WO2025166510A1 - Thermal conductive composition and heat dissipating member - Google Patents
Thermal conductive composition and heat dissipating memberInfo
- Publication number
- WO2025166510A1 WO2025166510A1 PCT/CN2024/076121 CN2024076121W WO2025166510A1 WO 2025166510 A1 WO2025166510 A1 WO 2025166510A1 CN 2024076121 W CN2024076121 W CN 2024076121W WO 2025166510 A1 WO2025166510 A1 WO 2025166510A1
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- WO
- WIPO (PCT)
- Prior art keywords
- thermal conductive
- conductive composition
- diamond particles
- composition according
- silicone resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3737—Organic materials with or without a thermoconductive filler
Definitions
- heat-dissipating members can be installed inside or outside the devices, for example, between electronic devices and housings, heat sinks or the like.
- the heat-dissipating members are usually formed of heat dissipating resin compositions, which are produced by dispersing and mixing thermal conductive fillers in a polymer matrix, for example, silicone resin.
- thermal conductive fillers such as aluminum nitride, alumina, magnesium oxide, boron nitride, however, super high thermal conductivity can’ t be achieved, for example, of above 15W/m ⁇ K.
- diamond powder is introduced in the field of heat dissipation of electronic devices due to its natural high conductivity of around 1000W/m ⁇ K, and electric insulativity at room temperature.
- it due to its inert chemical property, it’s difficult for the diamond powder to be mixed and dispersed well with polymer matrix and other types of fillers such as aluminum nitride and alumina, and therefore, its thermal conductive effect and thus heat dissipation benefit can’t be utilized to a maximum extent.
- the present inventor has found that by surface treating diamond particles having a controlled particle size with a particular surface treating agent, the diamond particles can be easily and homogenously dispersed in the polymer matrix, resulting in a thermal conductive composition having improved flowability and storage stability, and excellent thermal conductivity.
- the present invention provides a thermal conductive composition, comprising a polymer matrix, and diamond particles having an average particle size D50 of about 20 to 150 ⁇ m which are surface treated with an alkylalkoxysilane compound having about 9 to 16 carbon atoms in the alkyl group in an amount of more than 0.03 wt. %and less than 0.7wt. %based on the weight of diamond particles.
- the present invention provides a heat dissipating member obtained by curing the thermal conductive composition.
- the thermal conductive composition according to the present invention comprises a polymer matrix and surface-treated diamond particles.
- the thermal conductive composition exhibits improved flowability and thermal conductivity, and at the same time exhibits excellent storage stability and thixotropy, which are desirable for dispensing process in the manufacturing of electronic assembly.
- the thermal conductive composition according to the present invention comprises a polymer matrix.
- the polymer matrix suitable for use in the present invention can be of any type conventionally used in a thermal conductive polymer composition material.
- suitable polymer matrix include, but are not limited to, resins, for example, silicone resins, epoxy resins and polyurethane resins, and silicone oil, for example, methylphenyl silicone oil, dimethylsilicone oil, and modified silicone oil.
- epoxy resins mention may be made of epoxy compounds having at least one, preferably two or more epoxy groups, examples of which include bisphenol-type epoxy resin, novolac-type epoxy resin, diphenyl-type epoxy resin, and naphthalene-type epoxy resin etc.
- the thermal conductive composition according to the present invention comprises a silicone resin.
- the silicone resin may be condensation curable type silicone resin, or addition reaction-curable type silicone resin, with addition reaction-curable type silicone resin being more preferable.
- the unsaturated group-containing polyorganosiloxane is preferably a polyorganosiloxane having alkenyl group, more preferably vinyl group, examples of which include vinyl-terminated polyorganosiloxane, for example, vinyl-terminated polydimethylsiloxane, vinyl-terminated polydimethylmethylvinylsiloxane, vinyl-terminated polydimethylmethylphenylsiloxane, vinyl-terminated polydimethyldiphenylsiloxane.
- the thermal conductive composition according to the present invention comprises diamond particles as described below as a thermal conductive filler.
- the diamond particles to be used have an average particle size D50 of about 20 to 150 ⁇ m, preferably about 25 to 130 ⁇ m. If the average particle size is lower than about 20 ⁇ m, generally synthetic diamond particles of below 20 ⁇ m have irregular shape which will affect thermal conductivity and viscosity of the composition. If the average particle size is larger than about 150 ⁇ m, the filler will affect the bondline thickness (BLT) and compression force of electronic assembly.
- BLT bondline thickness
- the diamond particles to be used in the thermal conductive composition according to the invention have been surface treated with an alkylalkoxy silane compound comprising about 9 to 16, preferably about 10 to 16, more preferably about 11 to 15 carbon atoms in the alkyl group.
