CN117511222A - Heat conduction gasket and preparation method thereof - Google Patents
Heat conduction gasket and preparation method thereof Download PDFInfo
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- CN117511222A CN117511222A CN202311375841.6A CN202311375841A CN117511222A CN 117511222 A CN117511222 A CN 117511222A CN 202311375841 A CN202311375841 A CN 202311375841A CN 117511222 A CN117511222 A CN 117511222A
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- resin
- heat
- heat conducting
- powder
- gasket
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- 238000002360 preparation method Methods 0.000 title abstract description 95
- 239000000843 powder Substances 0.000 claims abstract description 177
- 229920005989 resin Polymers 0.000 claims abstract description 150
- 239000011347 resin Substances 0.000 claims abstract description 150
- -1 fluoroalkyl trimethoxy silane Chemical compound 0.000 claims abstract description 43
- 239000003607 modifier Substances 0.000 claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000084 colloidal system Substances 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 35
- 238000003825 pressing Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005062 Polybutadiene Substances 0.000 claims description 12
- 229920002857 polybutadiene Polymers 0.000 claims description 12
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 10
- 239000006254 rheological additive Substances 0.000 claims description 8
- IJROHELDTBDTPH-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F IJROHELDTBDTPH-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- NYIKUOULKCEZDO-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F NYIKUOULKCEZDO-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- 230000006835 compression Effects 0.000 abstract description 36
- 238000007906 compression Methods 0.000 abstract description 36
- 239000004020 conductor Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 65
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 47
- 230000035882 stress Effects 0.000 description 34
- 239000000463 material Substances 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 7
- 230000017525 heat dissipation Effects 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000001905 inorganic group Chemical group 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000377 silicon dioxide Chemical group 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FBSNEJXXSJHKHX-UHFFFAOYSA-N CC1=C(C(C=C1)([Pt]C)C)C Chemical compound CC1=C(C(C=C1)([Pt]C)C)C FBSNEJXXSJHKHX-UHFFFAOYSA-N 0.000 description 1
- YGBYJRVGNBVTCQ-UHFFFAOYSA-N C[Pt](C)C.[CH]1C=CC=C1 Chemical compound C[Pt](C)C.[CH]1C=CC=C1 YGBYJRVGNBVTCQ-UHFFFAOYSA-N 0.000 description 1
- YDNLRUSAWWOAFZ-UHFFFAOYSA-N C[Pt]C1C=CC=C1 Chemical compound C[Pt]C1C=CC=C1 YDNLRUSAWWOAFZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Abstract
The application relates to the technical field of heat conducting materials, in particular to a heat conducting gasket and a preparation method thereof. The heat-conducting gasket comprises the following components in percentage by mass: 2-6% of resin A; 2-6% of resin B; 0.72 to 1.45 percent of modifier; 90-95% of heat conducting powder; the components of the A resin and the B resin both comprise addition type organic silicon resin; the resin A comprises a catalyst, wherein the mass ratio of the catalyst to the resin A is (2-5): 100; the resin B comprises a cross-linking agent, and the mass ratio of the cross-linking agent to the resin B is (4-8): 100; the modifier comprises a surface modifier, and the surface modifier is fluoroalkyl trimethoxy silane or fluoroalkyl triethoxy silane. In addition, the present application relates to two methods of making thermally conductive gaskets. The heat conducting gasket has the advantages of high rebound capability and low compression stress.
Description
Technical Field
The application relates to the technical field of heat conducting materials, in particular to a heat conducting gasket and a preparation method thereof.
Background
With the rapid development of electronic technology, electronic components are rapidly developed in the directions of high performance, densification, high precision and high power, and the heat productivity of the electronic components is greatly improved, wherein the electronic components with larger heat productivity are commonly called as heat generating components. In order to ensure that the heating element can stably work, a heat radiating device is usually added on the heating element to help the heating element radiate heat, so that whether the heat can be rapidly conducted out of the heating element determines the working performance and the reliability of the heating element.
The heat conducting gasket is a high-performance gap filling heat conducting material widely used in thermal interface materials, and has good heat conducting function and high rebound rate. The high rebound rate of the heat conduction gasket can enable the heat conduction gasket to keep good close contact with the heating element and the heat dissipation device all the time, the situation of falling or false contact due to vibration, aging and other factors is avoided, the existence of low-heat-conductivity air between the heating element and the heat dissipation device interface is eliminated, more heat conduction channels are formed, and therefore the effect of heat transfer from the heating element to the heat dissipation device is improved.
In practical application, in order to ensure that the heat dissipation device and the heating element are in good and sufficient contact with the heat conduction gasket, proper pressure needs to be kept between the heat dissipation device and the heating element to co-extrude the heat conduction gasket, so that the heat conduction gasket can generate internal stress due to compression. Generally, the internal stress generated by compression of the thermal pad cannot exceed the use safety range of the heating element so as to prevent the semiconductor device from being damaged, and therefore, the thermal pad needs to have lower compression stress.
However, the rebound rate and the compression stress of the common heat-conducting gasket are mutually restricted, and the heat-conducting gasket commonly used in the market at present has high rebound rate and relatively high compression stress, or has poor rebound rate when the compression stress is low, so that a good filling effect can not be exerted between the heating element and the heat-dissipating device.
In view of this, there is a need to develop a thermally conductive gasket having both high rebound ability and low compressive stress.
