CN115926738B - Heat-conducting insulating silica gel for high-strength semiconductor packaging and preparation method thereof - Google Patents
Heat-conducting insulating silica gel for high-strength semiconductor packaging and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 46
- 239000000741 silica gel Substances 0.000 title claims abstract description 46
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 10
- 239000004065 semiconductor Substances 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229920002545 silicone oil Polymers 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims abstract description 22
- 230000001070 adhesive effect Effects 0.000 claims abstract description 22
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 20
- 239000003085 diluting agent Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 30
- 229920002554 vinyl polymer Polymers 0.000 claims description 29
- 239000007822 coupling agent Substances 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 9
- 230000005484 gravity Effects 0.000 claims description 8
- 238000002161 passivation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052582 BN Inorganic materials 0.000 claims description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- DDCDEKHXBABHHI-UHFFFAOYSA-N acetylene cyclohexanol Chemical compound C1(CCCCC1)O.C#C DDCDEKHXBABHHI-UHFFFAOYSA-N 0.000 claims description 6
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 6
- 229910021485 fumed silica Inorganic materials 0.000 claims description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229920002050 silicone resin Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000002633 protecting effect Effects 0.000 abstract description 4
- 239000000499 gel Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
The invention belongs to the technical field of heat-conducting silica gel, and discloses a high-strength heat-conducting insulating silica gel for semiconductor packaging and a preparation method thereof, wherein the heat-conducting insulating silica gel comprises the following raw materials in parts by weight: 6 to 10 parts of base material, 5.6 to 20 parts of reactive diluent, 0.5 to 5 parts of hydrogen-containing silicone oil, 0.1 to 2 parts of reinforcing agent, 1 to 5 parts of adhesive, 0.05 to1 part of catalyst, 0.01 to1 part of inhibitor and 250 to 400 parts of heat conducting filler; the heat-conducting insulating silica gel prepared by the invention is an addition type single-component high-temperature rapid curing gel, has low viscosity, convenient use, low ring body content, environment friendliness, high body strength, good adhesion to a lid frame and a PCB (printed Circuit Board), good heat conduction, and capability of timely radiating heat generated by a chip and a substrate and protecting the chip from being damaged by high temperature.
Description
Technical Field
The invention relates to a heat-conducting insulating silica gel for high-strength semiconductor packaging and a preparation method thereof, belonging to the technical field of heat-conducting insulating silica gels.
Background
The prior experiment proves that: every 2 ℃ of the temperature of the electronic component is increased, the reliability is reduced by 10%; the lifetime at a temperature rise of 50℃is only 1/6 of that at a temperature rise of 25 ℃. Along with the improvement of the 5G operation speed, the power consumption of the 5G mobile phone chip is about 11W, which is about 2.5 times that of the 4G mobile phone, and certainly more heat is generated, however, the volumes of the integrated circuit chip and the electronic components are continuously reduced, the internal structural design is more compact, the machine body is evolved towards non-metallization, and the problem of compensating the heat dissipation by the extra heat dissipation design is already a problem to be solved in the electronic equipment.
The organic silicon is selected as a semiconductor packaging material for bonding a PCB and a nickel plating Lid for protecting an internal chip due to its excellent weather resistance, excellent high and low temperature resistance, good adhesion and hydrophobicity, excellent electrical performance, chemical corrosion resistance and the like. Although the organic silicon sealant can provide effective protection and fixation for the bonding related components, the heat conductivity coefficient of the common silica gel can not meet the requirement of the heating component on heat conduction, the use of the organic silicon sealant can prevent the heat dissipation of the heating component, and the heat accumulation can seriously affect the stability and the service life of the service performance of the corresponding component. In order to widen the application range of the sealant, the heat conduction performance of the organic silicon sealant can be improved by adding a heat conduction filler.