- alkylalkoxysilane compound examples include, but are not limited to, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, methyl-octyldimethoxysilane, methyl-octyldiethoxysilane, methydecyldimethoxysilane, methyldodecyldimethoxysilane, methylhexadecyldimethoxysilane.
- the amount of the silane compound to be used as a surface treating agent is greater than 0.03wt. %and smaller than 0.07wt. %, and preferably is about 0.04 to 0.55wt. %, relative to the weight of the diamond particles.
- a method for surface treating the diamond particles with the silane compound is not especially limited, and as known in the art, there can be used, for example, a wet treatment method, a dry treatment method, or a combination thereof.
- the wet treatment method comprises the steps of adding the diamond particles in a solution in which the silane compound is dispersed, mixing the mixture and then heat treating the mixture at a temperature of normally about 50 to 90 °C.
- the thermal conductive composition may contain from 25 to 75 wt. %, preferably from 35 to 65 wt. %of the diamond particles, based on the total weight of the composition.
- the thermal conductive composition may further preferably comprise other thermal conductive fillers conventionally used in the art than the diamond particles.
- thermal conductive fillers include, but are not limited to, alumina, magnesium oxide, zinc oxide, boron nitride, aluminum nitride, etc. This other thermal conductive filler may be used in a single type or in combination of two or more types.
- the thermal conductive fillers may have an average particle size D50 of 0.1 to 200 ⁇ m.
- the thermal conductive composition according to the invention may further comprise other additives conventionally used for heat dissipating member, for example, reactor inhibitor, dispersant, antioxidant, thermal stabilizer, pigments, and flame retardant according to actual needs.
- additives conventionally used for heat dissipating member for example, reactor inhibitor, dispersant, antioxidant, thermal stabilizer, pigments, and flame retardant according to actual needs.
- the thermal conductive composition comprises a dispersant, to facilitate dispersion of the thermal conductive fillers in the polymer matrix of the composition.
- a dispersant silicone-based or non-silicone based dispersant can be used, for example, polydimethylsiloxane, hydroxyl-functional polydimethylsiloxane, fatty acids, polyacrylates.
- the amount of the dispersant to be used in the composition may be, based on the total weight of the composition, from about 0.1 to 5wt. %, preferably about 0.5 to 2wt. %.
- the thermal conductive composition according to the invention can be prepared by mixing the polymer matrix, the diamond particles, and further optionally other thermal conductive fillers, and additives as described above.
- a two-component curing type silicone resin is used as the polymer matrix, and in this case, as described above, the thermal conductive composition can be prepared by mixing a first component comprising the unsaturated group-containing polyorganosiloxane and a second component comprising the hydrogen group-containing polyorganosiloxane, which have been prepared separately.
- the diamond particles, the other thermal conductive fillers and the optional additives can be comprised in either or both of the first component and the second component.
- the first component can be prepared by mixing the unsaturated group-containing polyorganosiloxane, the platinum compound catalyst, the diamond particles, other thermal conductive fillers, and additives comprising for example a dispersant, a reaction inhibitor and a pigment
- the second component can be prepared by mixing the hydrogen group-containing polyorganosiloxane, the diamond particles, other thermal conductive fillers, and an additive for example a pigment.
- the mixing can be done by any known mixing apparatus, which can be selected by a skilled person according to practical requirement, at a temperature of normally from about 20°C to 140°C, preferably about 60°C to 120°C.
- a planetary mixer, a kneader, a static mixer, or any combination thereof can be used.
- the thermal conductive composition according to the present invention exhibits an excellent property portfolio of initial flow rate, aged flow rate, thixotropy, and storage stability.
- the present invention provides a heat dissipating member, which is obtained by curing the above thermal conductive composition.
- the thermal conductive composition can be cured by heating, or without being heated.
- the composition can be cured at normal temperature, for example about 25°C after 24 to 48 hours, or the composition can be cured by heating at about 60-80°C for about 0.5 to 2 hours.
- the obtained heat dissipating member according to the present invention has an excellent thermal conductivity of above 15.00 W/m ⁇ K.
- the heat dissipating member according to the present invention is suitable for use in a wide variety of electronic devices and electronic components, for example, CPUs, chipsets, hard disk drives, power transistors, etc.
