CN113956669A - Anti-fatigue thermal interface material and preparation method thereof - Google Patents
Anti-fatigue thermal interface material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention discloses an anti-fatigue thermal interface material and a preparation method thereof. The anti-fatigue thermal interface material comprises (A) 1-30 parts by mass of double-end vinyl silicone oil; (B) 1-10 parts by mass of hydrogen-containing silicone oil at the double ends; (C) 0.5-3 parts by mass of hydrogen-containing MQ resin; (D) 0.001-0.1 parts by mass of a catalyst; (E) 0.001-0.03 parts by mass of inhibitor; (F) 0.1-1.0 parts by mass of a silane coupling agent; (G) 60-95 parts by mass of heat-conducting filler. The thermal interface material provided by the invention takes hydrogen-containing MQ resin as a cross-linking agent, generates multifunctional cross-linking points in a cross-linking network, improves the inherent fracture energy of the organic silicon, and thus does not damage the thermal conductivity of the thermal interface materialThe anti-fatigue property of the material is improved, the heat conductivity coefficient of the prepared thermal interface material can reach 10W/mK at most, and the anti-fatigue fracture energy is more than or equal to 50J/m2。
Description
Technical Field
The invention relates to the technical field of thermal interface materials, in particular to an anti-fatigue thermal interface material and a preparation method thereof.
Background
Thermal management of semiconductor devices has long been an important research topic in the research, development and design of electronic applications. Both circuit design variations and advances in processing technology can affect the amount of heat dissipated during operation. Thermal interface materials are primarily used as a critical path for heat transfer from a heat-generating device to a heat-dissipating structure (e.g., a heat sink, heat spreader, or vapor chamber). Thermal interface materials can effectively reduce package thermal resistance and help maintain proper operating temperatures to ensure device performance and reliability [1 ]. Various types of thermal interface materials have been widely used in electronic packaging and thermal management. Polymeric thermal interface materials have high flexibility and are commonly used in wearable electronics, which are mainly composed of polymers (silicone, epoxy, polyurethane, etc.) and thermally conductive fillers (alumina, aluminum, zinc oxide, aluminum nitride, boron nitride, etc.).
Emerging technologies such as fifth generation mobile communications (5G), internet of things (IoT), Machine Learning (ML), and Artificial Intelligence (AI) require large and fast data communications and data storage. These technological trends have prompted semiconductor engineers to develop electronic devices with higher integration and power density. This makes the warpage of the heat spreader and the chip directly due to the mismatch of thermal expansion coefficients more obvious, so the interface material not only needs to have a higher thermal conductivity coefficient, but also puts new demands on its fatigue resistance to prevent the thermal interface material from being damaged by multiple cycles of cooling and heating [2 ].
However, most of the thermal interface materials concerned at present are heat-conducting property, stability [3], reworkability [4], flexibility [5, 6] and the like, and are rarely related to fatigue resistance. This is because the thermal conductivity and fatigue resistance of the thermal interface material are a pair of spears. The addition of high levels of thermally conductive fillers can increase the thermal conductivity, but at the same time results in a decrease in the polymer matrix content, which means a decrease in the fatigue resistance of the thermal interface material.
Reference documents:
[1]Prasher R.Thermal Interface Materials:Historical Perspective,Status,and Future Directions.Proceedings of the IEEE.2006；94(8):1571-86。
[2]S.Li,T.Sinha,T.J.Davis,K.Sikka and P.Bodenweber,"Modeling and experimental study of thin bond line thermal interface material failure,"2013 IEEE 63rd Electronic Components and Technology Conference,2013,803-806,
[3] king red jade; a very bright; chentianan, a stable low oil permeability two-component heat conducting gel and a preparation method thereof, Chinese invention patent, patent application number: CN 202011594488.7.
[4] A very bright; guo presents and resolute; chentianan, a heat-conducting gel with good reworkability and a preparation method thereof, Chinese invention patent, patent application number: CN 202010070850.4.
[5] Queen; a very bright; chentian An; guo presents and resolute; royal ruby, a low viscosity, low modulus, high thermal conductivity, single-component gel and a preparation method thereof, Chinese invention patents, patent application numbers: CN 202011277212.6.