Disclosure of Invention
In order to enable the gasket to have high rebound capability and low compression stress at the same time, the application provides a heat-conducting gasket and a preparation method thereof.
In a first aspect, the present application provides a heat conductive gasket, which adopts the following technical scheme:
a heat-conducting gasket comprises the following components in percentage by mass:
2-6% of resin A;
2-6% of resin B;
0.72 to 1.45 percent of modifier;
90-95% of heat conducting powder;
the components of the A resin and the B resin both comprise addition type organic silicon resin;
the resin A comprises a catalyst, wherein the mass ratio of the catalyst to the resin A is (2-5): 100;
the resin B comprises a cross-linking agent, and the mass ratio of the cross-linking agent to the resin B is (4-8): 100;
the modifier comprises a surface modifier, and the surface modifier is fluoroalkyl trimethoxy silane or fluoroalkyl triethoxy silane.
By adopting the technical scheme, the fluoroalkyl trimethoxy silane and fluoroalkyl triethoxy silane molecules are provided with the organophilic group and the inorganic group, and the inorganic group can be chemically bonded with the surface of the heat conducting powder, so that the fluoroalkyl trimethoxy silane and fluoroalkyl triethoxy silane molecules are tightly coated on the surface of the heat conducting powder particles through the acting force of the chemical bond; the organophilic groups of the fluoroalkyl trimethoxy silane and fluoroalkyl triethoxy silane molecules can be entangled or chemically reacted with the addition type organic silicon resin, so that the compatibility of the heat conduction powder and the addition type organic silicon resin can be improved through the fluoroalkyl trimethoxy silane and the fluoroalkyl triethoxy silane.
The molecule chains of the fluoroalkyl trimethoxy silane and the fluoroalkyl triethoxy silane are provided with a plurality of inert fluorine atoms, so that the fluoroalkyl trimethoxy silane and the fluoroalkyl triethoxy silane are easy to slide relative to surrounding molecules, friction force between the heat-conducting powder particles can be reduced after the fluoroalkyl trimethoxy silane and the fluoroalkyl triethoxy silane are coated on the surfaces of the heat-conducting powder particles, friction force is small when adjacent powder particles are subjected to relative displacement, and compression stress of the heat-conducting gasket is further reduced.
The cross-linking agent is methyl hydrogen-containing siloxane with hydrogen content of (0.4-0.8)%, and viscosity of 15-40 mPa.s at 25deg.C, and comprises one or both of linear methyl hydrogen-containing siloxane and cyclic hydrogen-containing polysiloxane.
The catalyst is one or a mixture of more of trimethyl methyl cyclopentadienyl platinum, dimethyl- [ (trimethyl silicon) methyl ] -methyl cyclopentadienyl platinum and (trimethyl) (1, 4-cyclooctadiene) platinum.
The organic silicon resin with good elasticity, mechanical property and weather resistance is prepared by adopting the resin A and the resin B and adopting vinyl end-capped polydimethylsiloxane as the base material, wherein the curing process mainly comprises the cross-linking of vinyl of the base material and a cross-linking agent containing Si-H bonds; under the action of a platinum catalyst, additives such as a heat conducting filler, a modifier and the like are matched to be used as functional auxiliary agents, and the three-dimensional reticular structure is formed by carrying out a hydrosilylation reaction at room temperature, so that the solidification is completed, the prepared heat conducting gasket has good rebound rate and service life, and can fill the gap between a heating element and a radiating element to play a role in buffering and damping.
In one particular embodimentIn an embodiment, the A resin is methyl vinyl siloxane or vinyl triethoxysilane, and the B resin comprises vinyl-terminated polydimethylsiloxane. Wherein the vinyl-containing polysiloxane has the general formula (Me) 3- n Vi n SiO 1/2 )a(Ph 2 SiO) b (ViMeSiO) c (SiO 2 ) d Vi represents vinyl, me represents methyl, ph represents phenyl; a. b, c and d are all greater than 0; n has a value of 0 or 1; (a+b+c)/d=0.6-1.5; the viscosity of the polysiloxane containing vinyl is 600-1000 mPa.s, and the alkenyl content is 0.2-0.8mmol/g.
By adopting the technical scheme, the viscosity and the consumption of the base body raw materials are adjusted, so that the viscosity and the strength of the heat conduction material are controlled, the heat conduction gasket is better applied to being clamped between the heating body and the heat dissipation member, and the adhesion between the heating surface and the heat dissipation member is improved.
In a specific embodiment, the B resin further comprises a polybutadiene epoxy resin; the mass ratio of the vinyl-terminated polydimethylsiloxane to the polybutadiene epoxy resin is 1:0.5-0.9.
By adopting the technical scheme, the polybutadiene epoxy resin basically does not generate low molecular volatile matters when being solidified, the volume shrinkage rate of the adhesive layer is small, the linear expansion coefficient is also small, so that the internal stress is small, the influence on the adhesive strength is small, and the creep of the polybutadiene epoxy resin is small, so that the adhesive layer has good dimensional stability, has larger viscosity and very good tensile toughness, enhances the integrity of gasket materials, and improves the impact resistance and the wear resistance.
In a specific embodiment, the modifier comprises a surface modifier that is one or more of tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, nonafluorohexyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, and nonafluorohexyltrimethoxysilane.
In a specific embodiment, the modifier further comprises a rheology modifier, wherein the rheology modifier is at least one of ethyl acetate, toluene, ethylbenzene, acetone, ethanol, isopropanol and alkane solvents, and the mass ratio of the surface modifier to the rheology modifier is 1:0.6-0.9.