- Raw Diamond particles-A average particle size of 115 ⁇ m, specific surface area of 0.050 m 2 /g, available from Guangzhou Fanya Jiarong Trading Co., Ltd.;
- Raw Diamond particles-B average particle size of 45 ⁇ m, specific surface area of 0.140 m 2 /g, available from Guangzhou Fanya Jiarong Trading Co., Ltd.;
- Raw Diamond particles-C average particle size of 25 ⁇ m, specific surface area of 0.25 m 2 /g, available from Guangzhou Fanya Jiarong Trading Co., Ltd.;
- Vinyl-terminated polysiloxane trade name: RH-Vi321, available from Ningbo Runhe High-tech Material Co., Ltd.;
- Hydride-terminated polydimethylsiloxane trade name: XL1-7501, available from Nusil Technology LLC.;
- Trimethyl-terminated polymethyhydrogenlsiloxane trade name: RH-H33, available from Ningbo Runhe High-tech Material Co., Ltd.;
- Polydimethylsiloxane trade name: KF-96-50CS, available from Shin-Etsu;
- Platinum Catalyst Karstedt Catalyst, having a Pt content of 2%, trade name: CAT1-50, available from Nusil Technology LLC;
- Inhibitor 1, 3, 5, 7-tetramethyl-1, 3, 5, 7-tetravinyl-cyclotetrasiloxane, trade name: XL-119, available from Nusil Technology LLC;
- Filler dispersant trade name: LP-X-21879, available from BYK;
- Pigment trade name: Sunfast Blue 15: 4 &Sunfast Green 7, available from Qingdao Sun Chemical Corporation;
- Aluminum Nitride-1 average particle size of 120 ⁇ m, trade name: AN120, available from Suzhou Ginet New Material Technology Co., Ltd.;
- Aluminum Nitride-2 average particle size of 25 ⁇ m, trade name: AN30, available from Suzhou Ginet New Material Technology Co., Ltd.;
- Aluminum Nitride-3 average particle size of 5 ⁇ m, trade name: AN5, available from Suzhou Ginet New Material Technology Co., Ltd.;
- Alumina average particle size of 0.3 ⁇ m, trade name: Y06-1, available from Suzhou Ginet New Material Technology Co., Ltd.
- Part A (a first component) was prepared by first mixing the ingredients except for the inhibitor and platinum catalyst in a planetary mixer at a speed of 25 rpm and at normal temperature for 30 minutes, and then at a speed of 20rpm and at a temperature of 100 to 150°C for 1 hour, and cooling to 30°C, followed by adding the inhibitor and platinum catalyst and mixing for additional 30 minutes.
- Part B was prepared by mixing the respective ingredients in a planetary mixer at a speed of 25 rpm and at normal temperature for 30 minutes, and then at a speed of 20rpm and at a temperature of 100 to 150°C for 1 hour, and cooling to 30°C.
- the thermal conductive compositions were then applied on the test plate of LW-9389 Thermal Tester, with test condition being 80°C for 30 minutes and the compositions were online cured. The cured products were then subjected to a thermal conductivity test.
- Viscosity was measured at 25°C on a Rheometer (Discovery HR-30, manufactured by TA instruments Inc. ) using a plate-plate geometry with a 25mm in diameter plate at a 1.0mm gap and at a shear rate of 0.1s -1 and 1.0s -1 .
- the thixotropy was calculated by the following equation:
- Example 7 using treated diamond particles having a greater average particle size in Example 6 further improves the combined properties of thixotropy, flow rate reliability and thermal conductivity to some extent. According to the present invention, therefore, the average particle size of the diamond particles should be controlled to be not lower than about 20 ⁇ m.
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Abstract
The present invention relates to a thermal conductive composition, and a heat dissipating member comprising the thermal conductive composition.
Description
The present invention relates to a thermal conductive composition, and a heat dissipating member comprising the thermal conductive composition.
In electronic devices, integrated electronic components generate heat, which may cause failures. In recent years, with the increasing demand for compactness and high performance of electronic components, the power density of semiconductor components continues to increase, with the heat flux also increasing. Especially these years, as cloud computing and 5G/6G technology grows up, the heat dissipation of electronic device is becoming more and more important.
To dissipate heat generated from the electronic components, heat-dissipating members can be installed inside or outside the devices, for example, between electronic devices and housings, heat sinks or the like. The heat-dissipating members are usually formed of heat dissipating resin compositions, which are produced by dispersing and mixing thermal conductive fillers in a polymer matrix, for example, silicone resin. With traditional thermal conductive fillers such as aluminum nitride, alumina, magnesium oxide, boron nitride, however, super high thermal conductivity can’ t be achieved, for example, of above 15W/m·K.
In recent years, diamond powder is introduced in the field of heat dissipation of electronic devices due to its natural high conductivity of around 1000W/m·K, and electric insulativity at room temperature. However, due to its inert chemical property, it’s difficult for the diamond powder to be mixed and dispersed well with polymer matrix and other types of fillers such as aluminum nitride and alumina, and therefore, its thermal conductive effect and thus heat dissipation benefit can’t be utilized to a maximum extent.
