the surface.

[4] The resin composition according to claim 3, wherein the metal filler is aluminum flakes.

[5] The deviation according to any one of claims 2 to 4, wherein the metal powder is selected from the group consisting of iron, copper, nickel, titanium, chromium, and an alloy containing at least one of these metals. The rosin composition according to any one of the above.

[6] The low melting point alloy is Sn—Cu, Sn—Al, Sn—Zn, Sn—Pt, Sn—Mn, Sn—Ag,

6. The resin composition according to claim 2, wherein the resin composition is at least one alloy selected from the group consisting of Sn—Au, Al—Li, and Zn—U.

7. The resin composition according to any one of claims 2 to 6, wherein the deflection temperature under load of the thermoplastic resin is 100 ° C or higher.

8. The resin composition according to any one of claims 2 to 7, wherein the thermal conductivity is 2WZm'K or more.

[9] The matrix resin is a thermosetting resin and contains 5 to 65 νol% of the electrically insulating filler, 1 to 10 vol% of the metal powder, and 1 to 10 vol% of the low melting point alloy. The rosin composition according to claim 1.

10. The resin composition according to claim 9, wherein the electrically insulating filler is a metal filler and a soot or an inorganic filler having an acid film on the surface.

[II] The metal powder according to claim 9 or 10, wherein the metal powder is any one selected from iron, copper, nickel, titanium, chromium, and an alloy force including at least one of these metals and also an alloying force. Fat composition.

[12] The low melting point alloy is Bi-Sn, Bi-In, In-Zn, In-Sn, In-Ag, In-Na ゝ Na The at least one alloy selected from the group consisting of —Sn, Na—Au, Na—Ba, Na—Li, Li—Ag, Li—Ca, and Li—Ba. The resin composition according to one.

13. The resin composition according to any one of claims 9 to 12, wherein the deflection temperature under load of the thermosetting resin is 100 ° C or higher.

[14] The resin composition according to any one of [9] to [13], wherein the thermal conductivity is 2 WZm′K or more.

[15] Matrix resin 15 vol% or more, an electrically insulating filler, an insulating heat conductive resin composition containing a metal powder having a melting point of 500 ° C. or higher and a low melting point alloy having a melting point of 500 ° C. or lower Molded product made of physical strength.

16. The molded article according to claim 15, wherein the molded article is a printed board containing a thermosetting resin as a matrix resin.

17. The molded product according to claim 15, wherein the molded product is an LED module case containing a thermosetting resin as a matrix resin.

18. The molded product according to claim 15, wherein the molded product is a heat radiating container for electronic parts containing a thermosetting resin as a matrix resin.

[19] A mixed powder containing 15% by volume or more of matrix resin, an electrically insulating filler, a metal powder having a melting point of 500 ° C or higher, and a low melting point alloy having a melting point of 500 ° C or lower is heated to produce a low melting point. A method for producing an insulating thermally conductive resin composition in which an alloy is mixed in a semi-molten state in which a solid phase part and a liquid phase part are mixed, matrix resin is kneaded in a molten state, and the mixture is formed into a desired shape.