CN115820181B - Underfill based on composite nano-filler, and preparation method and application thereof - Google Patents
Underfill based on composite nano-filler, and preparation method and application thereof Download PDFInfo
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- CN115820181B CN115820181B CN202211565594.1A CN202211565594A CN115820181B CN 115820181 B CN115820181 B CN 115820181B CN 202211565594 A CN202211565594 A CN 202211565594A CN 115820181 B CN115820181 B CN 115820181B
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- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000000945 filler Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003822 epoxy resin Substances 0.000 claims abstract description 45
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 45
- 239000002105 nanoparticle Substances 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 239000011258 core-shell material Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003292 glue Substances 0.000 claims abstract description 16
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 63
- 238000002156 mixing Methods 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 23
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 20
- -1 phenolic aldehyde amine Chemical class 0.000 claims description 17
- 150000002191 fatty alcohols Chemical group 0.000 claims description 16
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 8
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 3
- 238000004100 electronic packaging Methods 0.000 claims description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
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- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 3
- 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
- 239000000243 solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical group C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of filling glue preparation, and discloses an underfill based on composite nano-filler, and a preparation method and application thereof. The underfill based on the composite nano-filler comprises epoxy resin, polyol, a curing agent, a curing accelerator, a coupling agent, core-shell structure composite nano-particles, a dispersing agent and a defoaming agent. According to the invention, the epoxy resin is modified by combining the ferroferric oxide and the silicon dioxide, so that the ageing resistance, the material strength and the chemical corrosion resistance of the obtained underfill are further improved; meanwhile, the curing speed of the obtained underfill is moderate by matching the polyol, the curing agent and the curing accelerator, so that the working performance of the underfill is improved. The preparation process is simple, and the required reaction conditions are mild. Meanwhile, the underfill adhesive has excellent working performance and mechanical property, and ensures higher reliability of packaged components.
Description
Technical Field
The invention relates to the technical field of filling glue preparation, in particular to an underfill glue based on composite nano-filler, and a preparation method and application thereof.
Background
With the fourth industrial revolution, people start to walk into the intelligent age, chip manufacturing is an indispensable product in the intelligent age, and with the development of the chip packaging industry, more severe requirements are also put forward on chip packaging materials. Since a wafer (die) made of a single crystal silicon material has a thermal expansion coefficient far lower than that of a substrate, an underfill is widely used for a chip packaging material in order to protect the wafer (die), bumps (bump) and enhance the reliability of a chip. In chip packaging, the addition of underfill to the wafer (die) and substrate can improve the reliability and reduce the interface stress caused by the difference in thermal expansion coefficients of bump (bump) and substrate. The underfill is usually made of an epoxy resin system, has the excellent characteristics of high toughness, corrosion resistance, high viscosity, insulation and the like, but the product of the underfill is high in brittleness, easy to crack, and poor in damp and heat resistance and impact resistance after the epoxy resin is cured by adopting a common curing system. Therefore, the performance of the underfill is improved by various methods such as matrix modification, curing agent modification, filler introduction and the like in the prior art so as to meet the requirements of practical application. As the inorganic nano particles have surface effect and interface effect, the strength, toughness, heat resistance and the like of the obtained product are greatly improved after the inorganic nano particles are added into an epoxy resin curing system.
However, most of fillers adopted by the existing underfill are inorganic fillers, and the inorganic fillers have poor compatibility with an epoxy resin system, so that the fluidity of the fillers of the underfill is inconsistent with that of the resin, the filling effect is affected, and the performance of a chip is further affected. In addition, the existing underfill is generally modified by adopting a single nano filler, and the mechanical property of the underfill cannot meet the application requirements of high-quality chips. Based on this, development of an underfill having good compatibility with raw materials and excellent mechanical properties is highly demanded in the art.