After extensive research, the present inventor has found that by surface treating diamond particles having a controlled particle size with a particular surface treating agent, the diamond particles can be easily and homogenously dispersed in the polymer matrix, resulting in a thermal conductive composition having improved flowability and storage stability, and excellent thermal conductivity.
In one aspect, the present invention provides a thermal conductive composition, comprising a polymer matrix, and diamond particles having an average particle size D50 of about 20 to 150μm which are surface treated with an alkylalkoxysilane compound having about 9 to 16 carbon atoms in the alkyl group in an amount of more than 0.03 wt. %and
less than 0.7wt. %based on the weight of diamond particles.
In another aspect, the present invention provides a heat dissipating member obtained by curing the thermal conductive composition.
Hereinafter the present invention will be described in more detail. Each aspect so described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
Unless otherwise defined, all terms used in the disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of the ordinary skill in the art to which this invention belongs to.
As used herein, the singular forms “a” , “an” and “the” include both singular and plural referents unless the context clearly dictates otherwise.
The terms “comprising” and “comprises” as used herein are synonymous with “including” , “includes” or “containing” , “contains” , and are inclusive or open-ended and do not exclude additional, non-recited members, elements or process steps.
The recitation of numerical end points includes all numbers and fractions subsumed within the respective ranges, as well as the recited end points.
Thermal conductive composition:
The thermal conductive composition according to the present invention comprises a polymer matrix and surface-treated diamond particles. By comprising diamond particles which are surface treated as described below as a thermal conductive filler, the thermal conductive composition exhibits improved flowability and thermal conductivity, and at the same time exhibits excellent storage stability and thixotropy, which are desirable for dispensing process in the manufacturing of electronic assembly.
Polymer matrix:
The thermal conductive composition according to the present invention comprises a polymer matrix. The polymer matrix suitable for use in the present invention can be of any type conventionally used in a thermal conductive polymer composition material. Examples of suitable polymer matrix include, but are not limited to, resins, for example, silicone resins,
epoxy resins and polyurethane resins, and silicone oil, for example, methylphenyl silicone oil, dimethylsilicone oil, and modified silicone oil.
As the epoxy resins, mention may be made of epoxy compounds having at least one, preferably two or more epoxy groups, examples of which include bisphenol-type epoxy resin, novolac-type epoxy resin, diphenyl-type epoxy resin, and naphthalene-type epoxy resin etc.
In a preferred embodiment, as the polymer matrix, the thermal conductive composition according to the present invention comprises a silicone resin. The silicone resin may be condensation curable type silicone resin, or addition reaction-curable type silicone resin, with addition reaction-curable type silicone resin being more preferable.
The addition reaction-curable type silicone resin is known to be one comprising an unsaturated group-containing polyorganosiloxane as a base polymer, a hydrogen group-containing polyorganosiloxane as a curing agent, and a platinum compound as a curing catalyst.
The unsaturated group-containing polyorganosiloxane is preferably a polyorganosiloxane having alkenyl group, more preferably vinyl group, examples of which include vinyl-terminated polyorganosiloxane, for example, vinyl-terminated polydimethylsiloxane, vinyl-terminated polydimethylmethylvinylsiloxane, vinyl-terminated polydimethylmethylphenylsiloxane, vinyl-terminated polydimethyldiphenylsiloxane.
The hydrogen group-containing polyorganosiloxane is a polyorganosiloxane having at least one, preferably two or more, hydrogen atoms directly bonded to a silicon atom, to be served as a curing agent. Examples of the hydrogen group-containing polyorganosiloxane include, hydride-terminated polydimethylsiloxane, trimethyl-terminated polymethyhydrogensiloxane, hydride-terminated polydimethylmethylhydrogensiloxane, hydride-terminated polydimethylmethylphenylsiloxane, hydride-terminated polydimethyldiphenylsiloxane. The hydrogen group-containing polyorganosiloxane is comprised in the silicone resin in such an amount that the number of the hydrogen atom directly bonded to a silicon atom is 0.2 to 5.0, preferably 0.5 to 1.5, relative to one unsaturated group of the unsaturated group-containing polyorganosiloxane.
The platinum compound is a curing catalyst which promotes a reaction between the unsaturated group of the unsaturated group-containing polyorganosiloxane and the hydrogen group of the hydrogen group-containing polyorganosiloxane to obtain a cured product. Examples of the platinum compound include, chloroplatinic acid, dichlorobis (triphenylphosphine) platinum (II) , platinum chloride, platinum oxide, and complexes of platinum compounds, for example, a platinum olefin complex, a platinum vinylsiloxane complex, a platinum phosphorous complex, a platinum alcohol complex. The amount of the platinum compound to be used is about 0.1 to 300 ppm, preferably about
100 to 200 ppm as the platinum element, based on the total weight of the unsaturated group-containing polyorganosiloxane and the hydrogen group-containing polyorganosiloxane.