[6] Zhao Xiuying; the firewood is beautiful; luyin coming; wu-si bamboo; li Jing Chao; the Fubo, a high-softness low-seepage heat-conducting silica gel and a preparation method thereof, Chinese invention patent, patent application number: CN 201811490759.7.
Disclosure of Invention
In view of the above technical problems, the present invention provides an anti-fatigue thermal interface material and a method for preparing the same. By converting monofunctional crosslinking points of a polymer main chain in the traditional thermal interface material into multifunctional crosslinking points, the inherent fracture energy of the organic silicon is improved, so that the thermal interface material with high heat conductivity and fatigue resistance is prepared.
In order to achieve the purpose, the invention adopts the technical scheme that:
in a first aspect, the present invention provides an anti-fatigue thermal interface material, which is a thermally conductive gel made from the following components:
(A) 1-30 parts of double-end vinyl silicone oil;
(B) 1-10 parts by mass of hydrogen-containing silicone oil at the double ends;
(C) 0.5-3 parts by mass of hydrogen-containing MQ resin;
(D) 0.001-0.1 parts by mass of a catalyst;
(E) 0.001-0.03 parts by mass of inhibitor;
(F) 0.1-1.0 parts by mass of a silane coupling agent;
(G) 60-95 parts by mass of heat-conducting filler.
In certain specific embodiments, the mass part of (a) the double-ended vinyl silicone oil is 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, or any mass part therebetween.
In some specific embodiments, the mass part of the (B) hydrogen-containing silicone oil at both ends is 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts or any mass part therebetween.
In certain specific embodiments, the mass parts of the (C) hydrogen-containing MQ resin are 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 2 parts, 3 parts, or any mass parts therebetween.
In certain specific embodiments, the mass part of the (D) catalyst is 0.001 parts, 0.002 parts, 0.003 parts, 0.004 parts, 0.005 parts, 0.006 parts, 0.007 parts, 0.008 parts, 0.009 parts, 0.01 parts, 0.05 parts, 0.1 parts, or any mass part therebetween.
In certain specific embodiments, the mass parts of the (E) inhibitor are 0.001 parts, 0.002 parts, 0.003 parts, 0.004 parts, 0.005 parts, 0.006 parts, 0.007 parts, 0.008 parts, 0.009 parts, 0.01 parts, 0.015 parts, 0.02 parts, 0.025 parts, 0.03 parts, or any mass parts therebetween.
In certain specific embodiments, the mass part of the (F) silane coupling agent is 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, or any mass part therebetween.
In certain specific embodiments, the mass part of the (G) thermally conductive filler is 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, or any mass part therebetween.
In a preferred embodiment, the viscosity of the vinyl-terminated silicone oil (A) is 50 to 500mm2(S), the content of vinyl is 0.1-3.0%.
In a preferred embodiment, the viscosity of the hydrogen-containing silicone oil at both ends of (B) is 8 to 1000mm2(ii)/S, hydrogen content is 0.009-0.2%.
As a preferred embodiment, the hydrogen content of the (C) hydrogen-containing MQ resin is 0.1% to 2.0%.
As a preferred embodiment, the (D) catalyst is at least one selected from the group consisting of chloroplatinic acid, a chloroplatinic acid-isopropyl alcohol complex, and a chloroplatinic acid-divinyltetramethyldisiloxane complex.
As a preferred embodiment, the (E) inhibitor is selected from at least one of ethynylcyclohexanol, 2-phenyl-3-butyn-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-ethynyl-3-ol, 3, 5-dimethyl-1-ethynyl-3-ol, and 3-methyl-1-dodecyn-3-ol.
As a preferred embodiment, the (F) silane coupling agent is at least one selected from the group consisting of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane and hexadecyltrimethoxysilane.
As a preferred embodiment, the (G) thermally conductive filler is selected from at least one of aluminum oxide, aluminum, zinc oxide, aluminum hydroxide, magnesium hydroxide.
Preferably, the particle size of the heat conductive filler is 0.3 to 100 μm.
In the technical scheme of the invention, the thermal conductivity coefficient of the anti-fatigue thermal interface material is 1.0-10.0W/mK, and the anti-fatigue fracture energy is more than or equal to 50J/m2。
In certain specific embodiments, the fatigue-resistant thermal interface material has a thermal conductivity of 1.0W/mK, 2.0W/mK, 3.0W/mK, 4.0W/mK, 5.0W/mK, 6.0W/mK, 7.0W/mK, 8.0W/mK, 9.0W/mK, 10.0W/mK, or any thermal conductivity therebetween.