Disclosure of Invention
The invention aims to provide an underfill based on composite nano-filler, a preparation method and application thereof, and aims to solve the problems that the existing underfill is poor in inorganic filler dispersibility and influences the working performance of the underfill due to poor compatibility of inorganic filler and epoxy resin, and the mechanical properties of the existing underfill cannot be obviously improved and cannot meet the application requirements of high-quality chips due to the fact that the existing underfill is modified by single nano-filler.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The invention provides an underfill based on composite nano-filler, which comprises the following components in parts by weight:
40-80 parts of epoxy resin, 1-8 parts of polyol, 8-15 parts of curing agent, 1-2 parts of curing accelerator, 0.5-1 part of coupling agent, 30-50 parts of core-shell structure composite nano particles, 0.2-1 part of dispersing agent and 0.5-1.5 parts of defoaming agent.
Preferably, the epoxy resin is bisphenol a type epoxy resin and/or alicyclic epoxy resin; the polyalcohol is one or more of pentaerythritol, xylitol and sorbitol; the curing agent is a phenolic aldehyde amine curing agent and/or an anhydride curing agent; the curing accelerator is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
Preferably, the coupling agent is vinyltriethoxysilane and/or vinyltrimethoxysilane; the dispersing agent is fatty alcohol polyoxyethylene ether and/or fatty amine polyoxyethylene ether; the defoaming agent is one or more of polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether and polyoxypropylene glycerol ether.
Preferably, in the core-shell structure composite nanoparticle, ferroferric oxide is used as a core and silicon dioxide is used as a shell.
Preferably, the preparation of the core-shell structure composite nanoparticle comprises the following steps:
Mixing ferric trichloride, ferric dichloride and a solvent, sequentially adding alkali liquor 1 and citric acid for reaction, and performing aftertreatment to obtain a ferroferric oxide nucleus; and mixing and reacting the citric acid glue solution of the ferroferric oxide nucleus, the surfactant, the alkali liquor 2 and the tetraethoxysilane to obtain the core-shell structure composite nano particle.
Preferably, the alkali liquor 1 and the alkali liquor 2 are ammonia water; the surfactant is polyethylene glycol octyl phenyl ether and/or cyclohexane; the mol volume ratio of the ferric trichloride to the ferric dichloride to the solvent is 1-2 mmol:0.5 to 1mmol: 20-25 mL; the addition amount of the alkali liquor 1 is that the pH value of the mixed liquor obtained by mixing ferric trichloride, ferric dichloride and a solvent is 8.5-10; the volume ratio of the citric acid to the solvent is 1: 55-65; the concentration of the citric acid glue solution of the ferroferric oxide nucleus body is 4-5 mg/mL; the volume ratio of the citric acid glue solution, the surfactant, the alkali liquor 2 and the tetraethoxysilane of the ferroferric oxide nucleus body is 1-1.2: 75-90: 0.5 to 0.8:1 to 1.5.
Preferably, the reaction is carried out under the protection gas, the reaction temperature is 70-90 ℃, and the reaction time is 1-2 h; the mixing reaction time is 15-20 h.
The invention also provides a preparation method of the underfill based on the composite nano-filler, which comprises the following steps:
Mixing epoxy resin, polyol, a curing agent, a curing accelerator, a coupling agent, core-shell structure composite nano particles, a dispersing agent and a defoaming agent, and then reacting to obtain the underfill based on the composite nano filler.
Preferably, the vacuum degree of the reaction is-0.08 to-0.05 MPa, the reaction temperature is 20-30 ℃, and the reaction time is 2-3 h.