Through adopting above-mentioned technical scheme, contain long-chain alkyl and silica bond in the surface modifier molecule, long-chain alkyl can with the heat conduction powder surface interaction, strengthen its adhesive force, silica bond improves the heat conduction powder and adds the compatibility of addition type organic silicon resin, strengthen chemical stability, because surfactant molecule has great activity, the molecule is easy to agglomerate, and then influence its even cladding heat conduction powder, through surfactant and rheology modifier's complex formula, can effectively improve the efficiency of surfactant even cladding heat conduction powder granule, practice thrift surfactant's quantity, also can increase the heat conduction channel of heat conduction powder, strengthen thermal conductivity, and effectively reduce the frictional force between the heat conduction powder granule, thereby reduce the compressive stress of heat conduction gasket.
In a specific embodiment, the heat conducting powder comprises non-spherical heat conducting powder and spherical heat conducting powder, and the mass ratio of the non-spherical heat conducting powder to the spherical heat conducting powder is (0-1): 5.
by adopting the technical scheme, the non-spherical heat conducting powder has good heat conducting effect; when the heat conducting powder is spherical, and adjacent powder particles are subjected to relative displacement, the spherical heat conducting powder can reduce friction force between the adjacent powder particles, and is beneficial to reducing compression stress of the heat conducting gasket.
In the organic silicon resin system, the heat conduction capability and the rebound rate of the prepared heat conduction gasket can be balanced by compounding the non-spherical heat conduction powder and the spherical heat conduction powder.
In a specific embodiment, the heat conductive powder includes a small particle size heat conductive powder having a particle size of 0.5 to 120 μm and a large particle size heat conductive powder having a particle size of 140 to 180 μm.
Through adopting above-mentioned technical scheme, there is more spaces between the big particle diameter powder granule of adjacent to hold organic silicon resin, thereby can reduce the compressive stress of heat conduction gasket when not reducing heat conduction gasket resilience.
The interface contact between the large-particle-size heat conducting powder particles is less, and the interface thermal resistance is lower, so that the addition of the large-particle-size heat conducting powder in the organic silicon resin system is beneficial to improving the heat conducting capacity of the heat conducting gasket.
The small-particle-size heat conducting powder can enable more heat conducting powder to be filled in the organic silicon resin system with the same volume, so that the heat conducting powder forms the maximum stacking degree, and the heat conducting capability of the heat conducting gasket is improved.
In the organic silicon resin system, through the compounding of small-particle-size heat conducting powder and large-particle-size heat conducting powder, a plurality of small-particle-size heat conducting powder particles are distributed around the large-particle-size heat conducting powder particles, so that the small-particle-size heat conducting powder particles and the large-particle-size heat conducting powder particles are easier to contact each other and form a heat conducting passage, and meanwhile, when the heat conducting gasket deforms, the small-particle-size heat conducting powder particles are easier to flexibly displace in the organic silicon resin system, and further, the compression stress of the heat conducting gasket can be reduced while the heat conducting performance of the heat conducting gasket is not reduced.
In a specific embodiment, the mass ratio of the large-particle-diameter heat conducting powder to the small-particle-diameter heat conducting powder is (5-15): 1.
in a specific embodiment, the heat conductive powder is selected from one or more of α -alumina, zirconia, magnesia, zinc oxide, silicon nitride, silicon carbide; preferably, the thermally conductive powder is selected from alpha-alumina.
In a second aspect, the present application provides a method for preparing a heat conductive gasket, which adopts the following technical scheme:
a preparation method of a heat conduction gasket comprises the following steps:
s1, mixing the resin A, the resin B and the modifier in a proportion under vacuum at 15-28 ℃ for 15-20min to obtain a primary colloid;
s2, adding heat conduction powder into the primary colloid obtained in the step 1 at 15-28 ℃, and mixing for 20-30min under vacuum to obtain a first colloid;
and S3, carrying out delay pressing on the first colloid obtained in the step S3 to obtain a sheet, thus obtaining the heat-conducting gasket.
By adopting the technical scheme, the modifier is firstly mixed into the organic silicon resin system, then the heat conduction powder is added for vacuum mixing, so that the interface thermal resistance of the organic silicon resin system and the heat conduction filler is reduced, the interface thermal resistance is reduced, the interface compatibility of the heat conduction powder and the organic silicon resin system is improved, and the heat conductivity is further improved.
In a third aspect, the present application provides a method for preparing a heat conductive gasket, which adopts the following technical scheme:
a preparation method of a heat conduction gasket comprises the following steps:
s1, spraying a modifier on the heat-conducting powder according to the proportion at 15-28 ℃ to obtain dry modified powder;
s2, mixing the resin A, the resin B and the dry modified powder obtained in the step S1 under vacuum at 15-28 ℃ for 35-45min to obtain a second colloid;
and S3, carrying out delay pressing on the second colloid obtained in the step S2 to obtain a sheet, thus obtaining the heat-conducting gasket.
By adopting the technical scheme, the heat-conducting powder is modified and then mixed into the organic silicon resin system, so that the coating rate of the modifier on the surfaces of the heat-conducting powder particles can be improved, the friction force between adjacent heat-conducting powder particles can be reduced when the adjacent powder particles relatively displace, and the compression stress of the heat-conducting gasket can be further reduced.