The invention provides a preparation method of the anti-fatigue thermal interface material, which comprises the following steps:
stirring the double-end vinyl silicone oil, the double-end hydrogen-containing silicone oil, the hydrogen-containing MQ resin, the inhibitor, the silane coupling agent and the heat-conducting filler for the first time, adding the catalyst, and stirring for the second time;
preferably, the stirring temperature of the primary stirring is 60-150 ℃, the stirring speed is 500-1000 r/min, and the stirring time is 0.5-2.0 h;
preferably, the stirring temperature of the secondary stirring is 20-40 ℃, the stirring speed is 100-500 rpm, and the stirring time is 0.5-2.0 h.
Preferably, the primary stirring and the secondary stirring are vacuum stirring, and the vacuum degree of the vacuum is less than or equal to-90.0 kPa.
The technical scheme has the following advantages or beneficial effects:
according to Lake-Thomas theory, the fatigue resistance of a material is mainly determined by the inherent fracture energy (Γ) of the material0) Determining, the expression of which is: gamma-shaped0＝UfX m; wherein U isfThe energy required for the destruction of a single polymer chain, and m is the number of polymer chains per unit area of crack propagation. From the above expression, it can be seen that the inherent cleavage energy is mainly determined by m, i.e., the number of polymer chains per unit area of crack propagation, in the case where the number of molecular chains is constant.
Therefore, the invention takes addition type thermosetting organic silicon as base resin, and improves the number of macromolecular chains on the unit area of crack propagation, namely the m value, by changing the traditional silicon hydrogen crosslinking agent into a crosslinking agent containing hydrogen MQ resin with multiple functionality, thereby improving the inherent breaking energy of the material. In a cross-linking network generated by a silicon-hydrogen cross-linking agent used in the traditional thermal interface material, cross-linking points are monofunctional cross-linking points, and after the hydrogen-containing MQ resin is adopted, multifunctional cross-linking points can be formed in the thermal interface material, so that the number of macromolecular chains on the unit area of crack propagation is increased, the inherent breaking energy of the macromolecular chains is improved, and the anti-fatigue property is enhanced.
According to the invention, the monofunctional crosslinking point of the traditional polymer main chain is changed into the multifunctional crosslinking point, so that the inherent fracture energy of the organic silicon is improved, high heat conductivity is realized without depending on high-filling-amount heat-conducting filler, the fatigue resistance of the thermal interface material is improved while the heat conductivity of the thermal interface material is not damaged, the prepared thermal interface material has the highest heat conductivity coefficient of 10W/mK, and the fatigue fracture resistance is more than or equal to 50J/m2。
Drawings
Fig. 1 is a schematic structural diagram of a thermal interface material in the prior art and a thermal interface material provided by the present invention.
FIG. 2 is a schematic diagram of the fatigue resistance test of the thermal interface materials of examples 1-5 and comparative example 1.
Detailed Description
The following examples are only a part of the present invention, and not all of them. Thus, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without making creative efforts, belong to the protection scope of the invention.
In the present invention, all the equipment, materials and the like are commercially available or commonly used in the industry, if not specified. The methods in the following examples are conventional in the art unless otherwise specified.
In the invention, the structure of the double-end vinyl silicone oil is shown as the formula (I):
in the formula (I), m is 1-100, and n is 1-50.
In the invention, the structure of the hydrogen-containing silicone oil at the double ends is shown as the formula (II):
in the formula (I), m is 1-100, and n is 1-50.
In the invention, the structure of the hydrogen-containing MQ resin is shown as the formula (III):
wherein, the hydrogen content of the hydrogen-containing MQ resin is defined as: the mass fraction of H contained in each 1g of hydrogen-containing MQ resin.
In the following examples and comparative examples:
the double-end vinyl silicone oil is purchased from New chemical material Co., Ltd, Zhejiang Runshe, and has the trade names of RH-Vi395 (example 1), RH-Vi1311 (examples 2, 4 and 5) and RH-Vi1325 (example 3).