The invention also provides application of the underfill based on the composite nano-filler in an electronic packaging chip.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the underfill is prepared from composite nano-filler, namely core-shell structure composite nano-particles, and the epoxy resin is modified by combining ferroferric oxide and silicon dioxide, so that the ageing resistance, the material strength and the chemical corrosion resistance of the obtained underfill are further improved; compared with nano particles obtained by combining ferroferric oxide with silicon dioxide and single silicon dioxide nano particles, the nano particles obtained by combining ferroferric oxide with silicon dioxide have higher combining ability with epoxy resin, so that the dispersibility of the nano particles in the epoxy resin can be improved, and the fluidity of the obtained underfill is improved;
(2) According to the invention, the polyol, the curing agent and the curing accelerator are matched, so that the curing speed of the obtained underfill is moderate, and the working performance of the underfill is improved;
(3) The preparation process is simple, does not need large-scale equipment, has mild reaction conditions, and is suitable for large-scale popularization and application.
Detailed Description
The invention provides an underfill based on composite nano-filler, which comprises the following components in parts by weight:
40-80 parts of epoxy resin, 1-8 parts of polyol, 8-15 parts of curing agent, 1-2 parts of curing accelerator, 0.5-1 part of coupling agent, 30-50 parts of core-shell structure composite nano particles, 0.2-1 part of dispersing agent and 0.5-1.5 parts of defoaming agent.
In the underfill of the present invention, the amount of the epoxy resin is preferably 45 to 75 parts, more preferably 50 to 70 parts; the amount of the polyhydric alcohol to be used is preferably 2 to 7 parts, more preferably 3 to 6 parts; the amount of the curing agent is preferably 9 to 12 parts, more preferably 10 to 11 parts; the amount of the curing accelerator is preferably 1.2 to 1.8 parts, more preferably 1.3 to 1.7 parts; the amount of the coupling agent is preferably 0.6 to 0.9 part, more preferably 0.7 to 0.8 part; the dosage of the core-shell structure composite nano particles is preferably 35 to 45 parts, and more preferably 38 to 40 parts; the amount of the dispersant is preferably 0.5 to 0.9 part, more preferably 0.6 to 0.8 part; the amount of the defoaming agent is preferably 0.6 to 1.2 parts, more preferably 0.8 to 1 part.
In the present invention, the epoxy resin is preferably a bisphenol a-type epoxy resin and/or a cycloaliphatic epoxy resin, more preferably a bisphenol a-type epoxy resin; the bisphenol A type epoxy resin is preferably an E-55 bisphenol A type epoxy resin, an E-51 bisphenol A type epoxy resin and an E-44 bisphenol A type epoxy resin, and more preferably an E-55 bisphenol A type epoxy resin and/or an E-51 bisphenol A type epoxy resin; the alicyclic epoxy resin is preferably alicyclic epoxy resin S-21 and/or alicyclic epoxy resin CER-170, and more preferably alicyclic epoxy resin S-21.
In the present invention, the polyhydric alcohol is preferably one or more of pentaerythritol, xylitol and sorbitol, and more preferably pentaerythritol or sorbitol.
In the present invention, the curing agent is preferably a phenolic amine curing agent and/or an acid anhydride curing agent, and more preferably a phenolic amine curing agent; the phenolic amine curing agent is preferably one or more of phenolic amine curing agent KM-260, phenolic amine curing agent T-33 and phenolic amine curing agent T-31, and more preferably phenolic amine curing agent KM-260; the acid anhydride curing agent is preferably one or more of phthalic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride and dodecylsuccinic anhydride, and more preferably one or more of phthalic anhydride, pyromellitic anhydride and dodecylsuccinic anhydride.
In the present invention, the curing accelerator is preferably one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, and more preferably 2-ethyl-4-methylimidazole and/or 2-phenylimidazole.
In the present invention, the coupling agent is preferably vinyltriethoxysilane and/or vinyltrimethoxysilane, more preferably vinyltriethoxysilane or vinyltrimethoxysilane.