The improvement of the heat-conducting property is achieved by high filling of the filler, but the viscosity of the matrix is increased by excessively high filling amount, the sizing process is influenced, the flexibility of the solidified colloid is influenced, and the elongation is drastically reduced, so that the buffering and protecting effects of the solidified colloid on related parts are reduced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-strength heat-conducting insulating silica gel for semiconductor packaging and a preparation method thereof on the basis of the existing heat-conducting insulating silica gel technology. The heat-conducting insulating silica gel prepared by the invention is addition type single-component medium-high temperature rapid curing silica gel, is convenient to use, environment-friendly, good in heat conduction, high in body strength, good in adhesion to a base material, and capable of reducing the residual of the silica gel in a component during repair, and is beneficial to protecting the corresponding component of a chip.
The invention solves the technical problems as follows, and one of the purposes of the invention is to provide a heat-conducting and insulating silica gel for high-strength semiconductor packaging, which comprises the following components in parts by weight:
Further, the base material is formed by kneading methyl vinyl silicone oil, fumed silica and a structural control agent at a high temperature, and the mass ratio of the base material is (65-90): (5-15): (0.5-5).
Further, the methyl vinyl silicone oil is vinyl-terminated silicone oil or resin, the viscosity is 1000-100000 mPa.s, and the vinyl content is 0.02-2 wt%;
further, the fumed silica is one of R974 and DM-20 s.
Further, the structuring control agent is one of dimethyl dichlorosilane and hexamethyldisilazane.
Further, the reactive diluent is branched polyvinyl silicone oil containing reactive group vinyl, the viscosity is 300-2000 mPa.s, the vinyl content is 0.1-8wt%, the structural formula is shown in (1), but the reactive diluent is not limited to the structural formula (1).
In the formula (1), e, f, g, h has a value range of 1 to 100.
The beneficial effects of adopting the further scheme are as follows: the diluent has a comb-shaped structure, can effectively increase fluidity, reduce system viscosity, and simultaneously has a plurality of reactive groups, so that the cross-linking point can be increased, and the strength is improved to a certain extent.
Further, the structural formula of the hydrogen-containing silicone oil is shown as (2),
Wherein, R' = -CH 3 or-H, m=2-15, n=2-5.
Further, the reinforcing agent is hydrogen-containing polysilsesquioxane (RSiO 3/2) a, a=6, 8,10,12, and the structural outline is shown as a formula (3), wherein r= -OSi (CH 3)2 H).
Further, the synthesis method of the hydrogen-containing polysilsesquioxane serving as the reinforcing agent comprises the following steps:
Adding concentrated sulfuric acid into a 250ml three-neck flask, uniformly mixing tetraethoxysilane (A) and tetramethyl dihydrodisiloxane (B) according to a molar ratio of 2:1, adding the mixture into the flask while stirring, controlling the temperature at 60-90 ℃, and controlling the molar ratio of A to B to C to be 2:1: (3-6) adding deionized water (C), mechanically stirring, condensing and refluxing for 18-48H, centrifuging the lower layer, washing with absolute methanol, and drying at 40-50 ℃ in a vacuum drying oven for 8-20H to obtain the white hydrogen-containing polysilsesquioxane.
The beneficial effects of adopting the further scheme are as follows: hydrogen-containing polysilsesquioxane (RSiO 3/2) a, when a=6, has high hydrosilylation activity and can react with vinyl rapidly to form reinforcing points; when a=8, 10,12, the cage structure of the nano particles of the reinforcing agent of the structural formula (3) can also deform to stop the development of the microcrack tip of the resin, induce silver streaks or shear bands, or rearrange molecular chains, and promote the improvement of toughness.
Further, the structural formula of the adhesive is one or a mixture of two of the formulas (4) and (5).
Wherein j, m=1 to 4, k, n=1 to 3, 0.ltoreq.R1.ltoreq.3.
The beneficial effects of adopting the further scheme are as follows: by adding the adhesive, the adhesive strength of the heat-conducting insulating silica gel to different base materials can be obviously improved through the introduction of various groups.
Further, the catalyst is a platinum (0) -vinyl tetramethyl dihydro disiloxane complex, and the platinum content is 3000-10000 ppm.
Further, the inhibitor is any one of 2-methyl-3-butyn-2-ol, ethynyl cyclohexanol, and 3-methyl-1-pentyn-3-ol.