In a fourth aspect, the present application provides a method for preparing a heat conductive gasket, which adopts the following technical scheme:
a preparation method of a heat conduction gasket comprises the following steps:
s1, uniformly mixing heat conducting powder and a modifier according to a proportion at 15-28 ℃ to obtain a mixture; drying the mixture to obtain wet modified powder;
s2, mixing the resin A, the resin B and the wet modified powder obtained in the step 1 under vacuum at 15-28 ℃ for 35-45min to obtain a second colloid;
and S3, carrying out delay pressing on the second colloid obtained in the step S2 to obtain a sheet, thus obtaining the heat-conducting gasket.
By adopting the technical scheme, the modifier is firstly mixed into the heat-conducting powder, so that the heat-conducting powder is fully contacted with the modifier, the heat-conducting powder is fully modified, the combination efficiency with the organic silicon resin system is enhanced, and the heat-conducting property of the prepared heat-conducting gasket is enhanced.
In summary, the present application has the following beneficial effects:
1. the modifier is coated on the surface of the heat conducting powder particles, so that the friction force when adjacent powder particles are subjected to relative displacement is reduced, and the compression stress of the heat conducting gasket is reduced.
2. By compounding the small-particle-size heat conducting powder and the large-particle-size heat conducting powder, the compression stress of the heat conducting gasket can be reduced while the heat conducting performance of the heat conducting gasket is not reduced.
3. The modifier is coated on the surface of the heat conducting powder particle to improve the compatibility of the heat conducting powder and the addition type organic silicon resin.
Detailed Description
The present application is described in further detail below with reference to examples.
Raw materials
Some of the starting materials used in the preparation examples and examples:
polydimethylsiloxane CAS number: 9016-00-6, model: JN-201; polybutadiene epoxy CAS no: 129288-65-9, model: KMK5000; alpha-alumina CAS number: 1344-28-1; heptadecafluorodecyl trimethoxysilane CAS number: 83048-65-1; heptadecafluorodecyl triethoxysilane CAS number: 101947-16-4; polymethylhydrosiloxane CAS number: 63148-57-2, model: HG-3203; tetramethyl dihydro disiloxane CAS No.: 3277-26-7 model: C7H6O2 methyl cyclopentadienyl platinum CAS number: 94442-22-5; 1-ethynyl cyclohexanol CAS number: 78-27-3; polymethylhydrosiloxane and tetramethyl dihydrodisiloxane are used as cross-linking agents and 1-ethynyl cyclohexanol is used as inhibitor.
The relevant raw materials used in the examples and comparative examples, which were not noted, were conventional products commercially available.
Preparation example
Preparation of resin A
Preparation example 1
196g of vinyltriethoxysilane with the viscosity of 1000 mPas and the vinyl content of 0.2mmol/g and 4g of trimethylcyclopentadienyl platinum are accurately weighed in proportion at 25 ℃, added into a stirrer, uniformly mixed and dispersed, and then vacuumized and defoamed.
Preparation example 2
193g of methyl vinyl siloxane with the viscosity of 1000 mPas and the vinyl content of 0.8mmol/g and 7g of dimethyl- [ (trimethyl silicon) methyl ] -methylcyclopentadienyl platinum are accurately weighed in proportion at 25 ℃, added into a stirrer, uniformly mixed and dispersed, and then vacuumized and defoamed.
Preparation example 3
At 25 ℃, 190g of methyl vinyl siloxane with the viscosity of 600 mPas and the vinyl content of 0.8mmol/g and 10g of (trimethyl) (1, 4-cyclooctadiene) platinum are accurately weighed according to a proportion, added into a stirrer, uniformly mixed and dispersed, and then vacuumized and defoamed.
Preparation of resin B
Preparation example 4
191.5g of vinyl-terminated polydimethylsiloxane (alkenyl content is 0.8 mmol/g), 8g of polymethylhydrosiloxane (hydrogen content is 0.8%, viscosity is 40 mPa.s at 25 ℃) and 0.5g of 1-ethynyl cyclohexanol are weighed, sequentially added into a stirrer, uniformly mixed and stirred, and then vacuumized and defoamed for standby to obtain resin B;
preparation example 5
183.5g of vinyl-terminated polydimethylsiloxane (alkenyl content is 0.8 mmol/g), 16g of tetramethyl dihydro disiloxane (hydrogen content is 0.8%, viscosity is 40 mPa.s at 25 ℃) and 0.5g of 1-ethynyl cyclohexanol are weighed, sequentially added into a stirrer, uniformly mixed and stirred, and then vacuumized and defoamed for standby to obtain resin B;
preparation example 6
127.7g of vinyl-terminated polydimethylsiloxane (alkenyl content is 0.8 mmol/g), 63.8g of polybutadiene epoxy resin, 8g of polymethyl hydrogen-containing siloxane (hydrogen content is 0.8%, viscosity is 40 mPa.s at 25 ℃) and 0.5g of 1-ethynyl cyclohexanol are weighed, sequentially added into a stirrer, uniformly mixed and stirred, and then vacuumized and defoamed for standby to obtain resin B;
preparation example 7
Weighing 100.8g of vinyl-terminated polydimethylsiloxane (alkenyl content is 0.8 mmol/g), 90.7g of polybutadiene epoxy resin, 8g of polymethyl hydrogen-containing siloxane (hydrogen content is 0.8%, viscosity is 40 mPa.s at 25 ℃) and 0.5g of 1-ethynyl cyclohexanol, sequentially adding into a stirrer, uniformly mixing and stirring, and vacuumizing for standby to obtain resin B;
examples
Example 1
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat-conducting powder and 7.2g of heptadecafluorodecyl trimethoxysilane, wherein 456.4g of 0.5 mu m spherical alpha-alumina and 456.4g of 140 mu m spherical alpha-alumina are selected as the heat-conducting powder.
Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6 and heptadecafluorodecyl trimethoxysilane at 25 ℃ in proportion under the pressure of-0.09 MPa for 15min at the stirring speed of 50rpm to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 2
A thermally conductive gasket comprising the following components: 60g of the A resin obtained in preparation example 3, 25.5g of the B resin obtained in preparation example 5, 900g of heat conducting powder and 14.5g of tridecafluorooctyltriethoxysilane, wherein the heat conducting powder comprises 450g of 40 μm spherical alpha-alumina and 450g of 140 μm spherical alpha-alumina.
Stirring the resin A prepared in preparation example 3, the resin B prepared in preparation example 5 and tridecafluorooctyl triethoxysilane at-0.09 MPa for 20min at 28 ℃ and 50rpm to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 3
A thermally conductive gasket comprising the following components: 30g of the A resin obtained in preparation example 2, 30g of the B resin obtained in preparation example 4, 930g of heat-conducting powder and 10g of nonafluorohexyl trimethoxysilane, wherein 465g of 120-mu m spherical alpha-alumina and 465g of 140-mu m spherical alpha-alumina are used as the heat-conducting powder.
Stirring the resin A prepared in preparation example 2, the resin B prepared in preparation example 4 and nonafluorohexyl trimethoxysilane at the temperature of 28 ℃ according to the proportion under the pressure of-0.09 MPa for 15min at the stirring speed of 50rpm to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 4
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 2, 20g of the B resin obtained in preparation example 7, 950g of heat conducting powder and 10g of heptadecafluorodecyl trimethoxysilane, wherein 475g of 120-mu m spherical alpha-alumina and 475g of 140-mu m spherical alpha-alumina are selected as the heat conducting powder.
Stirring the resin A prepared in preparation example 2, the resin B prepared in preparation example 7 and heptadecafluorodecyl trimethoxysilane at 25 ℃ in proportion under the pressure of-0.09 MPa for 15min at the stirring speed of 50rpm to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 5
A thermally conductive gasket comprising the following components: 30g of the A resin obtained in preparation example 2, 30g of the B resin obtained in preparation example 7, 930g of heat conducting powder, 10g of nonafluorohexyl trimethoxysilane and 465g of 120-mu m spherical alpha-alumina and 465g of 140-mu m spherical alpha-alumina are selected as the heat conducting powder.
Stirring the resin A prepared in preparation example 2, the resin B prepared in preparation example 7 and nonafluorohexyl trimethoxysilane at 25 ℃ in proportion under the pressure of-0.09 MPa for 15min at the stirring speed of 50rpm to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 6
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat-conducting powder, 4.5g of heptadecafluorodecyl trimethoxysilane and 2.7g of ethanol, wherein 456.4g of 0.5 mu m spherical alpha-alumina and 456.4g of 140 mu m spherical alpha-alumina are selected as the heat-conducting powder.
Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6, heptadecafluorodecyl trimethoxysilane and ethanol at-0.09 MPa for 15min at 25 ℃ to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 7
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat-conducting powder, 4.5g of heptadecafluorodecyl trimethoxysilane and 2.7g of ethyl acetate, wherein 456.4g of 0.5 mu m spherical alpha-alumina and 456.4g of 140 mu m spherical alpha-alumina are selected as the heat-conducting powder.
Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6, heptadecafluorodecyl trimethoxysilane and ethyl acetate at-0.09 MPa for 15min at 25 ℃ to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 8
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat-conducting powder, 3.8g of heptadecafluorodecyl trimethoxysilane and 3.4g of ethanol, wherein 456.4g of 0.5 mu m spherical alpha-alumina and 456.4g of 140 mu m spherical alpha-alumina are selected as the heat-conducting powder.
Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6, heptadecafluorodecyl trimethoxysilane and ethanol at-0.09 MPa for 15min at 25 ℃ to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 9
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat conducting powder, 3.8g of heptadecafluorodecyl trimethoxysilane and 3.4g of ethanol, wherein the heat conducting powder comprises 57.1g of 40-mu m spherical alpha-alumina and 885.7g of 150-mu m spherical alpha-alumina.
Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6, heptadecafluorodecyl trimethoxysilane and ethanol at-0.09 MPa for 15min at 25 ℃ to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 10
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat conducting powder, 3.8g of heptadecafluorodecyl trimethoxysilane and 3.4g of ethanol, wherein the heat conducting powder is 0.5 mu m spherical alpha-alumina 120g and 140 mu m spherical alpha-alumina 810g.
Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6, heptadecafluorodecyl trimethoxysilane and ethanol at-0.09 MPa for 15min at 25 ℃ to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 11
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat conducting powder, 3.8g of heptadecafluorodecyl trimethoxysilane and 3.4g of ethanol, wherein the heat conducting powder comprises 152.1g of 120-mu m spherical alpha-alumina and 760.7g of 180-mu m spherical alpha-alumina.
Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6, heptadecafluorodecyl trimethoxysilane and ethanol at-0.09 MPa for 15min at 25 ℃ to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 12
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat conducting powder, 3.8g of heptadecafluorodecyl trimethoxysilane and 3.4g of ethanol, wherein the heat conducting powder comprises 152.1g of 40-mu m spherical alpha-alumina and 760.7g of 150-mu m spherical alpha-alumina.
Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6, heptadecafluorodecyl trimethoxysilane and ethanol at-0.09 MPa for 15min at 25 ℃ to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 13
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat conducting powder, 3.8g of heptadecafluorodecyl trimethoxysilane and 3.4g of ethanol, wherein the heat conducting powder comprises 738.1g of 150-mu m spherical alpha-alumina, 152.1g of 150-mu m non-spherical alpha-alumina and 147.6g of 40-mu m spherical alpha-alumina.
Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6, heptadecafluorodecyl trimethoxysilane and ethanol at-0.09 MPa for 15min at 25 ℃ to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 14
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 910g of a heat conductive powder and 10g of heptadecafluorodecyl trimethoxysilane, wherein 45 g of 0.5 mu m spherical alpha-alumina and 455g of 140 mu m spherical alpha-alumina are selected as the heat conductive powder. Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6 and heptadecafluorodecyl trimethoxysilane at 25 ℃ in proportion under the pressure of-0.09 MPa for 15min at the stirring speed of 50rpm to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 15
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat conducting powder, 2g of heptadecafluorodecyl trimethoxysilane and 5.2g of ethanol, wherein 456.4g of 0.5 mu m spherical alpha-alumina and 456.4g of 140 mu m spherical alpha-alumina are selected as the heat conducting powder.
Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6 and heptadecafluorodecyl trimethoxysilane at 25 ℃ in proportion under the pressure of-0.09 MPa for 15min at the stirring speed of 50rpm to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Example 16
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat conducting powder, 3.8g of heptadecafluorodecyl trimethoxysilane and 3.4g of ethanol, wherein the heat conducting powder is selected from 150 mu m spherical alpha-alumina 738.1g, 150 mu m non-spherical alpha-alumina 147.6g and 40 mu m spherical alpha-alumina 57.1g.
Uniformly stirring heptadecafluorodecyl trimethoxysilane and ethanol at the temperature of 28 ℃ under the pressure of-0.09 MPa according to the proportion, S1 spraying a mixture of heptadecafluorodecyl trimethoxysilane and ethanol on heat conducting powder at the temperature of 15-28 ℃ according to the proportion to obtain dry modified powder;
s2, mixing the resin A, the resin B and the dry modified powder obtained in the step S1 under vacuum at 28 ℃ for 35-45min to obtain a second colloid;
and S3, carrying out delay pressing on the second colloid obtained in the step S2 to obtain a sheet, thus obtaining the heat-conducting gasket.
Example 17
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat conducting powder, 3.8g of heptadecafluorodecyl trimethoxysilane and 3.4g of ethanol, wherein the heat conducting powder is selected from 150 mu m spherical alpha-alumina 738.1g, 150 mu m non-spherical alpha-alumina 147.6g and 40 mu m spherical alpha-alumina 57.1g.
S1, uniformly stirring heptadecafluorodecyl trimethoxysilane and ethanol at 15 ℃ under the pressure of-0.09 MPa according to the proportion, and uniformly mixing heat conduction powder, heptadecafluorodecyl trimethoxysilane and ethanol to obtain a mixture; drying the mixture to obtain wet modified powder;
s2, mixing the resin A, the resin B and the wet modified powder obtained in the step 1 under vacuum at 15-28 ℃ for 35-45min to obtain a third colloid;
and S3, carrying out delay pressing on the third colloid obtained in the step S2 to obtain a sheet, thus obtaining the heat-conducting gasket.
Example 18
A thermally conductive gasket comprising the following components: 30g of the A resin obtained in preparation example 2, 30g of the B resin obtained in preparation example 6, 930g of heat conducting powder, 10g of nonafluorohexyl trimethoxysilane and 465g of 120-mu m spherical alpha-alumina and 465g of 140-mu m spherical alpha-alumina are selected as the heat conducting powder.
Stirring the resin A prepared in preparation example 2, the resin B prepared in preparation example 6 and nonafluorohexyl trimethoxysilane at 25 ℃ in proportion under the pressure of-0.09 MPa for 15min at the stirring speed of 50rpm to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Comparative example
Comparative example 1
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6 and 912.8g of heat conducting powder, wherein 456.4g of 0.5 mu m spherical alpha-alumina and 456.4g of 140 mu m spherical alpha-alumina are selected as the heat conducting powder.
Stirring the resin A prepared in preparation example 1 and the resin B prepared in preparation example 6 at-0.09 MPa according to a proportion at 25 ℃ for 15min at a stirring speed of 50rpm to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Comparative example 2
A thermally conductive gasket comprising the following components: 20g of the A resin obtained in preparation example 1, 60g of the B resin obtained in preparation example 6, 912.8g of heat conducting powder and 7.2g of polyvinylpyrrolidone, wherein 456.4g of 0.5 mu m spherical alpha-alumina and 456.4g of 140 mu m spherical alpha-alumina are selected as the heat conducting powder.
Stirring the resin A prepared in preparation example 1, the resin B prepared in preparation example 6 and polyvinylpyrrolidone at-0.09 MPa for 15min at 25 ℃ to obtain a primary colloid; adding the heat conducting powder into the primary colloid for 3 times in equal amount, and stirring under the pressure of-0.09 MPa for 20min at the stirring speed of 35rpm to obtain a first colloid; and (5) carrying out extension pressing to obtain a sheet material with the thickness of 2mm, thus obtaining the heat conducting gasket.
