CN116004183A - High-temperature-resistant adhesive for microelectronic device and preparation method thereof - Google Patents
High-temperature-resistant adhesive for microelectronic device and preparation method thereof Download PDFInfo
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- CN116004183A CN116004183A CN202310051106.3A CN202310051106A CN116004183A CN 116004183 A CN116004183 A CN 116004183A CN 202310051106 A CN202310051106 A CN 202310051106A CN 116004183 A CN116004183 A CN 116004183A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 70
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 70
- 238000004377 microelectronic Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 49
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 40
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 40
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 23
- 239000003822 epoxy resin Substances 0.000 claims description 21
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 17
- 239000000919 ceramic Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 11
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- -1 trimellitic anhydride acyl chloride Chemical class 0.000 claims description 11
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 10
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 7
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- 230000007423 decrease Effects 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
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- 229910001067 superalloy steel Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 6
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 6
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- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
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Abstract
At present, polyimide organic adhesives, although having good heat resistance, undergo cracking at high temperatures to cause a decrease in adhesive strength, and their application at high temperatures of 500 ℃ is greatly limited. Therefore, the adhesive with high temperature resistance and high bonding strength is prepared, and has important application value in the field of microelectronic devices. The invention discloses a high-temperature-resistant adhesive for a microelectronic device and a preparation method of the high-temperature-resistant adhesive for the microelectronic device. The high-temperature-resistant adhesive for the microelectronic device can resist the high temperature of 500 ℃, has extremely high heat-resistant stability, and has excellent adhesive strength and peeling strength, and can effectively ensure the stable operation of the microelectronic device in an ultra-high temperature environment when being applied to the microelectronic device.
Description
Technical Field
The invention relates to the technical field of high-temperature-resistant adhesives, in particular to a high-temperature-resistant adhesive for a microelectronic device and a preparation method thereof.
Background
The development of science and technology is very advanced, especially the rapid development of advanced fields such as aerospace technology and microelectronics, and higher requirements are also put forward on the material and material properties in the fields, especially the high temperature resistance, mechanical properties, chemical stability and the like. The development of high temperature resistant organic adhesives has become an international research project, and the high temperature resistant organic adhesives are capable of being used continuously for about 5 years at a high temperature of 120-175 ℃, or capable of being used continuously for 2-4 ten thousand hours at a high temperature of 200-230 ℃, or capable of being used continuously for 200-1000 hours at a high temperature of 260-370 ℃, or capable of being used cumulatively for 24-200 hours at a temperature of 370-430 ℃, or capable of being used for 2-10 minutes at a temperature of 540-815 ℃.
Polyimide material is used as a polymer material with outstanding performance, and has more outstanding effect in many aspects, especially in some advanced technical industries. Polyimide materials have excellent high temperature resistance, radiation resistance and low dielectric constants, and can be used as functional adhesive materials in the microelectronics field in general, and in large-scale and even very-large-scale integrated circuit boards in particular.
At present, polyimide organic adhesives, although having good heat resistance, undergo cracking at high temperatures to cause a decrease in adhesive strength, and their application at high temperatures of 500 ℃ is greatly limited. Therefore, the adhesive with high temperature resistance and high bonding strength is prepared, and has important application value in the field of microelectronic devices.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a high-temperature-resistant adhesive for a microelectronic device and a preparation method thereof.
A preparation method of a high-temperature-resistant adhesive for a microelectronic device comprises the following steps:
s1, adding 4, 4-diaminodiphenylmethane into 1-methyl-2-pyrrolidone, stirring for 1-3 hours at room temperature under the protection of nitrogen, adding trimellitic anhydride acyl chloride into the mixture under the stirring state, continuously reacting for 2-4 hours, adding maleimide and water, shearing for 1-2 hours, filtering, adding the mixture into ethanol solution, soaking for 2-5 hours, filtering, drying and crushing to obtain a prepolymer a;
s2, adding dimethyl dichlorosilane, diphenyl dichlorosilane and a catalyst into water, adding an organic solvent into the water under a stirring state, dropwise adding boric acid into the water under a stirring state, standing, removing a water layer, titrating a solvent layer to be neutral by adopting alkali liquor after washing, distilling toluene under reduced pressure at 60-80 ℃, condensing under reduced pressure at 140-150 ℃, dropwise adding a mixed solution of hydroquinone and n-propanol under the protection of nitrogen, continuing stirring for 1-2h, and performing autoclaved distillation to obtain a prepolymer b;
s3, adding the prepolymer b into absolute ethyl alcohol, uniformly stirring, adding the prepolymer a, the organic silicon resin, the epoxy resin, the chopped ceramic fiber and the tetrabutyl orthotitanate, uniformly mixing, adding the amino carborane, curing for 2-4 hours at 80-90 ℃, heating to 200-240 ℃, performing heat treatment for 10-20min, and cooling to room temperature to obtain the high-temperature-resistant adhesive for the microelectronic device.