Further, the heat conducting filler is one or a mixture of two of surface passivation aluminum powder with the particle size of 2.5um and spherical boron nitride with the particle size of 50um, which are treated by titanate coupling agent.
Further, the structure of the titanate coupling agent for treating the heat-conducting filler is shown as a formula (6),
Wherein x=2 to 3, y=2 to 3, and z=1 to 5.
The beneficial effects of adopting the further scheme are as follows: the aluminum powder is subjected to surface passivation, and the surface is coated by compact aluminum oxide, so that the aluminum powder is converted into an insulator from a good electric conductor, and the change of the heat conduction property of the aluminum powder is very small. After the heat conducting powder is modified by the titanate coupling agent with the structure, the surface of the heat conducting powder is coated by the coupling agent, the compatibility of the heat conducting powder and a silica gel system can be effectively increased by introducing a silica chain end, a stress concentration point is not easy to form, the viscosity is effectively reduced, and meanwhile, the strength of a matrix is improved. The heat conducting powder treated by the titanate coupling agent with the structure is also suitable for adhesives of resin systems such as epoxy, polyurethane and the like, can realize the filling of the powder with high mass fraction, and has no obvious decrease in strength.
The second purpose of the invention is to provide a preparation method of the heat-conducting insulating silica gel, which comprises the following steps:
(1) Preparing a base material: the mass of methyl vinyl silicone oil or resin, fumed silica and a structuring control agent is calculated according to the following proportion (65-90): (5-15): (0.5-5), sequentially adding into a kneader, mixing at the rotation speed of 50-200 rpm and the temperature of 120 ℃ for 1-4 hours, and vacuumizing to obtain the base material.
(2) Preparing hydrogen-containing polysilsesquioxane serving as a reinforcing agent:
Adding concentrated sulfuric acid into a 250ml three-neck flask, uniformly mixing tetraethoxysilane (A) and tetramethyl dihydrodisiloxane (B) according to a molar ratio of 2:1, adding the mixture into the flask while stirring, controlling the temperature at 60-90 ℃, and controlling the molar ratio of A to B to C to be 2:1: (3-6) adding deionized water (C), mechanically stirring, condensing and refluxing for 18-48h, centrifuging the lower layer, washing with absolute methanol, and drying in a vacuum drying oven at 40-50 ℃ for 8-20h to obtain the white hydrogen-containing polysilsesquioxane.
(3) Heat conductive powder treatment: titanate coupling agent and ethanol are mixed according to the proportion of 1:1, premixing, namely adding the heat conducting powder into a high-speed mixer for rotating at a speed of 800-1500r/min, discharging water vapor at a temperature of 90-100 ℃, and then, conducting powder according to the mass ratio: titanate coupling agent: ethanol= (88-99): (0.3-3): (0.3-3), adding the pretreated titanate coupling agent, stopping discharging when the temperature reaches 105 ℃, and sealing and packaging for standby.
(4) Preparing heat conduction insulating silica gel: adding 6-10 parts of base material, 5.6-20 parts of active diluent and 0.05-1 part of catalyst into a double-planetary gravity stirrer at room temperature, and uniformly mixing in vacuum; adding 250-400 parts of heat conducting filler, uniformly mixing in vacuum, adding 1-5 parts of adhesive, 0.01-1 part of inhibitor, uniformly mixing in vacuum, then adding 0.1-2 parts of reinforcing agent, uniformly mixing in vacuum, finally adding 0.5-5 parts of hydrogen-containing silicone oil, fully and uniformly stirring in vacuum, discharging, and sealing and preserving to obtain the heat conducting insulating silica gel.