The silicone resin may be of either one-component curing type or two-component curing type. In a preferred embodiment, the silicone resin is a two-component curing type silicone resin. When a two-component curing type silicone resin is used in the thermal conductive composition, the composition can be prepared by mixing a first component comprising the unsaturated group-containing polyorganosiloxane as described above with a second component comprising the hydrogen group-containing polyorganosiloxane as described above. In this case, the diamond particles and optionally other thermal conductive fillers as described below can be added in one or both of the first component and the second component.
The thermal conductive composition may contain from 2 to 30 wt. %, preferably from 4 to 20 wt. %of the polymer matrix, based on the total weight of the composition.
Diamond particles:
The thermal conductive composition according to the present invention comprises diamond particles as described below as a thermal conductive filler.
The diamond particles to be used have an average particle size D50 of about 20 to 150μm, preferably about 25 to 130μm. If the average particle size is lower than about 20μm, generally synthetic diamond particles of below 20μm have irregular shape which will affect thermal conductivity and viscosity of the composition. If the average particle size is larger than about 150μm, the filler will affect the bondline thickness (BLT) and compression force of electronic assembly.
The diamond particles to be used in the thermal conductive composition according to the invention have been surface treated with an alkylalkoxy silane compound comprising about 9 to 16, preferably about 10 to 16, more preferably about 11 to 15 carbon atoms in the alkyl group.
The alkylalkoxy silane compound includes alkyltrialkoxysilanes and dialkyldialkoxysilanes, in which the number of carbon atoms of the alky group in the case of alkyltrialkoxysilanes or at least one alkyl group in the case of dialkyldialkoxysilanes is about 9 to 16, preferably about 10 to 16, more preferably about 11 to 15. Among these, alkyltrialkoxysilanes are preferred.
Examples of the alkylalkoxysilane compound include, but are not limited to, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tetradecyltrimethoxysilane,
tetradecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, methyl-octyldimethoxysilane, methyl-octyldiethoxysilane, methydecyldimethoxysilane, methyldodecyldimethoxysilane, methylhexadecyldimethoxysilane.
The amount of the silane compound to be used as a surface treating agent is greater than 0.03wt. %and smaller than 0.07wt. %, and preferably is about 0.04 to 0.55wt. %, relative to the weight of the diamond particles.
It has been found that shorter carbon chain of the alky group in the silane compound can’ t give enough coverage for diamond particles surface and cause weak compatibility of the diamond particles with the polymer matrix, and even higher treating amount of the silane compound cannot compensate for it, while too high amount of the silane compound will lead to higher thixotropy, lower flow rate of the composition and meanwhile deteriorate the storage stability of the composition, which is not favorable to 2K dispensing. Meanwhile, lower treating amount of the silane compound can’ t give enough coverage for diamond particles surface, even with a long carbon chain of the alky group in the silane compound.
Without wishing to be bound by theory, therefore, it is believed that by surface treating the diamond particles having a particular range of average particle size with a particular type and amount of silane compound, the obtained surface-treated diamond particles can be homogeneously dispersed in the polymer matrix, and improve the flow rate, thermal conductivity, thixotropy and storage stability of the obtained composition.
A method for surface treating the diamond particles with the silane compound is not especially limited, and as known in the art, there can be used, for example, a wet treatment method, a dry treatment method, or a combination thereof.
The wet treatment method comprises the steps of adding the diamond particles in a solution in which the silane compound is dispersed, mixing the mixture and then heat treating the mixture at a temperature of normally about 50 to 90 ℃.
The dry treatment method typically comprises the steps of mixing the diamond particles and the silane compound, and then heat treating the mixture at a temperature of normally about 50 to 90℃.
The thermal conductive composition may contain from 25 to 75 wt. %, preferably from 35 to 65 wt. %of the diamond particles, based on the total weight of the composition.
Other thermal conductive fillers:
The thermal conductive composition may further preferably comprise other thermal conductive fillers conventionally used in the art than the diamond particles. Examples of other thermal conductive fillers include, but are not limited to, alumina, magnesium oxide,
zinc oxide, boron nitride, aluminum nitride, etc. This other thermal conductive filler may be used in a single type or in combination of two or more types.
The thermal conductive fillers may have an average particle size D50 of 0.1 to 200μm.
If present, these other thermal conductive filler can be incorporated in the composition in an amount of about 30 to 60wt. %, for example about 40 to 55wt. %, for example about 50wt. %, based on the total weight of the composition.