The double-end hydrogen-containing silicone oil is purchased from Zhejiang Runzhe chemical new materials Co., Ltd, and has the trade names of RH-H518 (example 1), RH-DH01 (example 2), RH-DH07 (example 3), RH-H6 (examples 4 and 5) and RH-H45 (comparative example 1).
The hydrogen-containing MQ resin is purchased from Shandong Dayiyi chemical Co., Ltd and is marked by DY-HMQ 103.
Example 1:
the viscosity is 50mm2(S) 2.5 parts by mass of a vinyl-terminated silicone oil having a vinyl content of 1.70% and a viscosity of 8mm2S, 1.3 parts by mass of hydrogen-containing silicone oil at both ends having a hydrogen content of 0.18%, 0.519 parts by mass of hydrogen-containing MQ resin having a hydrogen content of 0.1% (MQ ratio: 0.6), 0.45 parts by mass of alumina having a particle diameter of 100 μm, 45 parts by mass of aluminum having a particle diameter of 50 μm, 5 parts by mass of zinc oxide having a particle diameter of 0.3 μm, 0.001 parts by mass of ethynylcyclohexanol and 0.6 parts by mass of decyltrimethoxysilane were added to a 2.0-liter double planetary mixer. Heating to 150 deg.CThe mixture was stirred at a speed of 50rpm for 2.0 hours under a vacuum of-90.0 kPa.
The above mixture was cooled to room temperature, and then 0.08 parts by mass of chloroplatinic acid-divinyltetramethyldisiloxane complex was added. Stirring was continued at 100rpm for 2.0h at 20 ℃ vacuum-90.0 kPa.
The mixture was poured into a 50mL rubber tube using a 2.0L planetary self-contained filling machine to give an antifatigue thermal interface material, which was stored at-35 ℃.
Example 2
The viscosity is 500mm2(15.5 parts by mass) of a vinyl-terminated silicone oil having a vinyl content of 0.43% and a viscosity of 1000mm2S, double-ended hydrogen-containing silicone oil (7 parts by mass) having a hydrogen content of 0.009%, hydrogen-containing MQ resin (MQ ratio of 0.7) (2 parts by mass) having a hydrogen content of 2.0%, aluminum (40 parts by mass) having a particle size of 100 μm, aluminum (30 parts by mass) having a particle size of 50 μm, zinc oxide (5 parts by mass) having a particle size of 0.3 μm, 2-phenyl-3-butyn-2-ol (0.02 parts by mass), and hexadecyltrimethoxysilane (0.479 parts by mass) were added to a 2.0-L double planetary mixer. The temperature was raised to 90 ℃ and the mixture was stirred at 50rpm for 0.5 hour under a vacuum of-90.0 kPa.
The above mixture was cooled to room temperature, and then 0.001 part by mass of chloroplatinic acid-isopropyl alcohol complex was added. Stirring was continued at 100rpm for 1.0h at 40 ℃ vacuum-90.0 kPa.
The mixture was poured into a 50mL rubber tube using a 2.0L planetary self-contained filling machine to give an antifatigue thermal interface material, which was stored at-35 ℃.
Example 3
The viscosity is 250mm2(30 parts by mass) of a vinyl-terminated silicone oil having a vinyl content of 0.63%/S, and a viscosity of 40mm2S, double-ended hydrogen-containing silicone oil (8.7 parts by mass) having a hydrogen content of 0.07%, hydrogen-containing MQ resin (MQ ratio of 0.75) (1 part by mass) having a hydrogen content of 1.0%, alumina (30 parts by mass) having a particle size of 50 μm, alumina (20 parts by mass) having a particle size of 20 μm, alumina (10 parts by mass) having a particle size of 5.0 μm, 2-methyl-3-butynyl-2-ol (0.03 part by mass), and hexadecyltrimethoxysilane (0.269 part by mass) were added to a 2.0-liter double planetary mixer. The temperature is increased to 60 ℃,the mixture was stirred at 100rpm for 1.0 hour under a vacuum of-90.0 kPa.
The above mixture was cooled to room temperature, and then 0.001 part by mass of chloroplatinic acid-isopropyl alcohol complex was added.
Stirring was continued at 100rpm for 1.0h at 40 ℃ vacuum-90.0 kPa.
The mixture was poured into a 50mL rubber tube using a 2.0L planetary self-contained filling machine to give an antifatigue thermal interface material, which was stored at-35 ℃.