In the present invention, the dispersant is preferably fatty alcohol polyoxyethylene ether and/or fatty amine polyoxyethylene ether, and more preferably fatty alcohol polyoxyethylene ether; the fatty alcohol polyoxyethylene ether is preferably fatty alcohol polyoxyethylene ether AEO-3 and/or fatty alcohol polyoxyethylene ether AEO-9, and further preferably fatty alcohol polyoxyethylene ether AEO-9; the fatty amine polyoxyethylene ether is preferably fatty amine polyoxyethylene ether AC-1860 and/or fatty amine polyoxyethylene ether AC-1815, and further preferably fatty amine polyoxyethylene ether AC-1860.
In the present invention, the defoaming agent is preferably one or more of polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether and polyoxypropylene glycerol ether, and more preferably polyoxyethylene polyoxypropylene pentaerythritol ether and/or polyoxyethylene polyoxypropylene alcohol amine ether.
The polyol, the curing agent and the curing accelerator are combined, wherein the curing speed of an epoxy resin system can be adjusted by adding the polyol, and the underfill with moderate curing speed can be obtained by combining the polyol, the curing agent and the curing accelerator, so that the working performance and the toughness of the underfill are improved.
In the composite nanoparticle with the core-shell structure, ferroferric oxide is used as a core and silicon dioxide is used as a shell.
In the invention, the preparation of the core-shell structure composite nanoparticle comprises the following steps:
Mixing ferric trichloride, ferric dichloride and a solvent, sequentially adding alkali liquor 1 and citric acid for reaction, and performing aftertreatment to obtain a ferroferric oxide nucleus; and mixing and reacting the citric acid glue solution of the ferroferric oxide nucleus, the surfactant, the alkali liquor 2 and the tetraethoxysilane to obtain the core-shell structure composite nano particle.
In the invention, the specific steps of mixing ferric trichloride, ferric dichloride and a solvent, and then sequentially adding alkali liquor 1 and citric acid for reaction are as follows: mixing ferric trichloride, ferric dichloride and a solvent, adding alkali liquor 1 under the condition of introducing protective gas, stirring and mixing, and then adding citric acid for reaction;
The shielding gas is preferably nitrogen or argon, and more preferably nitrogen; the stirring and mixing time is preferably 20 to 40min, more preferably 25 to 35min, and the stirring and mixing temperature is preferably 70 to 85 ℃ and more preferably 75 to 80 ℃; the stirring and mixing speed is preferably 500-800 r/min, and more preferably 600-700 r/min;
The reaction is carried out under a shielding gas, preferably nitrogen or argon, more preferably nitrogen; the reaction temperature is preferably 70 to 90 ℃, more preferably 75 to 85 ℃; the reaction time is preferably 1 to 2 hours, more preferably 1.5 hours.
In the invention, the post-treatment is specifically implemented by the following steps: sequentially carrying out centrifugal separation, washing and drying on the product obtained by the reaction;
The rotation speed of the centrifugal separation is preferably 1000-2000 r/min, and more preferably 1200-1800 r/min; the time for the centrifugal separation is preferably 10 to 30 minutes, more preferably 15 to 25 minutes; the reagent used for the washing is preferably water, and the number of times of washing is preferably 2 to 4 times, more preferably 3 times; the drying temperature is preferably 60 to 70 ℃, and more preferably 65 to 68 ℃; the drying time is preferably 10 to 30 minutes, more preferably 15 to 25 minutes.
In the invention, the concrete steps of mixing and reacting the citric acid glue solution of the ferroferric oxide nucleus, the surfactant, the alkali solution 2 and the tetraethoxysilane are as follows: mixing a citric acid glue solution of a ferroferric oxide nucleus body, a surfactant and an alkali liquor 2, and then dropwise adding tetraethoxysilane for mixing reaction;
The dropping speed is preferably 0.8-1.6 mL/min, and more preferably 1-1.4 mL/min; the mixing reaction time is preferably 15 to 20 hours, more preferably 16 to 18 hours.
