Silicon-free heat-conducting gel as well as preparation method and application thereof
By developing a silicone-free thermal conductive gel formulation and preparation method, the problem of silicone oil precipitation in organosilicon thermal conductive gels at high temperatures has been solved, achieving stable use at high temperatures and high thermal conductivity, making it suitable for electronic devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHENZHEN DEYIMENG ELECTRONICS CO LTD
- Filing Date
- 2025-12-12
- Publication Date
- 2026-04-14
AI Technical Summary
Existing silicone thermal conductive gels release small silicone oil molecules at high temperatures, which can contaminate precision optical devices or cause short circuits, making them difficult to use stably in high-temperature environments.
The formulation employs a silicone-free thermally conductive gel, comprising a base resin, thermally conductive filler, and specific treatment agents. Inorganic thermally conductive powder is prepared through stirring and heat treatment, avoiding the formation of siloxane volatiles and enhancing high-temperature and voltage resistance.
Silicone-free thermal conductive gel remains stable at high temperatures, prevents contamination from volatile siloxanes, and possesses excellent thermal conductivity and voltage resistance, making it suitable for sensitive electronic devices.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of thermal interface materials technology, specifically to a silicon-free thermal conductive gel, its preparation method, and its application. Background Technology
[0002] Thermal interface materials refer to a class of materials applied between heat dissipation devices and heat dissipation devices to reduce contact thermal resistance. Currently, thermal grease, thermal pads, and thermal gels are commonly used thermal interface materials. Among them, thermal gels are amorphous and can fill any gaps that thermal pads cannot accommodate, achieving efficient heat conduction. In addition, thanks to their slight cross-linking properties, thermal gels are not prone to drying out or becoming brittle during use. Currently, the most commonly used thermal gels on the market are silicone thermal gels, which have excellent interfacial contact performance and are easy to apply. However, traditional silicone thermal gels will release small silicone oil molecules at high temperatures, contaminating precision optical devices (such as cameras and sensors) or causing short circuits, making them difficult to use in high-temperature environments.
[0003] Therefore, there is an urgent need to develop a thermally conductive gel that is resistant to high temperatures and has high thermal conductivity and high voltage resistance, so that it can be used normally and stably as a thermal interface material under high heat conditions. Summary of the Invention
[0004] To address the shortcomings of existing technologies, this invention proposes a silicone-free thermal conductive gel, its preparation method, and its application. The silicone-free thermal conductive gel provided by this invention has high temperature resistance and voltage resistance, as well as high thermal conductivity, which can meet the high requirements of modern electronic devices for thermal interface materials.
[0005] This invention provides a silicone-free thermally conductive gel, comprising, by weight, the following components: 20-200 parts of base resin, such as 20, 40, 60, 80, 100, 120, 140, 160, 180, or 200 parts; 850-970 parts of thermally conductive filler, such as 800, 820, 840, 860, 880, 900, 920, 940, 960, 980, or 1000 parts; wherein the base resin comprises the following components: 1-50 parts of base oil A, such as 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts; base oil B... 1-10 parts, such as 1, 2, 4, 6, 8, 10 parts; plasticizer 1-30 parts, such as 1, 5, 10, 15, 20, 25, 30 parts; anti-aging agent 0.1-2 parts, such as 0.1, 0.2, 0.4, 0.5, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2 parts; the thermally conductive filler includes the following components: treatment agent 0.1-20 parts, such as 0.1, 0.5, 1, 2, 5, 8, 10, 12, 15, 18, 20 parts; inorganic thermally conductive powder 850-950 parts, such as 850, 880, 900, 920, 950 parts; Wherein, the base oil A is at least one of pentaerythritol tetraoctanoate, neopentyl glycol dioctanoate, trimethylolpropane octanoate, and dipentaerythritol hexaester; The base oil B is at least one of alkyl naphthalene, polya-olefin synthetic oil (PAO), and polycarbonate polyol.
[0006] This invention provides a silicone-free thermal conductive gel through formulation design. Compared to silicone thermal conductive gels, this gel offers higher reliability, process compatibility, and long-term stability when applied to sensitive electronic devices, making it particularly suitable for scenarios with zero tolerance for silicone contamination. Furthermore, by using specific base oils A and B, this invention avoids a decrease in gel extrusion rate, which could affect dispensing efficiency, while ensuring the material's high-temperature resistance and voltage resistance.
[0007] Furthermore, the mass ratio of base oil A to base oil B is (5-10):1.
[0008] Furthermore, the viscosity of the base oil A is 5-200 mPa·s.
[0009] Furthermore, the viscosity of the base oil B is 5-5000 mPa·s.
[0010] Furthermore, the plasticizer is at least one of hydrogenated polybutadiene and hydrogenated polyisoprene.