Preferably, in S1, the mass ratio of the 4, 4-diaminodiphenylmethane to the 1-methyl-2-pyrrolidone to the trimellitic anhydride acid chloride to the maleimide is 5-10:60-100:5-10:0.1-1.
Preferably, in S1, the shear rate is 1000-2000r/min.
Preferably, in S2, the mass ratio of the mixed solution of dimethyl dichlorosilane, diphenyl dichlorosilane, a catalyst, an organic solvent, boric acid, hydroquinone and n-propanol is 2-10:1-5:0.1-0.2:20-30:1-2:1-4.
Preferably, in S2, the catalyst is a quaternary ammonium salt catalyst.
Preferably, in S2, the mass ratio of toluene to acetone is 1: 1-2. Acetone is miscible with water, and toluene is not miscible with water, but is miscible with the resulting resin. The invention uses water, toluene and acetone together, can make the reaction proceed in homogeneous phase, and at the same time, the advantage of toluene which is insoluble in water is preserved, i.e. the system reaction is mild, the organic layer solvent is decanted, the loss of solvent taken away by water is small, and at the same time, the residual water can be distilled out by azeotropy.
Preferably, in the mixed solution of the hydroquinone and the n-propanol of the S2, the mass ratio of the hydroquinone to the n-propanol is 10:1-4.
Preferably, in S3, the mass ratio of the prepolymer a to the prepolymer b to the silicone resin to the epoxy resin to the chopped ceramic fiber to the tetrabutyl orthotitanate to the amino carborane is 20-40:50-80:10-15:1-5:4-10:0.1-0.12:0.1-0.2.
Ceramic fiber is used as fiber light refractory material and has unique performance. The invention adopts ceramic fiber as reinforcing agent, can effectively improve the mechanical shock resistance of the product, and can effectively enhance the toughness of the adhesive on the basis of controlling the addition amount of the ceramic fiber and ensuring the adhesive to have certain hardness.
When the ceramic fiber exceeds the addition amount of the invention, the system is easy to generate holes, so that the toughness is reduced, and the ceramic fiber and the resin are obviously separated.
Preferably, in S3, the epoxy resin is bisphenol a type epoxy resin.
The high-temperature-resistant adhesive for the microelectronic device is prepared by adopting the preparation method of the high-temperature-resistant adhesive for the microelectronic device.
The technical effects of the invention are as follows:
the invention adopts trimellitic anhydride acyl chloride and 4, 4-diaminodiphenyl methane as monomers, wherein the trimellitic anhydride acyl chloride is dianhydride monomer, the reaction condition is mild, the side reaction is less, the 1-methyl-2-pyrrolidone and the free carboxyl of the product form hydrogen bond action, the attack of the carboxyl on the nearby amide group is effectively prevented, and maleimide is added to passivate the end group of the product, so that the progress of the side reaction is further reduced; because tertiary butyl diamine exists in the molecular structure of polyimide, the rigidity of polyimide is effectively softened after the polyimide is solidified, and the thermal stability of the polymer is enhanced and the flexibility of the product is greatly improved. In S2, boron atoms enter a molecular main chain to form boron-oxygen bonds, the bond energy of the boron-oxygen bonds is much higher than that of silicon-oxygen bonds, the main chain of the obtained prepolymer b is firmer, and the multifunctional boric acid can enable the inside of the molecule of the prepolymer b to present a bodily form network structure.
According to the invention, the prepolymer a, the prepolymer b and epoxy resin (especially bisphenol A type epoxy resin) are compounded, under the catalysis of tetrabutyl orthotitanate, stable-Si-O-C-is formed by curing treatment at 80-90 ℃, the bond energy is much larger than that of carbon-carbon bonds, and meanwhile, the formed network structure rich in-Si-O-Si-is coated on the surface of the prepolymer a, so that the network structure is not easy to be damaged even in a high-temperature environment of 200-240 ℃.