Example 4
Essentially identical to the formulation of example 2, except that the hydrogen-containing silicone oil at both ends is: viscosity 20mm2S, 8 parts by mass of hydrogen-containing silicone oil at both ends with a hydrogen content of 0.11%, and 1 part by mass of hydrogen-containing MQ resin with a hydrogen content of 2.0% (MQ ratio of 0.7).
Example 5
Essentially identical to the formulation of example 2, except that the hydrogen-containing silicone oil at both ends is: viscosity 20mm2(S), 6 parts by mass of hydrogen-containing silicone oil at both ends, the hydrogen content of which is 0.11%, and 3 parts by mass of hydrogen-containing MQ resin, the hydrogen content of which is 2.0% (MQ ratio is 0.7).
Comparative example 1
The same formulation as in example 2, except that no hydrogen-containing MQ resin was used, and 2 parts by mass of a viscosity of 17mm was used2and/S, double-end hydrogen-containing silicone oil with 0.12 percent of hydrogen content is substituted.
Effect testing
(1) And (3) testing the heat conductivity coefficient:
the invention adopts a steady state method to measure the heat conductivity coefficient in the vertical direction: the testing instrument is an LW-9389TIM resistance and conductivity measuring instrument, and comprises the following specific steps: placing the thermal interface composite material between the instrument bars, and establishing stable heat flow through the assembly; then monitoring the temperature in the strip at two or more points along its length; the temperature difference across the interface is calculated from the temperature readings obtained and used to determine the thermal conductivity of the interface.
(2) Anti-fatigue property:
the thermal interface materials of the above examples and comparative examples were tested for fatigue resistance at room temperature using a universal stretcher (Shimadzu, Japan, model AG-X plus 10N-10 kN).
As shown in FIG. 2, the length 2H of the sample of thermal interface material tested0Is 20mm, and has a width L02.0cm and 0.2mm thick. During testing, the initial clamping distance between the upper and lower chucks was fixed at 20mm, and the stretching rate was set at 10 mm/min. To obtain more accurate fatigue resistance, pure shear mode measurements were used. Firstly, measuring a stress-strain curve of a sample without a notch to obtain the strain energy density of the sample, then measuring the stress-strain curve of the sample with the notch to obtain the strain energy density of the sample with the notch, wherein the direction of the notch is vertical to the stretching direction, the length c is 2mm, and finally, calculating the fracture energy by adopting a single-edge fracture energy mode fracture energy calculation formula. And then, performing multiple cycle stretching below the fracture energy, drawing a relation curve of the crack propagation rate and the fracture energy, and obtaining a fracture energy threshold, namely the fatigue resistance. The formula for calculating the fatigue resistance is shown as the formula (I):
in the formula (I), the compound is shown in the specification,
the sample is unnotched at a uniaxial stretch ratio of lambdabStrain energy density of time, L0Is the width of the sample and is,2H0is the length of the sample, and L0Much less than 2H0λ is the elongation at break of the notched sample, and c is the notch length.
The thermal conductivity and fatigue resistance of the thermal interface materials of examples 1 to 5 and comparative example 1 were measured according to the above methods, and the results are shown in table 1:
TABLE 1
| Coefficient of thermal conductivity (W/m. K) | Anti-fatigue (J/m)2) | |
| Example 1 | 10.0 | 56 |
| Example 2 | 6.52 | 87 |
| Example 3 | 3.90 | 124 |
| Example 4 | 6.47 | 135 |
| Example 5 | 6.35 | 75 |
| Comparative example 1 | 6.40 | 24 |
As can be seen from table 1, the thermal interface materials provided in examples 1 to 5 have not only higher thermal conductivity, maintaining excellent thermal conductivity, but also higher fatigue resistance, compared to comparative example 1.
Through the embodiment and the proportion, the thermal interface material provided by the invention changes the common silicon-hydrogen cross-linking agent into the hydrogen-containing MQ resin, so that the number of macromolecular chains in the unit area of crack propagation is increased, and the fatigue resistance of the thermal interface material is improved. As shown in fig. 1: in the cross-linking network of the existing thermal interface material, the cross-linking points are monofunctional cross-linking points, and after the hydrogen-containing MQ resin is adopted, a plurality of hydrosilation groups are contained in the hydrogen-containing MQ resin and can generate hydrosilylation reaction with the vinyl silicone oil, so that the vinyl silicone oil is grafted on the hydrogen-containing MQ resin, multifunctional cross-linking can be realized, multifunctional cross-linking points are formed, the number of macromolecular chains on the unit area of crack propagation is increased, the inherent breaking energy is increased, and finally the fatigue resistance of the thermal interface material is improved.