[0011] Furthermore, the viscosity of the plasticizer is less than 5000 mPa·s. If the viscosity of the plasticizer is too high, it will affect the plasticizing effect and reduce the gel extrusion rate.
[0012] Further, the inorganic thermally conductive powder is at least one of zinc oxide with a particle size of 0.1-5 μm, aluminum oxide with a particle size of 1-150 μm, aluminum hydroxide with a particle size of 1-120 μm, aluminum nitride with a particle size of 10-150 μm, or boron nitride with a particle size of 10-150 μm.
[0013] Further, the treatment agent is at least one of isopropyltris(stearoyl)titanate, isopropyltris(dioctylpyrophosphoyloxy)titanate, tetraisopropyldi(dioctyl phosphite)titanate, isopropoxydistearatealuminum, isopropoxytris(vinyldioctyl)aluminate, or ethoxybis(ethyl acetoacetate)aluminum.
[0014] Further, the anti-aging agent is at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate.
[0015] The present invention also provides a method for preparing the aforementioned thermally conductive gel, comprising the following steps: Preparation of base resin: Weigh base oil A, base oil B, plasticizer and anti-aging agent according to the weight parts, stir at 30-100 r / min at 70℃-100℃ while simultaneously vacuuming for 0.5-1.5 h to obtain base resin; Preparation of thermally conductive filler: Weigh the inorganic thermally conductive powder and the treatment agent according to the weight parts, stir at 600-1000 r / min for 15-30 min at room temperature, then stir at 30-100 r / min for 0.5-1 h at 65-120℃, and at the same time heat-treat at 80-130℃ for 1.5-3 h under vacuum to obtain the pretreated thermally conductive filler; Preparation of thermally conductive gel: The base resin and thermally conductive filler are mixed and heat-treated at 90℃-120℃ while being vacuum-kneaded for 0.5-2 hours. After cooling, the silicone-free thermally conductive gel is obtained.
[0016] Furthermore, in the preparation step of the thermally conductive filler, the inorganic thermally conductive powder and the treatment agent are mixed in a solvent and then stirred. The amount of solvent used can optionally be 50-100 parts by weight.
[0017] Furthermore, the solvent can be selected from any one of nonpolar solvents such as anhydrous ethanol, toluene, xylene, or solvent gasoline.
[0018] This invention also provides the application of the thermally conductive gel in new energy electronic devices, consumer electronic devices, microelectronic devices, optical devices, and semiconductor devices. In terms of optical device protection, the silicone-free thermally conductive gel of this invention can completely eliminate the phenomenon of siloxane volatiles forming oil films on the surface of camera lenses and laser sensors, thus avoiding image blurring. At the same time, in terms of semiconductor safety protection, the silicone-free thermally conductive gel can prevent silicon migration that leads to IC solder joint corrosion failure.
[0019] In summary, compared with the prior art, the present invention achieves the following technical effects: (1) The silicone-free thermal conductive gel provided by the present invention has excellent high temperature resistance and can be used stably at high temperature for a long time. (2) The silicone-free thermal conductive gel provided by the present invention also has high thermal conductivity and does not harden or powder after long-term high-temperature use, and still maintains the gel state. (3) The silicone-free thermal conductive gel provided by the present invention also has excellent voltage resistance. (4) The silicone-free thermal conductive gel provided by the present invention also has a good gap-filling function, and the gap thickness can be as low as 0.2 mm. (5) The silicone-free thermal conductive gel provided by the present invention has a high extrusion rate, a simple preparation process, and can be mass-produced. Detailed Implementation
[0020] To enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0021] Example The present invention will be further illustrated below with reference to specific embodiments and comparative embodiments. The following specific embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the following embodiments, and are not in particular limited to the types of raw materials used in the following specific embodiments.
[0022] I. The sources of raw materials for the examples and comparative examples are as follows: Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this invention are all commercially available. The quantities used in the examples and comparative examples are in parts by weight. The inorganic thermally conductive powder used is as follows: Table 1. Inorganic thermally conductive powder formulation
[0023] II. Performance Testing Methods (1) Thermal conductivity and thermal resistance test: The thermal conductivity of the thermally conductive gel was measured according to the standard test method of ASTM D5470-2017 for thermally conductive and electrically insulating materials. (2) Breakdown voltage test: Refer to standard ASTM D149-20 Standard test method for dielectric breakdown voltage and dielectric strength of solid electrical insulating materials at commercial power frequency.