In the invention, the alkali liquor 1 and the alkali liquor 2 are preferably ammonia water, and the mass concentration of the ammonia water is preferably 20-40%, and more preferably 25-35%; the surfactant is preferably polyethylene glycol octyl phenyl ether and/or cyclohexane, and more preferably polyethylene glycol octyl phenyl ether; the molar volume ratio of the ferric trichloride to the ferric dichloride to the solvent is preferably 1-2 mmol:0.5 to 1mmol:20 to 25mL, more preferably 1.2 to 1.5mmol:0.6 to 0.8mmol: 21-24 mL; the alkali liquor 1 is preferably added in such an amount that the pH value of the mixed liquor obtained by mixing ferric trichloride, ferric dichloride and a solvent is 8.5-10, and more preferably the pH value of the mixed liquor obtained by mixing ferric trichloride, ferric dichloride and a solvent is 9; the volume ratio of the citric acid to the solvent is preferably 1:55 to 65, more preferably 1: 60-62; the concentration of the citric acid glue solution of the ferroferric oxide nucleus body is preferably 4-5 mg/mL, and more preferably 4.2-4.5 mg/mL; the volume ratio of the citric acid glue solution, the surfactant, the alkali liquor 2 and the tetraethoxysilane of the ferroferric oxide nucleus is preferably 1-1.2: 75-90: 0.5 to 0.8:1 to 1.5, more preferably 1.1: 80-85: 0.6 to 0.7:1.2 to 1.4.
According to the invention, ferroferric oxide and silicon dioxide are combined to obtain the core-shell structure composite nano particles to modify the epoxy resin, so that the ageing resistance, the material strength and the chemical corrosion resistance of the obtained underfill are further improved; the core-shell structure composite nanoparticle has the properties of ferroferric oxide and silicon dioxide, and has higher binding capacity with the epoxy resin compared with the existing single silicon dioxide nanoparticle due to the effect of ferroferric oxide and the epoxy resin, so that the dispersibility of the core-shell structure composite nanoparticle in the epoxy resin can be improved, and the fluidity of the underfill is improved.
The invention also provides a preparation method of the underfill based on the composite nano-filler, which comprises the following steps:
Mixing epoxy resin, polyol, a curing agent, a curing accelerator, a coupling agent, core-shell structure composite nano particles, a dispersing agent and a defoaming agent, and then reacting to obtain the underfill based on the composite nano filler.
In the invention, the concrete steps of mixing epoxy resin, polyol, curing agent, curing accelerator, coupling agent, core-shell structure composite nano particles, dispersing agent and defoaming agent are as follows: firstly, mixing epoxy resin, polyalcohol, coupling agent, core-shell structure composite nano particles, dispersing agent and defoaming agent, and then adding curing agent and curing accelerator for reaction.
In the present invention, the vacuum degree of the reaction is preferably-0.08 to-0.05 MPa, and more preferably-0.07 to-0.06 MPa; the reaction temperature is preferably 20 to 30 ℃, and more preferably 25 to 28 ℃; the reaction time is preferably 2 to 3 hours, more preferably 2.5 hours.
The invention also provides application of the underfill based on the composite nano-filler in an electronic packaging chip.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparing core-shell structure composite nano particles:
Mixing 4mmol of ferric trichloride, 2mmol of ferric dichloride and 80mL of water in a reaction kettle, introducing nitrogen into the reaction kettle, heating, adding 30% ammonia water at the mass concentration under the condition of 75 ℃ and nitrogen protection to adjust the pH value of the mixed solution in the reaction kettle to 9, stirring and mixing at 600r/min for 30min, adding 480mL of citric acid, and reacting at 80 ℃ for 1h; centrifuging the obtained reaction solution in a centrifuge at 1500r/min for 20min, filtering to obtain solid substances, washing the solid substances with water for 3 times, and drying in a drying oven at 60deg.C for 20min to obtain ferroferric oxide nucleus;
Mixing ferroferric oxide nuclei with citric acid to obtain a glue solution with the concentration of 4 mg/mL; mixing 10mL of the glue solution with 800mL of polyethylene glycol octyl phenyl ether and 6mL of ammonia water with mass concentration of 25% to obtain a mixture, dropwise adding 12mL of ethyl orthosilicate into the mixture at the speed of 1.2mL/min for mixing reaction for 16h, and drying the product obtained by the mixing reaction at the temperature of 60 ℃ to obtain the core-shell structure composite nano particle.