The applicant states that the present invention provides a fatigue-resistant thermal interface material and a method for preparing the same through the above-mentioned examples, but the present invention is not limited to the above-mentioned process steps, i.e. it does not mean that the present invention must rely on the above-mentioned process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the contents of the present specification and the drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. An anti-fatigue thermal interface material, wherein the anti-fatigue thermal interface material is a thermally conductive gel made from the following components:
(A) 1-30 parts of double-end vinyl silicone oil;
(B) 1-10 parts by mass of hydrogen-containing silicone oil at the double ends;
(C) 0.5-3 parts by mass of hydrogen-containing MQ resin;
(D) 0.001-0.1 parts by mass of a catalyst;
(E) 0.001-0.03 parts by mass of inhibitor;
(F) 0.1-1.0 parts by mass of a silane coupling agent;
(G) 60-95 parts by mass of heat-conducting filler.
2. The fatigue-resistant thermal interface material according to claim 1, wherein the viscosity of the (A) double-terminal vinyl silicone oil is 50 to 500mm2(S), the content of vinyl is 0.1-3.0%.
3. The fatigue-resistant thermal interface material according to claim 1, wherein the viscosity of the hydrogen-containing silicone oil at both ends of (B) is 8 to 1000mm2(ii)/S, hydrogen content is 0.009-0.2%.
4. The fatigue-resistant thermal interface material as claimed in claim 1, wherein the hydrogen content of the (C) hydrogen-containing MQ resin is 0.1% to 2.0%.
5. The fatigue-resistant thermal interface material according to claim 1, wherein the (D) catalyst is at least one selected from the group consisting of chloroplatinic acid, a chloroplatinic acid-isopropyl alcohol complex, and a chloroplatinic acid-divinyltetramethyldisiloxane complex.
6. The fatigue-resistant thermal interface material of claim 1, wherein the (E) inhibitor is selected from at least one of ethynylcyclohexanol, 2-phenyl-3-butyn-2-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-ethynyl-3-ol, 3, 5-dimethyl-1-ethynyl-3-ol, and 3-methyl-1-dodecyn-3-ol.
7. The fatigue-resistant thermal interface material of claim 1, wherein the (F) silane coupling agent is at least one selected from the group consisting of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, and hexadecyltrimethoxysilane.
8. The fatigue-resistant thermal interface material of claim 1, wherein the (G) thermally conductive filler is selected from at least one of aluminum oxide, aluminum, zinc oxide, aluminum hydroxide, magnesium hydroxide;
preferably, the particle size of the heat-conducting filler is 0.3-100 μm.
9. The fatigue-resistant thermal interface material of any one of claims 1-8, wherein the thermal conductivity of the fatigue-resistant thermal interface material is 1.0-10.0W/mK, and the fatigue fracture resistance is not less than 50J/m2。
10. A method of making a fatigue-resistant thermal interface material as in any one of claims 1-8, comprising the steps of:
stirring the double-end vinyl silicone oil, the double-end hydrogen-containing silicone oil, the hydrogen-containing MQ resin, the inhibitor, the silane coupling agent and the heat-conducting filler for the first time, adding the catalyst, and stirring for the second time;
preferably, the stirring temperature of the primary stirring is 60-150 ℃, the stirring speed is 500-1000 r/min, and the stirring time is 0.5-2.0 h;
preferably, the stirring temperature of the secondary stirring is 20-40 ℃, the stirring speed is 100-500 rpm, and the stirring time is 0.5-2.0 h;
preferably, the primary stirring and the secondary stirring are vacuum stirring, and the vacuum degree of the vacuum is less than or equal to-90.0 kPa.
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| CN115627074A (en) * | 2022-09-22 | 2023-01-20 | 深圳先进电子材料国际创新研究院 | Anti-fatigue heat-conducting gel and preparation method thereof |
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