[0024] Example 1 Preparation of basic resin: 30 parts of pentaerythritol tetraoctyl ester with a viscosity of 30 mPa·s, 5 parts of polyalphaolefin synthetic oil with a viscosity of 500 mPa·s, 3 parts of hydrogenated polybutadiene with a viscosity of 1000 mPa·s, and 1.5 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were stirred at 50 r / min at 80℃ while being vacuumed for 0.5 hours, and then cooled to room temperature to obtain the basic resin; Preparation of thermally conductive materials: 10 parts of isopropyl tris(stearoyl) titanate, 78 parts of anhydrous ethanol and 912 parts of inorganic thermally conductive powder #1 were stirred at 800 r / min for 20 min at room temperature, then stirred at 50 r / min for 30 min at 75℃, and then stirred at 80 r / min at 90℃ while being vacuum heat-treated for 2 hours to obtain the pretreated thermally conductive filler. Preparation of thermally conductive gel: 40 parts of base resin and 960 parts of thermally conductive filler were heat-treated at 100°C while being vacuum-kneaded for 1 hour. After cooling, a silicone-free thermally conductive gel was obtained.
[0025] Example 2 Preparation of base resin: 32 parts of neopentyl glycol dioctyl ester with a viscosity of 20 mPa·s, 4 parts of polycarbonate polyol with a viscosity of 2000 mPa·s, 3 parts of hydrogenated polybutadiene with a viscosity of 1500 mPa·s, and 1 part of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate were stirred at 80 r / min at 90℃ while being vacuumed for 0.8 hours, and then cooled to room temperature to obtain the base resin; Preparation of thermally conductive fillers: 15 parts of tetraisopropyl di(dioctyl phosphite) titanate, 80 parts of toluene, and 905 parts of inorganic thermally conductive powder #2 were stirred at 900 r / min for 25 min at room temperature, then stirred at 60 r / min for 40 min at 80℃, and then stirred at 70 r / min at 90℃ while being vacuum heat-treated for 2 hours to obtain pretreated thermally conductive powder. Preparation of thermally conductive gel: 55 parts of base resin and 945 parts of thermally conductive filler were heat-treated at 110°C while being vacuum-kneaded for 1 hour. After cooling, a silicone-free thermally conductive gel was obtained.
[0026] Example 3 Preparation of basic resin: 28 parts of new dipentaerythritol hexaester with a viscosity of 100 mPa·s, 8 parts of alkyl naphthalene with a viscosity of 20 mPa·s, 2 parts of hydrogenated polyisoprene with a viscosity of 3000 mPa·s, and 2 parts of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate were stirred at 70 r / min at 75°C and vacuumed for 1 hour, and then cooled to room temperature to obtain the basic resin. Preparation of thermally conductive fillers: Nine parts of isopropoxydistearatealuminum, 90 parts of xylene, and 901 parts of inorganic thermally conductive powder #3 were stirred at 1000 r / min for 15 min at room temperature, then stirred at 100 r / min for 30 min at 85℃, and then stirred at 60 r / min at 100℃ while being vacuum heat-treated for 1.5 hours to obtain pretreated thermally conductive powder. Preparation of thermally conductive gel: 45 parts of base resin and 955 parts of thermally conductive filler were heat-treated at 100°C while being vacuum-kneaded for 1 hour. After cooling, a silicone-free thermally conductive gel was obtained.
[0027] Example 4 Preparation of base resin: 30 parts of trimethylolpropane octyl decanoate with a viscosity of 20 mPa·s, 6 parts of polyalphaolefin synthetic oil with a viscosity of 1000 mPa·s, 2.5 parts of hydrogenated polybutadiene with a viscosity of 3000 mPa·s, and 1.5 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] were stirred at 80 r / min at 80 °C while being vacuumed for 0.5 hours, and then cooled to room temperature to obtain the base resin; Preparation of thermally conductive fillers: 16 parts of isopropyl tris(stearoyl) titanate, 84 parts of anhydrous ethanol and 900 parts of inorganic thermally conductive powder #4 were stirred at 850 r / min for 15 min at room temperature, then stirred at 80 r / min for 45 min at 80℃, and then stirred at 70 r / min at 95℃ while being vacuum heat-treated for 1.5 hours to obtain pretreated thermally conductive powder. Preparation of thermally conductive gel: 35 parts of base resin and 965 parts of thermally conductive filler were heat-treated at 95°C while being vacuum-kneaded for 1.5 hours. After cooling, a silicone-free thermally conductive gel was obtained.
[0028] Example 5 The difference between Example 5 and Example 1 is that the mass ratio of base oil A (pentaerythritol tetraoctanoate) to base oil B (polyalphaolefin synthetic oil) is 2:1.
[0029] Example 6 The difference between Example 6 and Example 1 is that the mass ratio of base oil A (pentaerythritol tetraoctanoate) to base oil B (polyalphaolefin synthetic oil) is 15:1.