According to the invention, the resin is cured at 80-90 ℃ and then imidized by high-temperature treatment, and a great amount of experiments prove that when the temperature is lower than 200 ℃, the imidization degree is very small, and the applicant guesses that the pre-polymer a molecular chain is wrapped by a-Si-O-Si-network structure and cannot stretch, the interaction between the chains is large, the cyclization is not easy, and when the temperature is higher than 200 ℃, the imidization speed is very high, and meanwhile, the imidization degree tends to be stable along with the rise of the temperature, and when the temperature reaches 240 ℃, the imidization degree is very small, so that the effect of the temperature on imidization in the application is limited; the prepolymer a is fully and stably dispersed in a three-dimensional network structure after imidization, and the obtained adhesive can resist high temperature of 500 ℃ under the comprehensive action, has extremely high heat resistance stability, and has excellent adhesive strength and peeling strength, and can effectively ensure the stable operation of the microelectronic device in an ultra-high temperature environment when being applied to the microelectronic device.
Drawings
FIG. 1 is a graph showing the shear strength of the adhesives obtained in example 5, comparative example 1 and comparative example 2 at different temperatures.
FIG. 2 is a graph showing the peel strength of the adhesives obtained in example 5, comparative example 1 and comparative example 2 at different temperatures.
FIG. 3 is a graph showing the heat aging resistance of the adhesives obtained in example 5, comparative example 1 and comparative example 2 at 500 ℃.
FIG. 4 is a graph showing the shear strength of the adhesives obtained in example 5, comparative example 1, and comparative example 2 in natural environment/sealing environment for bonding of superalloy steel/superalloy steel.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1
A preparation method of a high-temperature-resistant adhesive for a microelectronic device comprises the following steps:
s1, adding 5kg of 4, 4-diaminodiphenylmethane into 60kg of 1-methyl-2-pyrrolidone, stirring for 1h at room temperature under the protection of nitrogen, adding 5kg of trimellitic anhydride acyl chloride into the mixture under the stirring state, continuously reacting for 2h, adding 0.1kg of maleimide and 20kg of water, shearing at the speed of 1000r/min for 1h, carrying out suction filtration, adding into an ethanol solution, soaking for 2h, filtering, drying and crushing to obtain a prepolymer a;
s2, adding 2kg of dimethyl dichlorosilane, 1kg of diphenyl dichlorosilane and 0.1kg of tetradecyl trimethyl ammonium chloride into 20kg of water, adding 20kg of organic solvent (composed of toluene and acetone according to the mass ratio of 1:1) into the mixture under stirring, dropwise adding 1kg of boric acid into the mixture under stirring, standing, removing a water layer, titrating a solvent layer to neutrality by adopting alkali liquor after washing, distilling toluene under reduced pressure at 60 ℃, condensing under reduced pressure at 140 ℃, dropwise adding 1kg of mixed solution of hydroquinone and n-propanol under nitrogen protection (the mass ratio of hydroquinone to n-propanol is 10:1), continuing stirring for 1h, and performing autoclaved distillation to obtain a prepolymer b;
s3, adding 50kg of prepolymer b into 100kg of absolute ethyl alcohol, uniformly stirring, adding 20kg of prepolymer a, 10kg of organic silicon resin, 1kg of bisphenol A type epoxy resin, 4kg of chopped ceramic fiber and 0.1kg of tetrabutyl orthotitanate, uniformly mixing, adding 0.1kg of amino carborane, curing for 2 hours at 80 ℃, then heating to 200 ℃, performing heat treatment for 10 minutes, and cooling to room temperature to obtain the high-temperature-resistant adhesive for the microelectronic device.