Example 2
Preparation of underfill based on composite nanofillers:
The raw materials and the dosage are as follows: 40 parts of E-55 bisphenol A epoxy resin, 2 parts of pentaerythritol, 2 parts of phenolic amine curing agent KM-26010, 1 part of 2-ethyl-4-methylimidazole, 0.5 part of vinyl triethoxysilane, 30 parts of core-shell structure composite nano particles obtained in example 1, 90.2 parts of fatty alcohol polyoxyethylene ether AEO-and 0.5 part of polyoxyethylene polyoxypropylene pentaerythritol ether;
the preparation process comprises the following steps: e-55 bisphenol A epoxy resin, pentaerythritol, vinyl triethoxysilane, the core-shell structure composite nano particles obtained in the embodiment 1, fatty alcohol polyoxyethylene ether AEO-9 and polyoxyethylene polyoxypropylene pentaerythritol ether are mixed, then phenolic amine curing agent KM-260 and 2-ethyl-4-methylimidazole are added, and the mixture is reacted for 2 hours under the conditions of vacuum degree of-0.08 MPa and temperature of 25 ℃ to obtain the underfill.
Example 3
Preparation of underfill based on composite nanofillers:
The raw materials and the dosage are as follows: 50 parts of E-51 bisphenol A type epoxy resin, 4 parts of pentaerythritol, 15 parts of phthalic anhydride, 1.5 parts of 2-ethyl-4-methylimidazole, 0.8 part of vinyl trimethoxy silane, 40 parts of core-shell structure composite nano particles obtained in example 1, 90.5 parts of fatty alcohol polyoxyethylene ether AEO-and 1 part of polyoxyethylene polyoxypropylene pentaerythritol ether;
The preparation process comprises the following steps: e-51 bisphenol A epoxy resin, pentaerythritol, vinyl trimethoxy silane, the core-shell structure composite nano particles obtained in the embodiment 1, fatty alcohol polyoxyethylene ether AEO-9 and polyoxyethylene polyoxypropylene pentaerythritol ether are mixed, phthalic anhydride and 2-ethyl-4-methylimidazole are added, and the mixture is reacted for 2 hours under the conditions of vacuum degree of-0.06 MPa and temperature of 25 ℃ to obtain the underfill.
Example 4
Preparation of underfill based on composite nanofillers:
the raw materials and the dosage are as follows: cycloaliphatic epoxy resin S-2170 parts, sorbitol 7 parts, phenolic amine curing agent T-33 parts, 2-methylimidazole 1 part, vinyltriethoxysilane 0.8 parts, core-shell structure composite nano particles obtained in example 140 parts, fatty alcohol polyoxyethylene ether AEO-90.5 parts and polyoxyethylene polyoxypropylene pentaerythritol ether 1.2 parts;
The preparation process comprises the following steps: firstly, mixing alicyclic epoxy resin S-21, sorbitol, vinyl triethoxysilane, the core-shell structure composite nano particles obtained in the embodiment 1, fatty alcohol polyoxyethylene ether AEO-9 and polyoxyethylene polyoxypropylene pentaerythritol ether, then adding phenolic amine curing agent T-33 and 2-methylimidazole, and reacting for 2 hours under the conditions of vacuum degree of-0.05 MPa and temperature of 25 ℃ to obtain the underfill.