Optional additives:
The thermal conductive composition according to the invention may further comprise other additives conventionally used for heat dissipating member, for example, reactor inhibitor, dispersant, antioxidant, thermal stabilizer, pigments, and flame retardant according to actual needs.
In a preferred embodiment, the thermal conductive composition comprises a dispersant, to facilitate dispersion of the thermal conductive fillers in the polymer matrix of the composition. By achieving more uniform dispersion of these fillers, the overall thermal conductivity of the composition can be further improved, allowing for more efficient heat dissipation. As the dispersant, silicone-based or non-silicone based dispersant can be used, for example, polydimethylsiloxane, hydroxyl-functional polydimethylsiloxane, fatty acids, polyacrylates.
The amount of the dispersant to be used in the composition may be, based on the total weight of the composition, from about 0.1 to 5wt. %, preferably about 0.5 to 2wt. %.
Preparation of the thermal conductive composition:
The thermal conductive composition according to the invention can be prepared by mixing the polymer matrix, the diamond particles, and further optionally other thermal conductive fillers, and additives as described above.
In an embodiment, a two-component curing type silicone resin is used as the polymer matrix, and in this case, as described above, the thermal conductive composition can be prepared by mixing a first component comprising the unsaturated group-containing polyorganosiloxane and a second component comprising the hydrogen group-containing polyorganosiloxane, which have been prepared separately. The diamond particles, the other thermal conductive fillers and the optional additives can be comprised in either or both of the first component and the second component. In an illustrative embodiment, the first component can be prepared by mixing the unsaturated group-containing polyorganosiloxane, the platinum compound catalyst, the diamond particles, other thermal conductive fillers, and additives comprising for example a dispersant, a reaction inhibitor
and a pigment, and the second component can be prepared by mixing the hydrogen group-containing polyorganosiloxane, the diamond particles, other thermal conductive fillers, and an additive for example a pigment.
The mixing can be done by any known mixing apparatus, which can be selected by a skilled person according to practical requirement, at a temperature of normally from about 20℃ to 140℃, preferably about 60℃ to 120℃. For example, a planetary mixer, a kneader, a static mixer, or any combination thereof can be used.
The thermal conductive composition according to the present invention exhibits an excellent property portfolio of initial flow rate, aged flow rate, thixotropy, and storage stability.
In another aspect, the present invention provides a heat dissipating member, which is obtained by curing the above thermal conductive composition. The thermal conductive composition can be cured by heating, or without being heated. For example, the composition can be cured at normal temperature, for example about 25℃ after 24 to 48 hours, or the composition can be cured by heating at about 60-80℃ for about 0.5 to 2 hours.
The obtained heat dissipating member according to the present invention has an excellent thermal conductivity of above 15.00 W/m·K.
The heat dissipating member according to the present invention is suitable for use in a wide variety of electronic devices and electronic components, for example, CPUs, chipsets, hard disk drives, power transistors, etc.
Examples:
The present invention will be described with reference to the following examples, which should not be construed as limiting the scope of the present invention in any way.
The following materials were used in the examples:
Octyltrimethoxysilane: Mw=234, Viscosity=2 mPa. s, trade name: KBM-3103C, available from Shin-Etsu;
Dodecyltriethoxysilane: Mw=333, available from Sigma Aldrich;
Hexadecyltrimethoxysilane: Mw=347, Viscosity= 7 mPa. s, trade name: Dynasylan 9116, available from Evonik;
Raw Diamond particles-A: average particle size of 115μm, specific surface area of 0.050 m2/g, available from Guangzhou Fanya Jiarong Trading Co., Ltd.;
Raw Diamond particles-B: average particle size of 45μm, specific surface area of 0.140 m2/g, available from Guangzhou Fanya Jiarong Trading Co., Ltd.;
Raw Diamond particles-C: average particle size of 25μm, specific surface area of 0.25
m2/g, available from Guangzhou Fanya Jiarong Trading Co., Ltd.;
Vinyl-terminated polysiloxane: trade name: RH-Vi321, available from Ningbo Runhe High-tech Material Co., Ltd.;
Hydride-terminated polydimethylsiloxane: trade name: XL1-7501, available from Nusil Technology LLC.;
Trimethyl-terminated polymethyhydrogenlsiloxane: trade name: RH-H33, available from Ningbo Runhe High-tech Material Co., Ltd.;
Polydimethylsiloxane: trade name: KF-96-50CS, available from Shin-Etsu;
Platinum Catalyst: Karstedt Catalyst, having a Pt content of 2%, trade name: CAT1-50, available from Nusil Technology LLC;
Inhibitor: 1, 3, 5, 7-tetramethyl-1, 3, 5, 7-tetravinyl-cyclotetrasiloxane, trade name: XL-119, available from Nusil Technology LLC;
Filler dispersant: trade name: LP-X-21879, available from BYK;
Pigment: trade name: Sunfast Blue 15: 4 &Sunfast Green 7, available from Qingdao Sun Chemical Corporation;
Aluminum Nitride-1: average particle size of 120μm, trade name: AN120, available from Suzhou Ginet New Material Technology Co., Ltd.;
Aluminum Nitride-2: average particle size of 25μm, trade name: AN30, available from Suzhou Ginet New Material Technology Co., Ltd.;
Aluminum Nitride-3: average particle size of 5μm, trade name: AN5, available from Suzhou Ginet New Material Technology Co., Ltd.;
Alumina: average particle size of 0.3μm, trade name: Y06-1, available from Suzhou Ginet New Material Technology Co., Ltd.