Compared with the prior art, the invention has the beneficial effects that:
the heat-conducting insulating silica gel provided by the invention is a single-component addition type organic silica gel, can be quickly solidified in a medium-high temperature environment, and is convenient and quick to use. The branched polyvinyl diluent reduces the viscosity of the system, and meanwhile, the added reactive groups play a certain role in improving the strength; the reinforcing agent can effectively improve the final strength of the silica gel, and reduce the viscosity while increasing the toughness; the addition and the combination of the adhesive can effectively improve the interface bonding performance, effectively bond the lid frame and the PCB, and protect the internal devices. The heat conducting powder treated by the titanate coupling agent can realize the filling of the powder with high mass fraction, so that the heat conducting performance of the silica gel is obviously improved, the heat generated in the chip is timely emitted, the viscosity of the colloid is not obviously increased, and the elongation is obviously improved.
Detailed Description
The principles and features of the present invention are described below in connection with examples, which are set forth only to illustrate the present invention and are not to be construed as limiting the scope of the invention.
(1) Preparing a base material: mixing evenly 0.6 part of hexamethyldisilazane serving as a structuring control agent with the viscosity of 60000mPa.s and the vinyl content of 1.25wt%, adding 8 parts of fumed silica R974, mixing for 1-4 hours at the temperature of 120 ℃ at the rotating speed of 100rpm, and vacuumizing to obtain a base material.
(2) Preparing hydrogen-containing polysilsesquioxane serving as a reinforcing agent:
adding concentrated sulfuric acid into a 250ml three-neck flask, uniformly mixing tetraethoxysilane (A) and tetramethyl dihydrodisiloxane (B) according to a molar ratio of 2:1, adding the mixture into the flask while stirring, controlling the temperature at 60-90 ℃, and controlling the molar ratio of A to B to C to be 2:1: (3-6) adding deionized water (C), mechanically stirring, condensing and refluxing for 18-48h, centrifuging the lower layer, washing with absolute methanol, and drying in a vacuum drying oven at 40-50 ℃ for 12h to obtain the white hydrogen-containing polysilsesquioxane cage type siloxane. The value of a in (RSiO 3/2) a is adjusted by controlling the amount of water used.
(3) Heat conductive powder treatment: 10 parts of a titanate coupling agent structure of formula (6), wherein x=2, y=3, z=3, are premixed with 10 parts of ethanol. 98 parts of heat conducting powder is added into a high-speed mixer at the rotating speed of 1000r/min, 2 parts of pretreated titanate coupling agent is added after the temperature reaches 100 ℃ and water vapor is discharged, stirring is continued, discharging is stopped when the temperature reaches 105 ℃, and sealing packaging is carried out for standby.
(4) Preparing heat conduction insulating silica gel: adding 6-10 parts of base material, 5.6-20 parts of active diluent and 0.05-1 part of catalyst into a double-planetary gravity stirrer at room temperature, and uniformly mixing in vacuum; adding 250-400 parts of heat conducting filler, uniformly mixing in vacuum, adding 1-5 parts of adhesive, 0.01-1 part of inhibitor, uniformly mixing in vacuum, then adding 0.1-2 parts of reinforcing agent, uniformly mixing in vacuum, finally adding 0.5-5 parts of hydrogen-containing silicone oil, fully and uniformly stirring in vacuum, discharging, and sealing and preserving to obtain the heat conducting insulating silica gel.
Example 1
Preparing heat conduction insulating silica gel: at room temperature, adding 8 parts of base material, 6 parts of active diluent with the viscosity of 400mPa.s and the vinyl content of 8wt% into a double-planetary gravity stirrer, and 0.5 part of platinum (0) -vinyl tetramethyl dihydro disiloxane complex catalyst with the platinum content of 5000ppm, and uniformly mixing in vacuum; 144 parts of the titanate-treated 2.5um surface passivation aluminum powder and 175 parts of the titanate-treated 50um spherical boron nitride are added, vacuum mixing is carried out again, 1.5 parts of an adhesive with a structure of (4) formula j=3 and k=2 and 1.5 parts of an adhesive with a structure of (5) formula m=2 and n=2 are added, vacuum mixing is carried out on 0.05 part of an acetylene-cyclohexanol inhibitor, then 0.5 part of (RSiO 3/2)6 and 0.5 part of (RSiO 3/2)8 reinforcing agent) are added, vacuum mixing is carried out, and finally 3.5 parts of hydrogen-containing silicone oil with a structure of R' = -H and m= 5,N =4 such as (2) are added, vacuum fully stirred uniformly, discharged and sealed and stored, thus obtaining the heat-conducting insulating silica gel.