[0030] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the base resin was not prepared in advance. Instead, polyalphaolefin synthetic oil, pentaerythritol tetraoctanoate, hydrogenated polybutadiene, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], isopropyltris(stearoyl) titanate, anhydrous ethanol, and inorganic thermally conductive powder #1 were directly added during the preparation of the thermally conductive gel.
[0031] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that base oil A pentaerythritol tetraoctanoate was not added to the base resin, and the weight of base oil B polyalphaolefin synthetic oil was 35 parts.
[0032] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that base oil B (polyalphaolefin synthetic oil) was not added to the base resin, and the weight of base oil A (pentaerythritol tetraoctanoate) was 35 parts.
[0033] Table 2 Performance test results of the examples and comparative examples
[0034] Examples 1-6 all utilize the specific base resin and thermally conductive filler of this invention to prepare thermally conductive gels. Through special formulation design, the resulting silicone-free thermally conductive gels not only meet the thermal conductivity requirements but also exhibit excellent high-temperature resistance and voltage resistance. Specifically, the thermal conductivity reaches over 10 W / (m·K), and the thermal resistance is less than 0.28 cm⁻¹. 2 With a temperature of ℃ / W and a breakdown voltage of over 6.8kV / mm, it does not harden or powder after long-term temperature resistance of 150℃*1000h, and still maintains a gel state. Furthermore, its thermal conductivity and voltage breakdown resistance are basically balanced, enabling long-term stable use.
[0035] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A silicone-free thermally conductive gel, characterized in that, By weight, it includes the following components: 20-200 parts of base resin 850-970 parts of thermally conductive filler; The base resin comprises the following components: Base oil A1-50 parts Base oil B 1-10 parts Plasticizer 1-30 parts Anti-aging agent 0.1-2 parts; The thermally conductive filler comprises the following components: Treatment agent 0.1-20 parts 850-950 parts of inorganic thermally conductive powder; Wherein, the base oil A is at least one of pentaerythritol tetraoctanoate, neopentyl glycol dioctanoate, trimethylolpropane octanoate, and dipentaerythritol hexaester; The base oil B is at least one of alkyl naphthalene, polya-olefin synthetic oil, and polycarbonate polyol.
2. The thermally conductive gel according to claim 1, characterized in that, The mass ratio of base oil A to base oil B is (5-10):
1.
3. The thermally conductive gel according to claim 1, characterized in that, The viscosity of the base oil A is 5-200 mPa·s.
4. The thermally conductive gel according to claim 1, characterized in that, The viscosity of the base oil B is 5-5000 mPa·s.
5. The thermally conductive gel according to claim 1, characterized in that, The plasticizer is at least one of hydrogenated polybutadiene, hydrogenated polyisoprene, tributyl acetylacetate, dioctyl adipate, and diisononyl adipate.
6. The thermally conductive gel according to claim 5, characterized in that, The viscosity of the plasticizer is less than 5000 mPa·s.
7. The thermally conductive gel according to claim 1, characterized in that, The inorganic thermally conductive powder is at least one of zinc oxide with a particle size of 0.1-5 μm, aluminum oxide with a particle size of 1-150 μm, aluminum hydroxide with a particle size of 1-120 μm, aluminum nitride with a particle size of 10-150 μm, or boron nitride with a particle size of 10-150 μm.
8. The thermally conductive gel according to claim 1, characterized in that, The treatment agent is at least one of isopropyltris(stearoyl)titanate, isopropyltris(dioctylpyrophosphoyloxy)titanate, tetraisopropyldi(dioctyl phosphite)titanate, isopropoxydistearatealuminum, isopropoxytris(vinyldioctyl)aluminate, or ethoxybis(ethyl acetoacetate)aluminum.
9. A method for preparing the thermally conductive gel according to any one of claims 1-8, characterized in that, Includes the following steps: Preparation of base resin: Weigh base oil A, base oil B, plasticizer and anti-aging agent according to the weight parts, stir at 30-100 r / min at 70℃-100℃ while vacuuming for 0.5-1.5 h to obtain base resin; Preparation of thermally conductive filler: Weigh the inorganic thermally conductive powder and the treatment agent according to the weight parts, stir at 600-1000 r / min for 15-30 min at room temperature, then stir at 30-100 r / min for 0.5-1 h at 65-120℃, and at the same time heat-treat at 80-130℃ for 1.5-3 h under vacuum to obtain the pretreated thermally conductive filler; Preparation of thermally conductive gel: The base resin and thermally conductive filler are mixed and heat-treated at 90℃-120℃ while being vacuum-kneaded for 0.5-2 hours. After cooling, the silicone-free thermally conductive gel is obtained.
10. The application of the thermally conductive gel according to any one of claims 1-8 in new energy electronic devices, consumer electronic devices, microelectronic devices, optical devices and semiconductor devices.