Performance detection
The performance test of the heat conductive gaskets prepared in examples 1-18 and comparative examples 1-2 was performed as follows:
a. and (3) heat conduction coefficient test: reference is made to ASTM D5470 standard test; b. hardness testing: reference is made to ASTM D2240 standard test; c. and (3) rebound rate test: according to ASTM D575-91 standard; instantaneous compressive stress at 50% compression set: reference ASTM D575 standard test; residual compressive stress after 10min at 50% compression set: reference is made to ASTM D575 standard test.
The properties of the thermally conductive gaskets prepared in examples 1-18 and comparative examples 1-2 are shown in Table 1:
TABLE 1 Performance test results
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As can be seen from table 1, the rebound rate, the instantaneous compression stress at 50% compression set and the residual compression stress after 10min at 50% compression set of the thermal pad prepared in example 1 are all better than those of comparative example 1, which demonstrates that the thermal pad prepared in example 1 has both high rebound ability and low compression stress.
As can be seen from comparative examples 14 and 1, with the increase in the content of heptadecafluorodecyl trimethoxysilane in the heat conductive gasket component, the instantaneous compression stress at 50% compression set and the residual compression stress after 10min at 50% compression set of the prepared heat conductive gasket are both significantly reduced, indicating that increasing the content of the modifier in the heat conductive gasket component is beneficial to reducing the compression stress of the prepared heat conductive gasket. This may be due to the presence of a plurality of relatively inert fluorine atoms in the molecular chain of the modifier, so that the heat conductive powder particles are liable to relatively slide with surrounding molecules, thereby reducing friction between the heat conductive powder particles, reducing friction when adjacent heat conductive powder particles relatively displace, further reducing compression stress of the heat conductive gasket, increasing heat conductive channels of the heat conductive powder, and enhancing heat conductivity.
As is clear from comparative examples 15 and 6, as the mass ratio of ethanol to heptadecafluorodecyl trimethoxysilane in the heat conductive gasket component continues to increase, the heat conductivity is improved, but the heat conductive gasket is deteriorated in rebound performance, compression stress and the like, probably because the fluidity of the heat conductive powder is increased due to excessive ethanol, and heptadecafluorodecyl trimethoxysilane is relatively less, resulting in deterioration of the bonding property of the heat conductive powder to the resin.
In comparative examples 1, 6-8, the surfactant and the rheology modifier are compounded in the modifier, so that the surfactant can better disperse and coat the heat-conducting powder, the bonding efficiency of the heat-conducting powder and the matrix resin is enhanced, and the friction force between the particles of the heat-conducting powder is reduced, thereby reducing the compression stress of the heat-conducting gasket.
Compared with the heat-conducting gasket prepared in comparative example 2, the heat-conducting gasket prepared in example 1 has better heat conductivity, rebound rate and other heat-conducting properties, and the compression stress is obviously reduced, so that the friction force can be reduced when adjacent powder particles are relatively displaced by fluoroalkyl trimethoxysilane and fluoroalkyl triethoxysilane, and the compression stress of the heat-conducting gasket is further reduced.
In comparison of example 3 with example 5 and example 18, the polybutadiene epoxy resin with larger viscosity and very good tensile toughness is compounded, so that the integrity of the gasket material is enhanced, the impact resistance and the wear resistance are improved, and the resilience of the heat-conducting gasket is further remarkably enhanced.
The polybutadiene epoxy resin is basically free of low-molecular volatile matters during curing, the volume shrinkage rate of the adhesive layer is small, the linear expansion coefficient is also small, so that the internal stress is small, the influence on the adhesive strength is small, and the creep deformation of the polybutadiene epoxy resin is small, so that the adhesive layer has good dimensional stability, has larger viscosity and very good tensile toughness, enhances the integrity of gasket materials, and improves the impact resistance and the wear resistance.
As can be seen from comparative examples 9 and 12, with the increase of the content of the large-particle-size heat conductive powder in the heat conductive powder, the rebound rate of the prepared heat conductive gasket is significantly increased, which means that increasing the content of the large-particle-size heat conductive powder in the heat conductive powder is beneficial to increasing the rebound rate of the prepared heat conductive gasket. This is probably because there is more space between adjacent large-particle-diameter powder particles to accommodate the silicone resin, so that the content of the large-particle-diameter heat conductive powder in the heat conductive powder can be improved, which is beneficial to improving the rebound rate of the prepared heat conductive gasket.
As can be seen from comparative examples 10 and 8, in example 10, by compounding the small-particle-size heat conductive powder and the large-particle-size heat conductive powder in a proper proportion, the instantaneous compression stress at 50% compression set and the residual compression stress at 50% compression set of the prepared heat conductive gasket are both superior to those of example 8, and the heat conductivity of the heat conductive gasket prepared in example 10 is not significantly reduced, which means that the rebound rate of the prepared heat conductive gasket is improved without reducing the heat conductivity of the heat conductive gasket by compounding the small-particle-size heat conductive powder and the large-particle-size heat conductive powder in a proper proportion. This is probably because the small-particle-diameter heat conductive powder particles are filled into the gaps of the large-particle-diameter heat conductive powder by compounding the small-particle-diameter heat conductive powder and the large-particle-diameter heat conductive powder in a proper proportion, so that the total filling amount is greatly increased, meanwhile, the small-particle-diameter heat conductive powder particles and the large-particle-diameter heat conductive powder particles are easier to contact each other and form a heat conductive path, and meanwhile, when the heat conductive gasket deforms, the small-particle-diameter heat conductive powder particles are easier to flexibly displace in the organic silicon resin system, and further, the compression stress of the heat conductive gasket can be reduced while the heat conductive property of the heat conductive gasket is not reduced.