Surface treatment of diamond particles:
Preparation Example 1:
100 parts by weight of raw diamond particles-A were added in a planetary mixer (PDDM-2, supplied by Ross) with a dispersion disk. 0.029 parts by weight of octyltrimethoxysilane as a surface treating agent is diluted with 3 times weight of ethanol and mixed into the diamond particles. The mixture was stirred at room temperature for 30 minutes, and thereafter heated at 80℃ for another 1 hour, thereby obtaining treated diamond particles 1.
Preparation Examples 2 to 9:
The same procedure as in Preparation Example 1 was carried out, except for changing the type or amount of surface treating agent as shown in Table 1. Treated diamond particles 2 to 9 were respectively obtained.
Preparation Example 10:
100 parts by weight of raw diamond particles-B were added in a planetary mixer from Ross with a dispersion disk. 0.200 parts by weight of dodecyltriethoxysilane as a surface treating agent is diluted with 3 times weight of ethanol and mixed into the diamond particles. The mixture was stirred at room temperature for 30 minutes, and thereafter heated at 80℃ for
another 1 hour, thereby obtaining treated diamond particles 10.
Preparation Examples 11 to 12:
The same procedure as in Preparation Example 10 was carried out, except for changing the amount of the surface treating agent as shown in Table 1. Treated diamond particles 11 to 12 were respectively obtained.
Preparation Example 13:
100 parts by weight of raw diamond particles-C were added in a planetary mixer from Ross with a dispersion disk. 0.044 parts by weight of dodecyltriethoxysilane as a surface treating agent is diluted with 3 times weight of ethanol and mixed into the diamond particles. The mixture was stirred at room temperature for 30 minutes, and thereafter heated at 80℃ for another 1 hour, thereby obtaining treated diamond particles 13.
Preparation Example 14:
The same procedure as in Preparation Example 13 was carried out, except for changing the amount of the surface treating agent to be 0.400 parts by weight as shown in Table 1. Treated diamond particles 14 were obtained.
Preparation of thermal conductive compositions:
Example 1 to 7 and Comparative Examples 1 to 10:
According to the formulation as shown in Table 2, Part A (a first component) was prepared by first mixing the ingredients except for the inhibitor and platinum catalyst in a planetary mixer at a speed of 25 rpm and at normal temperature for 30 minutes, and then at a speed of 20rpm and at a temperature of 100 to 150℃ for 1 hour, and cooling to 30℃, followed by adding the inhibitor and platinum catalyst and mixing for additional 30 minutes.
Part B was prepared by mixing the respective ingredients in a planetary mixer at a speed of 25 rpm and at normal temperature for 30 minutes, and then at a speed of 20rpm and at a temperature of 100 to 150℃ for 1 hour, and cooling to 30℃.
Part A and Part B were mixed in a static mixer to obtain the thermal conductive compositions of Examples 1 to 7 and Comparative Examples 1 to 10, which were then evaluated in the tests of viscosity, thixotropy, initial flow rate and aged flow rate.
The thermal conductive compositions were then applied on the test plate of LW-9389 Thermal Tester, with test condition being 80℃ for 30 minutes and the compositions were online cured. The cured products were then subjected to a thermal conductivity test.
The results of these tests were shown in Table 3.
The following test methods were employed in the Examples:
Viscosity:
Viscosity was measured at 25℃ on a Rheometer (Discovery HR-30, manufactured by TA instruments Inc. ) using a plate-plate geometry with a 25mm in diameter plate at a 1.0mm gap and at a shear rate of 0.1s-1 and 1.0s-1.
Thixotropy:
The thixotropy was calculated by the following equation:
Thixotropy=Viscosity@0.1s-1/Viscosity@1.0s-1
Flow rate:
Flow rate was tested with Nordson EFD dispenser (UltimusTM I-II) in a 30cc plastic EFD tube, with pressure of 90psi.