Example 2
A preparation method of a high-temperature-resistant adhesive for a microelectronic device comprises the following steps:
s1, adding 10kg of 4, 4-diaminodiphenylmethane into 100kg of 1-methyl-2-pyrrolidone, stirring for 3 hours at room temperature under the protection of nitrogen, adding 10kg of trimellitic anhydride acyl chloride into the mixture under the stirring state, continuously reacting for 4 hours, adding 1kg of maleimide and 60kg of water, shearing at the speed of 2000r/min for 2 hours, carrying out suction filtration, adding into ethanol solution, soaking for 5 hours, filtering, drying and crushing to obtain a prepolymer a;
s2, adding 10kg of dimethyl dichlorosilane, 5kg of diphenyl dichlorosilane and 0.2kg of tetradecyl trimethyl ammonium chloride into 30kg of water, adding 30kg of organic solvent (composed of toluene and acetone according to the mass ratio of 1:2) into the mixture under stirring, dropwise adding 2kg of boric acid into the mixture under stirring, standing, removing a water layer, titrating a solvent layer to neutrality by adopting alkali liquor after washing, distilling toluene under reduced pressure at 80 ℃, then condensing under reduced pressure at 150 ℃, dropwise adding 4kg of mixed solution of hydroquinone and n-propanol (the mass ratio of hydroquinone to n-propanol is 5:2) under nitrogen protection, continuing stirring for 2h, and performing autoclaved distillation to obtain a prepolymer b;
s3, adding 80kg of prepolymer b into 150kg of absolute ethyl alcohol, uniformly stirring, adding 40kg of prepolymer a, 15kg of organic silicon resin, 5kg of bisphenol A type epoxy resin, 10kg of chopped ceramic fiber and 0.12kg of tetrabutyl orthotitanate, uniformly mixing, adding 0.2kg of amino carborane, curing for 4 hours at 90 ℃, then heating to 240 ℃ for 20 minutes, and cooling to room temperature to obtain the high-temperature-resistant adhesive for the microelectronic device.
Example 3
A preparation method of a high-temperature-resistant adhesive for a microelectronic device comprises the following steps:
s1, adding 6kg of 4, 4-diaminodiphenylmethane into 90kg of 1-methyl-2-pyrrolidone, stirring for 1.5 hours at room temperature under the protection of nitrogen, adding 8kg of trimellitic anhydride acyl chloride into the mixture under the stirring state, continuously reacting for 2.5 hours, adding 0.8kg of maleimide and 30kg of water, shearing for 1.3 hours at the speed of 1800r/min, carrying out suction filtration, adding the mixture into an ethanol solution, soaking for 4 hours, filtering, drying and crushing to obtain a prepolymer a;
s2, adding 4kg of dimethyl dichlorosilane, 4kg of diphenyl dichlorosilane and 0.13kg of tetradecyl trimethyl ammonium chloride into 28kg of water, adding 23kg of organic solvent (composed of toluene and acetone according to the mass ratio of 1:1.2) into the mixture under stirring, dropwise adding 1.7kg of boric acid into the mixture under stirring, standing, removing a water layer, titrating the solvent layer to neutrality by adopting alkali liquor after washing, distilling toluene under reduced pressure at 65 ℃, then performing reduced pressure condensation at 147 ℃, dropwise adding 2kg of mixed solution of hydroquinone and n-propanol under nitrogen protection (the mass ratio of hydroquinone to n-propanol is 10:2), continuing stirring for 1.7h, and performing autoclaved distillation to obtain a prepolymer b;
s3, adding 60kg of prepolymer b into 140kg of absolute ethyl alcohol, uniformly stirring, adding 25kg of prepolymer a, 14kg of organic silicon resin, 2kg of bisphenol A type epoxy resin, 8kg of chopped ceramic fiber and 0.105kg of tetrabutyl orthotitanate, uniformly mixing, adding 0.17kg of amino carborane, curing for 3.5 hours at 82 ℃, heating to 210 ℃ for 17 minutes, and cooling to room temperature to obtain the high-temperature-resistant adhesive for the microelectronic device.