Example 2
Preparing heat conduction insulating silica gel: at room temperature, adding 8 parts of base material, 20 parts of active diluent with viscosity of 1000mPa.s and vinyl content of 2.3wt% and 0.5 part of platinum (0) -vinyl tetramethyl dihydro disiloxane complex catalyst with platinum content of 5000ppm into a double-planetary gravity stirrer, and uniformly mixing in vacuum; 144 parts of the titanate-treated 2.5um surface passivation aluminum powder and 175 parts of the titanate-treated 50um spherical boron nitride are added, vacuum mixing is carried out again, 1.5 parts of an adhesive with a structure of (4) formula j=3 and k=2 and 1.5 parts of an adhesive with a structure of (5) formula m=2 and n=2 are added, vacuum mixing is carried out on 0.05 part of an acetylene-cyclohexanol inhibitor, then 0.5 part of (RSiO 3/2)6 and 0.5 part of (RSiO 3/2)8 reinforcing agent) are added, vacuum mixing is carried out, and finally 3.5 parts of hydrogen-containing silicone oil with a structure of R' = -H and m= 5,N =4 such as (2) are added, vacuum fully stirred uniformly, discharged and sealed and stored, thus obtaining the heat-conducting insulating silica gel.
Example 3
Preparing heat conduction insulating silica gel: at room temperature, adding 8 parts of base material, 6 parts of active diluent with the viscosity of 400mPa.s and the vinyl content of 8wt% into a double-planetary gravity stirrer, and 0.5 part of platinum (0) -vinyl tetramethyl dihydro disiloxane complex catalyst with the platinum content of 5000ppm, and uniformly mixing in vacuum; adding 120 parts of the titanate-treated 2.5um surface passivation aluminum powder and 200 parts of the titanate-treated 50um spherical boron nitride, mixing again in vacuum, adding 1.5 parts of an adhesive with a structure of (4) formula j=3 and k=2 and 1.5 parts of an adhesive with a structure of (5) formula m=2 and n=2, mixing uniformly in vacuum, adding 0.05 part of an acetylene-cyclohexanol inhibitor, adding 0.5 part of (RSiO 3/2)6 and 0.5 part of (RSiO 3/2)8 reinforcing agent), mixing uniformly in vacuum, adding 3.5 parts of hydrogen-containing silicone oil with a structure of R' = -H and m= 5,N =4 such as (2), stirring uniformly in vacuum, discharging, sealing and preserving to obtain the heat-conducting insulating silica gel.
Example 4
Preparing heat conduction insulating silica gel: at room temperature, adding 8 parts of base material, 6 parts of active diluent with the viscosity of 400mPa.s and the vinyl content of 8wt% into a double-planetary gravity stirrer, and 0.5 part of platinum (0) -vinyl tetramethyl dihydro disiloxane complex catalyst with the platinum content of 5000ppm, and uniformly mixing in vacuum; 144 parts of the titanate-treated 2.5um surface passivation aluminum powder and 175 parts of the titanate-treated 50um spherical boron nitride are added, vacuum mixing is carried out again, 3 parts of adhesive with a structure of (4) formula j=3 and k=2 is added, 0.05 part of acetylene-cyclohexanol inhibitor is vacuum mixed uniformly, then 0.5 part of (RSiO 3/2)6 and 0.5 part of (RSiO 3/2)8 reinforcing agent) are added, vacuum mixing is carried out uniformly, and finally 3.5 parts of hydrogen-containing silicone oil with a structure of R' = -H and M= 5,N =4 like (2) are added, vacuum fully and uniformly stirred, then the mixture is discharged, and the mixture is sealed and stored to obtain the heat-conducting insulating silicone.