After storing the composition at 60℃ for 3 days, the test of flow rate was conducted again, to obtain an aged flow rate.
Thermal conductivity:
Thermal conductivity was tested in Longwin TIM Tester (LW-9389) according to ASTM 5470.
As can be seen from the results of Comparative Examples 1 to 5 in table 3, the use of raw diamond particles filler can improve the flow rate and thermal conductivity than traditional thermal conductive filler for example AlN having the same particle size, but the thermal conductivity and flow rate reliability still cannot meet our improved criteria of thermal conductivity of greater than 15W/m·K and flow rate loss of less than 15%.
From Comparative Example 6 and Comparative Example 7, we can see that the use of the silane compound having a shorter alkyl chain of C8 or less as a surface treating agent has little effect on thermal conductivity and flow rate regardless of the amount of agent from lower to higher.
From Examples 1 to 7 according to the present invention, we can see that by using the silane compound having an alky chain of >C8 to <C17 in an amount of greater than 0.03wt%and less than 0.7wt%can significantly improve thermal conductivity, flow rate, flow rate reliability and thixotropy.
Compared to Example 7, using treated diamond particles having a greater average particle size in Example 6 further improves the combined properties of thixotropy, flow rate reliability and thermal conductivity to some extent. According to the present invention, therefore, the average particle size of the diamond particles should be controlled to be not lower than about 20 μm.
Table 2:
Table 2-continued:
Claims (11)
- A thermal conductive composition, comprising a polymer matrix, and diamond particles having an average particle size D50 of about 20 to 150μm which are surface treated with an alkylalkoxysilane compound comprising 9 to 16 carbon atoms in the alkyl group in an amount of more than 0.03 wt. %and less than 0.7 wt. %, based on the weight of the diamond particles.
- The thermal conductive composition according to claim 1, wherein the diamond particles have an average particle size D50 of about 25 to 130μm.
- The thermal conductive composition according to claim 1, wherein the alkylalkoxysilane compound comprises 10 to 16, preferably 11 to 15 carbon atoms in the alkyl group.
- The thermal conductive composition according to any one of claims 1 to 3, wherein the amount of the alkylalkoxysilane compound is from 0.04 to 0.55wt. %, based on the weight of the diamond particles.
- The thermal conductive composition according to any one of claims 1 to 3, wherein the alkylalkoxysilane compound is selected from alkyltrialkoxysilanes, dialkyldialkoxysilanes or any combination thereof, preferably alkyltrialkoxysilanes.
- The thermal conductive composition according to any one of claims 1 to 3, wherein the alkylalkoxysilane compound is selected from octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, methyloctyldimethoxysilane, methydecyldimethoxysilane, methyldodecyldimethoxysilane, methylhexadecyl dimethoxysilane, or any combination thereof.
- The thermal conductive composition according to any one of claims 1 to 3, wherein the polymer matrix is a silicone resin, preferably an addition reaction-curable type silicone resin
- The thermal conductive composition according to claim 7, wherein the silicone resin comprises an unsaturated group-containing polyorganosiloxane as a base polymer, a hydrogen group-containing polyorganosiloxane as a curing agent, and a platinum compound as a curing catalyst.
- The thermal conductive composition according to claim 7 or 8, wherein the silicone resin is a two-component curing type silicone resin.
- A heat dissipating member, comprising the thermal conductive composition according to any one of claims 1 to 9.
- The heat dissipating member according to claim 10, wherein the heat dissipating member is obtained by curing the thermal conductive composition.
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| CN113508460A (en) * | 2019-03-29 | 2021-10-15 | 陶氏东丽株式会社 | Multicomponent type curable polyorganosiloxane composition, thermally conductive member, and heat dissipation structure |
| US20210332280A1 (en) * | 2018-11-07 | 2021-10-28 | Dow Global Technologies Llc | Thermally conductive composition and methods and devices in which said composition is used |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20030234074A1 (en) * | 2002-06-25 | 2003-12-25 | Bhagwagar Dorab Edul | Thermal interface materials and methods for their preparation and use |
| US20060292840A1 (en) * | 2003-11-05 | 2006-12-28 | Dow Corning Corporation | Thermally conductive grease and methods and devices in which said grease is used |
| CN111032665A (en) * | 2017-08-10 | 2020-04-17 | 信越化学工业株式会社 | Organosilicon compound and curable thermally conductive silicone composition |
| CN112204106A (en) * | 2018-05-31 | 2021-01-08 | 积水化学工业株式会社 | Heat radiation composition, heat radiation member, and filler assembly for heat radiation member |
| US20210332280A1 (en) * | 2018-11-07 | 2021-10-28 | Dow Global Technologies Llc | Thermally conductive composition and methods and devices in which said composition is used |
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