Example 4
A preparation method of a high-temperature-resistant adhesive for a microelectronic device comprises the following steps:
s1, adding 8kg of 4, 4-diaminodiphenylmethane into 70kg of 1-methyl-2-pyrrolidone, stirring for 2.5 hours at room temperature under the protection of nitrogen, adding 6kg of trimellitic anhydride acyl chloride into the mixture under the stirring state, continuously reacting for 3.5 hours, adding 0.2kg of maleimide and 50kg of water, shearing for 1.7 hours at the speed of 1200r/min, carrying out suction filtration, adding into ethanol solution, soaking for 3 hours, filtering, drying and crushing to obtain a prepolymer a;
s2, adding 8kg of dimethyl dichlorosilane, 2kg of diphenyl dichlorosilane and 0.17kg of tetradecyl trimethyl ammonium chloride into 22kg of water, adding 27kg of organic solvent (composed of toluene and acetone according to the mass ratio of 1:1.8) into the mixture under stirring, dropwise adding 1.3kg of boric acid into the mixture under stirring, standing, removing a water layer, titrating the solvent layer to neutrality by adopting alkali liquor after washing, distilling toluene under reduced pressure at 75 ℃, then performing reduced pressure condensation at 143 ℃, dropwise adding 3kg of mixed solution of hydroquinone and n-propanol under nitrogen protection (the mass ratio of hydroquinone to n-propanol is 10:3), continuing stirring for 1.3h, and performing autoclaved distillation to obtain a prepolymer b;
s3, adding 70kg of the prepolymer b into 120kg of absolute ethyl alcohol, uniformly stirring, adding 35kg of the prepolymer a, 12kg of organic silicon resin, 4kg of bisphenol A type epoxy resin, 6kg of chopped ceramic fiber and 0.115kg of tetrabutyl orthotitanate, uniformly mixing, adding 0.13kg of amino carborane, curing for 2.5 hours at 88 ℃, then heating to 230 ℃ for 13min, and cooling to room temperature to obtain the high-temperature-resistant adhesive for the microelectronic device.
Example 5
A preparation method of a high-temperature-resistant adhesive for a microelectronic device comprises the following steps:
s1, adding 7kg of 4, 4-diaminodiphenylmethane into 80kg of 1-methyl-2-pyrrolidone, stirring for 2 hours at room temperature under the protection of nitrogen, adding 7kg of trimellitic anhydride acyl chloride into the mixture under the stirring state, continuously reacting for 3 hours, adding 0.5kg of maleimide and 40kg of water, shearing at the speed of 1500r/min for 1.5 hours, carrying out suction filtration, adding into ethanol solution, soaking for 3.5 hours, filtering, drying and crushing to obtain a prepolymer a;
s2, adding 6kg of dimethyl dichlorosilane, 3kg of diphenyl dichlorosilane and 0.15kg of tetradecyl trimethyl ammonium chloride into 25kg of water, adding 25kg of organic solvent (composed of toluene and acetone according to the mass ratio of 1:1.5) into the mixture under stirring, dropwise adding 1.5kg of boric acid into the mixture under stirring, standing, removing a water layer, titrating the solvent layer to neutrality by adopting alkali liquor after washing, distilling toluene under reduced pressure at 70 ℃, then condensing under reduced pressure at 145 ℃, dropwise adding 2.5kg of mixed solution of hydroquinone and n-propanol under nitrogen protection (the mass ratio of hydroquinone to n-propanol is 4:1), continuing stirring for 1.5h, and performing autoclaved distillation to obtain a prepolymer b;
s3, adding 65kg of prepolymer b into 130kg of absolute ethyl alcohol, uniformly stirring, adding 30kg of prepolymer a, 13kg of organic silicon resin, 3kg of bisphenol A type epoxy resin, 7kg of chopped ceramic fiber and 0.11kg of tetrabutyl orthotitanate, uniformly mixing, adding 0.15kg of amino carborane, curing for 3 hours at 85 ℃, then heating to 220 ℃, performing heat treatment for 15 minutes, and cooling to room temperature to obtain the high-temperature-resistant adhesive for the microelectronic device.
Comparative example 1
A method for preparing an adhesive, comprising the steps of:
I. adding 6kg of dimethyl dichlorosilane, 3kg of diphenyl dichlorosilane and 0.15kg of tetradecyl trimethyl ammonium chloride into 25kg of water, adding 25kg of organic solvent (composed of toluene and acetone according to the mass ratio of 1:1.5) into the mixture under stirring, dropwise adding 1.5kg of boric acid into the mixture under stirring, standing, removing a water layer, titrating the solvent layer to neutrality by adopting alkali liquor after washing, distilling toluene under reduced pressure at 70 ℃, then condensing under reduced pressure at 145 ℃, dropwise adding 2.5kg of mixed solution of hydroquinone and n-propanol under nitrogen protection (the mass ratio of hydroquinone to n-propanol is 4:1), continuing stirring for 1.5h, and performing autoclaved distillation to obtain a prepolymer b;
II. Adding 95kg of prepolymer b into 130kg of absolute ethyl alcohol, uniformly stirring, adding 13kg of organic silicon resin, 3kg of bisphenol A type epoxy resin, 7kg of chopped ceramic fiber and 0.11kg of tetrabutyl orthotitanate, uniformly mixing, adding 0.15kg of amino carborane, curing for 3 hours at 85 ℃, heating to 220 ℃, performing heat treatment for 15 minutes, and cooling to room temperature to obtain the adhesive.