Example 5
Preparing heat conduction insulating silica gel: at room temperature, adding 8 parts of base material, 6 parts of active diluent with the viscosity of 400mPa.s and the vinyl content of 8wt% into a double-planetary gravity stirrer, and 0.5 part of platinum (0) -vinyl tetramethyl dihydro disiloxane complex catalyst with the platinum content of 5000ppm, and uniformly mixing in vacuum; 144 parts of the titanate-treated 2.5um surface passivation aluminum powder and 175 parts of the titanate-treated 50um spherical boron nitride are added, vacuum mixing is carried out again, 3 parts of an adhesive with a structure of (5) formula m=2 and n=2 is added, 0.05 part of an acetylene-cyclohexanol inhibitor is vacuum mixed uniformly, then 0.5 part of (RSiO 3/2)6 and 0.5 part of (RSiO 3/2)8 reinforcing agent) are added, vacuum mixing is carried out uniformly, and finally 3 parts of hydrogen-containing silicone oil with a structure of R' = -H and M= 5,N =4 like (2) are added, vacuum fully and uniformly stirred, then the mixture is discharged, and the mixture is sealed and stored to obtain the heat-conducting insulating silicone.
Comparative example 1: the difference from example 1 is that the added heat conductive powder was not treated with titanate coupling agent.
Comparative example 2: the difference from example 1 is that the titanate coupling agent selected is the titanate coupling agent KR-TTS.
Comparative example 3: the difference from example 1 is that the reactive diluent chosen is a terminal vinyl silicone oil having a viscosity of 500mPa.s and a vinyl content of 0.43% by weight.
Comparative example 4: the difference from example 1 is that the adhesives selected are silane coupling agents KH560 and KH570 1:1 and 1.5 parts of each.
Comparative example 5: the difference from example 1 is that the reinforcing agent selected is a commercially available HMQ resin having a hydrogen content of 0.8 wt%.
Testing
The curing conditions of the heat-conducting insulating silica gel are as follows: 125 deg.c for 2 hr.
The properties of the thermally conductive and insulating silica gels of the present invention of examples 1 to 5 and comparative examples 1 to 5 were tested by the following test.
1. Extrusion Rate test
Test conditions: 30cc rubber tube, aperture 2.4mm, pressure 0.6MPa.
The testing method comprises the following steps: the amount of gum discharged per minute is weighed in units of: g/min.
2. Thermal conductivity testing
And (3) preparing a heat conducting sheet: and defoaming the heat-conducting insulating silica gel, scraping the foam on a tetrafluoro plate, wherein the thickness is not less than 5mm, and the diameter is not less than 15mm.
The heat conductivity testing method comprises the following steps: the heat conductivity of the heat conductive sheet was measured with a heat conductive instrument in W/mK.
3. Tensile Strength and elongation at Break test
The test is carried out according to the test standard of GB/T528-2008 rubber tensile stress strain performance.
4. Adhesive strength test
And (3) defoaming the heat-conducting insulating silica gel, dispensing the heat-conducting insulating silica gel onto a PCB-Ni interface by using a dispensing machine, wherein the gap is 0.15mm, the diameter of the bonded heat-conducting insulating silica gel is about 6mm, and obtaining a drawing sample, and measuring the drawing strength of the drawing sample by using a chip pusher after the drawing sample is cured under the curing conditions.
The test results of examples 1 to 5 are shown in Table 1 and the test results of comparative examples 1 to 5 are shown in Table 2.
TABLE 1 Performance test results of the samples prepared in examples 1-5
TABLE 2 Performance test results of the samples prepared in comparative examples 1 to 5
Examples 1-5 have significantly improved extrusion rates and significantly improved strength and adhesion, although the thermal conductivity is not significantly different from that of comparative example 1; the titanate coupling agent has obvious treatment effect on the surface of powder, the powder is easy to disperse, the compatibility is good, the heat conduction is unchanged, the extrusion rate is improved, and the mechanical property and the adhesion are improved. In comparative examples 1-5 and comparative example 2, compared with KR-TTS, the titanate coupling agent provided by the invention has the advantages that the compatibility of powder and silica gel is better due to the introduction of the silica chain end, the extrusion rate is improved, the filling quantity of the powder can be correspondingly improved, the heat conduction can be further improved, the timely dissipation of heat generated by a chip is facilitated, meanwhile, the stress concentration point is reduced due to the improvement of the dispersibility, the strength after solidification is improved, the corresponding drawing strength is improved, and the elongation at break is obviously improved.