The foregoing are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (10)
1. A thermally conductive gasket, characterized in that: comprises the following components in percentage by mass:
2-6% of resin A;
2-6% of resin B;
0.72 to 1.45 percent of modifier;
90-95% of heat conducting powder;
the components of the A resin and the B resin both comprise addition type organic silicon resin;
the resin A comprises a catalyst, wherein the mass ratio of the catalyst to the resin A is (2-5): 100;
the resin B comprises a cross-linking agent, and the mass ratio of the cross-linking agent to the resin B is (4-8): 100;
the modifier comprises a surface modifier, and the surface modifier is fluoroalkyl trimethoxy silane or fluoroalkyl triethoxy silane.
2. A thermally conductive gasket as set forth in claim 1 wherein: the A resin comprises one or two of methyl vinyl siloxane or vinyl triethoxy silane, and the B resin comprises vinyl-terminated polydimethylsiloxane.
3. A thermally conductive gasket as set forth in claim 2 wherein: the B resin also comprises polybutadiene epoxy resin; the mass ratio of the vinyl-terminated polydimethylsiloxane to the polybutadiene epoxy resin is 1:0.5-0.9.
4. A thermally conductive gasket as set forth in claim 1 wherein: the surface modifier is one or more of tridecafluorooctyl triethoxysilane, heptadecafluorodecyl triethoxysilane, nonafluorohexyl triethoxysilane, heptadecafluorodecyl trimethoxysilane, tridecafluorooctyl trimethoxysilane and nonafluorohexyl trimethoxysilane.
5. A thermally conductive gasket as claimed in claim 4 wherein: the modifier also comprises a rheology modifier, wherein the rheology modifier is at least one of ethyl acetate, toluene, ethylbenzene, acetone, ethanol, isopropanol and alkane solvents, and the mass ratio of the surface modifier to the rheology modifier is 1:0.6-0.9.
6. A thermally conductive gasket as set forth in claim 1 wherein: the heat conducting powder comprises non-spherical heat conducting powder and spherical heat conducting powder, wherein the mass ratio of the non-spherical heat conducting powder to the spherical heat conducting powder is (0-1): 5.
7. a thermally conductive gasket as set forth in claim 1 wherein: the heat conducting powder comprises small-particle-size heat conducting powder and large-particle-size heat conducting powder, wherein the particle size of the small-particle-size heat conducting powder is 0.5-120 mu m, and the particle size of the large-particle-size heat conducting powder is 140-180 mu m.
8. A thermally conductive gasket as claimed in claim 5 wherein: the mass ratio of the large-grain-size heat-conducting powder to the small-grain-size heat-conducting powder is (5-15): 1.
9. the method for preparing a heat conductive gasket according to any one of claims 1 to 8, comprising the steps of:
s1, mixing the resin A, the resin B and the modifier in a proportion under vacuum at 15-28 ℃ for 15-20min to obtain a primary colloid;
s2, adding heat conduction powder into the primary colloid obtained in the step S1 at 15-28 ℃, and mixing for 20-30min under vacuum to obtain a first colloid;
and S3, carrying out delay pressing on the first colloid obtained in the step S2 to obtain a sheet, thus obtaining the heat-conducting gasket.
10. The method for preparing a heat conductive gasket according to any one of claims 1 to 8, comprising the steps of:
s1, spraying a modifier on the heat-conducting powder according to the proportion at 15-28 ℃ to obtain modified powder;
s2, mixing the resin A, the resin B and the modified powder obtained in the step S1 under vacuum at 15-28 ℃ for 35-45min to obtain a second colloid;
and S3, carrying out delay pressing on the second colloid obtained in the step S2 to obtain a sheet, thus obtaining the heat-conducting gasket.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211368303X | 2022-11-03 | ||
| CN202211368303.XA CN115612300A (en) | 2022-11-03 | 2022-11-03 | Heat-conducting gasket and preparation method thereof |
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| CN202211368303.XA Withdrawn CN115612300A (en) | 2022-11-03 | 2022-11-03 | Heat-conducting gasket and preparation method thereof |
| CN202311375841.6A Pending CN117511222A (en) | 2022-11-03 | 2023-10-23 | Heat conduction gasket and preparation method thereof |
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| CN103788661A (en) * | 2014-01-21 | 2014-05-14 | 万炜涛 | Stress controlled high-thermal-conductivity high polymer interface material and preparation method thereof |
| US10692797B2 (en) * | 2015-06-30 | 2020-06-23 | Laird Technologies, Inc. | Thermal interface materials with low secant modulus of elasticity and high thermal conductivity |
| CN108366511A (en) * | 2018-01-23 | 2018-08-03 | 苏州矽美科导热科技有限公司 | A kind of heat-conducting pad and preparation method thereof |
| CN114276688A (en) * | 2021-12-31 | 2022-04-05 | 四川天邑康和通信股份有限公司 | Flame-retardant high-elasticity heat-conducting gasket and preparation method thereof |
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