Comparative example 2
A method for preparing an adhesive, comprising the steps of:
s1, adding 7kg of 4, 4-diaminodiphenylmethane into 80kg of 1-methyl-2-pyrrolidone, stirring for 2 hours at room temperature under the protection of nitrogen, adding 7kg of trimellitic anhydride acyl chloride into the mixture under the stirring state, continuously reacting for 3 hours, adding 0.5kg of maleimide and 40kg of water, shearing at the speed of 1500r/min for 1.5 hours, carrying out suction filtration, adding into ethanol solution, soaking for 3.5 hours, filtering, drying and crushing to obtain a prepolymer a;
s3, adding 95kg of prepolymer a into 130kg of absolute ethyl alcohol, uniformly stirring, adding 13kg of organic silicon resin, 3kg of bisphenol A epoxy resin, 7kg of chopped ceramic fiber and 0.11kg of tetrabutyl orthotitanate, uniformly mixing, adding 0.15kg of amino carborane, curing for 3 hours at 85 ℃, then heating to 220 ℃, performing heat treatment for 15 minutes, and cooling to room temperature to obtain the adhesive.
The adhesives obtained in example 5 and comparative examples 1 to 2 were subjected to comparative tests, specifically as follows:
(1) Shear strength
Test pieces of each group were tested with reference to measurement of tensile shear strength of GB/T7124-2008 adhesive (rigid material to rigid material), and each group was repeated 3 times to average.
The shear strength was tested between superalloy steel/superalloy steel, siC/SiC, superalloy steel/composite, titanium alloy/titanium alloy, respectively, at room temperature, 200 ℃/10min, 400 ℃/10min, 500 ℃/10min, respectively. The results are shown in FIG. 1.
As can be seen from fig. 1: the adhesive obtained in example 5 had good adhesion properties to all four of the above-mentioned adhesive materials, and each test result was superior to that of the comparative example.
According to the invention, the prepolymer a, the prepolymer b and epoxy resin (especially bisphenol A type epoxy resin) are compounded, under the catalysis of tetrabutyl orthotitanate, stable-Si-O-C-is formed by curing treatment at 80-90 ℃, the bond energy is much larger than that of carbon-carbon bonds, meanwhile, the formed network structure rich in-Si-O-Si-is coated on the surface of the prepolymer a, imidization is carried out in a high-temperature environment of 200-240 ℃, and the prepolymer a is fully and stably dispersed in a three-dimensional network structure after imidization, so that the obtained adhesive can resist the high temperature of 500 ℃.
(2) Peel strength of
The peel strength is an important index of the mechanical property of the adhesive, and the peel strength of each group of samples on the surfaces of different materials at different temperatures is tested by adopting a 90-degree peeling mode. The results are shown in FIG. 2. As can be seen from fig. 2: the peel strength of the same material surface in each group of samples decreases with the increase of temperature, and the peel strength of the same sample surface at the same temperature and different materials is greatly different.
According to the invention, the prepolymer a, the prepolymer b and epoxy resin (especially bisphenol A type epoxy resin) are compounded, under the catalysis of tetrabutyl orthotitanate, stable-Si-O-C-is formed by curing treatment at 80-90 ℃, the bond energy is much larger than that of carbon-carbon bonds, meanwhile, the formed network structure rich in-Si-O-Si-is coated on the surface of the prepolymer a, imidization is carried out in a high-temperature environment of 200-240 ℃, and the prepolymer a is fully and stably dispersed in a three-dimensional network structure after imidization, so that the adhesive has excellent adhesive strength and peeling strength.
(3) Thermal aging resistance
Two silicon carbide pieces are respectively bonded by adopting each group of samples, then a muffle furnace is adopted to carry out 500 ℃ aging test on the silicon carbide bonding test pieces, the aging time is respectively 25h, 50h, 75h, 100h and 125h, and the tensile shear strength test is carried out on the bonding test pieces after high-temperature aging, so that the result is shown in figure 3.
As can be seen from fig. 3: the adhesive obtained in example 5 has no obvious change of tensile shear strength with the extension of time at 500 ℃, which shows that the adhesive obtained in the invention has good aging resistance at 500 ℃.