Compared with the comparative example 3, the reactive diluent disclosed by the invention is of a comb-shaped branched polyvinyl silicone oil, and compared with the inherent structure of the common section of vinyl silicone oil, the reactive diluent disclosed by the invention has the advantages that the fluidity can be effectively increased, the viscosity of a system is reduced, and meanwhile, a plurality of reactive groups are provided, so that the crosslinking point can be increased, and the strength is improved to a certain extent.
Examples 1 to 5 are significantly improved in the tensile strength and the failure mode is changed into bulk failure as compared with comparative example 4, so that it is apparent that the adhesive according to the present invention can significantly improve the adhesive strength of the thermally conductive insulating silica gel to different substrates by introducing various groups.
Examples 1-5 have higher tensile strength and higher elongation than comparative example 5, and hydrogen-containing polysilsesquioxane (RSiO 3/2) a, when a=6, has high hydrosilylation activity and can react with vinyl groups rapidly to form reinforcing points; when a=8, 10,12, the cage structure of the nano particles of the reinforcing agent of the structural formula (3) can also deform to stop the development of the microcrack tip of the resin, induce silver streaks or shear bands, or rearrange molecular chains, and promote the improvement of toughness. Has obvious reinforcing effect and can raise the breaking elongation.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (4)
1. The heat-conducting insulating silica gel for high-strength semiconductor packaging is characterized by comprising the following components in parts by weight:
6-10 parts of base material;
5.6-20 parts of reactive diluent;
0.5 to 5 portions of hydrogen silicone oil;
0.1-2 parts of reinforcing agent;
1-5 parts of adhesive;
0.05-1 part of catalyst;
0.01 to 1 part of inhibitor;
250-400 parts of heat conducting filler;
The base material is formed by kneading methyl vinyl silicone oil or vinyl silicone resin, fumed silica and a structural control agent, and the mass ratio of the base material is (65-90): (5-15): (0.5-5);
the reactive diluent is branched polyvinyl silicone oil containing reactive group vinyl, the viscosity is 300-2000 mPa.s, and the vinyl content is 0.1-8wt%; the structure of the reactive diluent is shown as (1),
In the formula (1), e, f, g, h has a value range of 1 to 100;
The reinforcing agent is hydrogen-containing polysilsesquioxane (RSiO 3/2) a, a=6, 8, 10, 12, wherein r= -OSi (CH 3)2 H;
The adhesive is one or a mixture of two of the formulas (4) and (5),
Wherein j, m=1 to 4, k, n=1 to 3, 0.ltoreq.R1.ltoreq.3;
The heat conducting filler is one or a mixture of two of surface passivation aluminum powder with the particle size of 2.5um and spherical boron nitride with the particle size of 50um, which are treated by titanate coupling agent;
the titanate coupling agent for treating the heat-conducting filler has a structure shown in a formula (6),
Wherein x=2 to 3, y=2 to 3, and z=1 to 5.
2. The heat-conducting insulating silica gel according to claim 1, wherein the methyl vinyl silicone oil is vinyl-terminated silicone oil, the viscosity is 1000-100000 mpa.s, and the vinyl content is 0.02-2 wt%; the structuring control agent is one of dimethyl dichlorosilane and hexamethyldisilazane; the catalyst is a platinum (0) -vinyl tetramethyl dihydro disiloxane complex, and the platinum content is 3000-10000 ppm; the inhibitor is any one of 2-methyl-3-butyn-2-ol, acetylene cyclohexanol and 3-methyl-1-pentyn-3-ol.
3. The heat-conducting insulating silica gel according to claim 1, wherein the structural formula of the hydrogen-containing silicone oil is shown as (2),
Wherein, R' = -CH 3 or-H, m=2-15, n=2-5.