(4) Normal temperature service life
And placing each group of samples in a natural environment and a sealing environment (simulated by a glue gun) respectively for different times to determine the shear strength of the bonded superalloy steel/superalloy steel. The normal temperature service life of each set of adhesives was determined by shear strength after curing, as shown in fig. 4.
As can be seen from fig. 4: the adhesives obtained in example 5 and comparative example 2 showed little change in shear strength in both natural and sealed environments, whereas the adhesive obtained in comparative example 1 showed a decrease in shear strength with time in natural environments. The applicant believes that: this is because the molecular chain of the prepolymer a is not wrapped by the network structure of-Si-O-Si-and is directly combined with epoxy resin to carry out imidization, so that the obtained adhesive is continuously stretched in natural environment, and the shearing strength is continuously reduced.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the high-temperature-resistant adhesive for the microelectronic device is characterized by comprising the following steps of:
s1, adding 4, 4-diaminodiphenylmethane into 1-methyl-2-pyrrolidone, stirring for 1-3 hours at room temperature under the protection of nitrogen, adding trimellitic anhydride acyl chloride into the mixture under the stirring state, continuously reacting for 2-4 hours, adding maleimide and water, shearing for 1-2 hours, filtering, adding the mixture into ethanol solution, soaking for 2-5 hours, filtering, drying and crushing to obtain a prepolymer a;
s2, adding dimethyl dichlorosilane, diphenyl dichlorosilane and a catalyst into water, adding an organic solvent into the water under a stirring state, dropwise adding boric acid into the water under a stirring state, standing, removing a water layer, titrating a solvent layer to be neutral by adopting alkali liquor after washing, distilling toluene under reduced pressure at 60-80 ℃, condensing under reduced pressure at 140-150 ℃, dropwise adding a mixed solution of hydroquinone and n-propanol under the protection of nitrogen, continuing stirring for 1-2h, and performing autoclaved distillation to obtain a prepolymer b;
s3, adding the prepolymer b into absolute ethyl alcohol, uniformly stirring, adding the prepolymer a, the organic silicon resin, the epoxy resin, the chopped ceramic fiber and the tetrabutyl orthotitanate, uniformly mixing, adding the amino carborane, curing for 2-4 hours at 80-90 ℃, heating to 200-240 ℃, performing heat treatment for 10-20min, and cooling to room temperature to obtain the high-temperature-resistant adhesive for the microelectronic device.
2. The method for preparing the high temperature resistant adhesive for the microelectronic device according to claim 1, wherein in S1, the mass ratio of 4, 4-diaminodiphenylmethane to 1-methyl-2-pyrrolidone to trimellitic anhydride chloride to maleimide is 5-10:60-100:5-10:0.1-1.
3. The method for producing a high temperature resistant adhesive for microelectronic devices according to claim 1, wherein in S1, the shear rate is 1000-2000r/min.
4. The method for preparing the high temperature resistant adhesive for the microelectronic device according to claim 1, wherein in the S2, the mass ratio of the mixed liquid of dimethyl dichlorosilane, diphenyl dichlorosilane, catalyst, organic solvent, boric acid, hydroquinone and n-propanol is 2-10:1-5:0.1-0.2:20-30:1-2:1-4.
5. The method for preparing a high temperature resistant adhesive for microelectronic devices according to claim 1, wherein in S2, the catalyst is a quaternary ammonium salt catalyst.
6. The method for preparing the high temperature resistant adhesive for the microelectronic device according to claim 1, wherein in S2, the mass ratio of toluene to acetone is 1: 1-2.
7. The method for preparing the high temperature resistant adhesive for the microelectronic device according to claim 1, wherein in the mixed solution of hydroquinone and n-propanol of S2, the mass ratio of hydroquinone to n-propanol is 10:1-4.
8. The method for preparing the high temperature resistant adhesive for the microelectronic device according to claim 1, wherein in S3, the mass ratio of the prepolymer a to the prepolymer b to the silicone resin to the epoxy resin to the chopped ceramic fiber to the tetrabutyl orthotitanate to the amino carborane is 20-40:50-80:10-15:1-5:4-10:0.1-0.12:0.1-0.2.
9. The method of manufacturing a high temperature resistant adhesive for microelectronic devices according to claim 1, wherein in S3, the epoxy resin is bisphenol a type epoxy resin.
10. A high temperature resistant adhesive for microelectronic devices, characterized in that it is prepared by the method for preparing a high temperature resistant adhesive for microelectronic devices according to any one of claims 1 to 9.
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