4. A method for preparing the heat conductive insulating silica gel according to any one of claims 1 to 3, comprising the steps of:
(1) Preparing a base material:
The mass of methyl vinyl silicone oil or vinyl silicone resin, fumed silica and a structuring control agent is calculated according to the following proportion (65-90): (5-15): (0.5-5), sequentially adding the materials into a kneader, mixing the materials for 1-4 hours at 120 ℃ at the rotating speed of 50-200 rpm, and vacuumizing to obtain a base material;
(2) Preparing hydrogen-containing polysilsesquioxane serving as a reinforcing agent:
Adding concentrated sulfuric acid into a 250ml three-neck flask, uniformly mixing tetraethoxysilane (A) and tetramethyl dihydrodisiloxane (B) according to a molar ratio of 2:1, adding the mixture into the flask while stirring, controlling the temperature at 60-90 ℃, and controlling the molar ratio of A to B to C to be 2:1: (3-6) adding deionized water (C), mechanically stirring, condensing and refluxing for 18-48H, centrifuging the lower layer, washing with absolute methanol, and drying at 40-50 ℃ in a vacuum drying oven for 8-20H to obtain white hydrogen-containing polysilsesquioxane cage type siloxane;
(3) Heat conductive powder treatment:
Titanate coupling agent and ethanol are mixed according to the proportion of 1:1, premixing, namely adding the heat conducting powder into a high-speed mixer for rotating at a speed of 800-1500r/min, discharging water vapor at a temperature of 90-100 ℃, and then, conducting powder according to the mass ratio: titanate coupling agent: ethanol= (88-99): (0.3-3): (0.3-3), adding the pretreated titanate coupling agent, stopping discharging when the temperature reaches 105 ℃, and sealing and packaging for later use;
(4) Preparing heat conduction insulating silica gel:
Adding 6-10 parts of base material, 5.6-20 parts of active diluent and 0.05-1 part of catalyst into a double-planetary gravity stirrer at room temperature, and uniformly mixing in vacuum; adding 250-400 parts of heat conducting filler, uniformly mixing in vacuum, adding 1-5 parts of adhesive, 0.01-1 part of inhibitor, uniformly mixing in vacuum, then adding 0.1-2 parts of reinforcing agent, uniformly mixing in vacuum, finally adding 0.5-5 parts of hydrogen-containing silicone oil, fully and uniformly stirring in vacuum, discharging, and sealing and preserving to obtain the heat conducting insulating silica gel.
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| CN102146208A (en) * | 2011-01-26 | 2011-08-10 | 广州市高士实业有限公司 | Preparation method of transparent dealcoholized single-component room temperature vulcanized silicone rubber |
| CN109504340A (en) * | 2018-11-20 | 2019-03-22 | 烟台德邦科技有限公司 | High-strength organic silicon heat-conducting sealant and preparation method thereof |
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| WO2015093329A1 (en) * | 2013-12-19 | 2015-06-25 | 東レ・ダウコーニング株式会社 | Silicone adhesive film and semiconductor device |
| CN109504341A (en) * | 2018-11-21 | 2019-03-22 | 烟台德邦科技有限公司 | Anti-poisoning high-adhesion organosilicon heat-conducting sealant and preparation method thereof |
| CN110894420A (en) * | 2019-11-11 | 2020-03-20 | 烟台德邦科技有限公司 | Boiling-resistant high-adhesion silica gel and preparation method thereof |
| CN110951451A (en) * | 2019-12-19 | 2020-04-03 | 肇庆皓明有机硅材料有限公司 | Packaging adhesive for LED and preparation method thereof |
| WO2022140877A1 (en) * | 2020-12-28 | 2022-07-07 | 广州市白云化工实业有限公司 | Addition-type silicone rubber having high adhesive strength and preparation method therefor |
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| CN102146208A (en) * | 2011-01-26 | 2011-08-10 | 广州市高士实业有限公司 | Preparation method of transparent dealcoholized single-component room temperature vulcanized silicone rubber |
| CN109504340A (en) * | 2018-11-20 | 2019-03-22 | 烟台德邦科技有限公司 | High-strength organic silicon heat-conducting sealant and preparation method thereof |
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