Example 5
Preparation of underfill based on composite nanofillers:
The raw materials and the dosage are as follows: 80 parts of E-51 bisphenol A type epoxy resin, 8 parts of sorbitol, 15 parts of dodecyl succinic anhydride, 1.5 parts of 2-phenylimidazole, 0.8 part of vinyl triethoxysilane, 40 parts of core-shell structure composite nano particles obtained in example 1, 90.5 parts of fatty alcohol polyoxyethylene ether AEO-and 1.2 parts of polyoxyethylene polyoxypropylene pentaerythritol ether;
The preparation process comprises the following steps: e-51 bisphenol A epoxy resin, sorbitol, vinyl triethoxysilane, the core-shell structure composite nano particles obtained in the example 1, fatty alcohol polyoxyethylene ether AEO-9 and polyoxyethylene polyoxypropylene pentaerythritol ether are mixed, dodecyl succinic anhydride and 2-phenylimidazole are added, and the mixture is reacted for 2.5 hours under the conditions of vacuum degree of-0.07 MPa and temperature of 30 ℃ to obtain the underfill.
The underfill materials obtained in examples 2 to 5 were tested for performance, the test items and the methods used are shown in Table 1, and the test results are shown in Table 2.
Table 1 test items for performance testing and method therefor
TABLE 2 results of Performance test of the underfill obtained in examples 2 to 5
As can be seen from Table 2, the curing time of the underfill obtained by the invention is longer than that of the conventional two-stage underfill (curing time is usually 20-25 min), and meanwhile, the fluidity is excellent, which indicates that the underfill of the invention has excellent working performance; and the thermal expansion coefficient and the elastic modulus of the underfill adhesive obtained by the invention are both superior to those of the common underfill adhesive (the thermal expansion coefficient is 50-53 mu m/m ℃ and the elastic modulus is 10-11 GPa). The underfill has excellent mechanical properties while having excellent working properties, and ensures higher reliability of packaging components.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The underfill based on the composite nano-filler is characterized by comprising the following components in parts by weight:
40-80 parts of epoxy resin, 1-8 parts of polyol, 8-15 parts of curing agent, 1-2 parts of curing accelerator, 0.5-1 part of coupling agent, 30-50 parts of core-shell structure composite nano particles, 0.2-1 part of dispersing agent and 0.5-1.5 parts of defoaming agent;
In the core-shell structure composite nanoparticle, ferroferric oxide is taken as a core and silicon dioxide is taken as a shell;
The preparation of the core-shell structure composite nanoparticle comprises the following steps:
Mixing ferric trichloride, ferric dichloride and a solvent, sequentially adding alkali liquor 1 and citric acid for reaction, and performing aftertreatment to obtain a ferroferric oxide nucleus; and mixing and reacting the citric acid glue solution of the ferroferric oxide nucleus, the surfactant, the alkali liquor 2 and the tetraethoxysilane to obtain the core-shell structure composite nano particle.
2. The underfill based on composite nanofillers according to claim 1, wherein the epoxy resin is bisphenol a type epoxy resin and/or cycloaliphatic epoxy resin; the polyalcohol is one or more of pentaerythritol, xylitol and sorbitol; the curing agent is a phenolic aldehyde amine curing agent and/or an anhydride curing agent; the curing accelerator is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
3. Underfill based on composite nanofillers according to claim 2, wherein the coupling agent is vinyltriethoxysilane and/or vinyltrimethoxysilane; the dispersing agent is fatty alcohol polyoxyethylene ether and/or fatty amine polyoxyethylene ether; the defoaming agent is one or more of polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether and polyoxypropylene glycerol ether.
4. The underfill based on composite nanofillers according to claim 1, wherein the lye 1 and lye 2 are ammonia water; the surfactant is polyethylene glycol octyl phenyl ether and/or cyclohexane; the mol volume ratio of the ferric trichloride to the ferric dichloride to the solvent is 1-2 mmol:0.5 to 1mmol: 20-25 mL; the addition amount of the alkali liquor 1 is that the pH value of the mixed liquor obtained by mixing ferric trichloride, ferric dichloride and a solvent is 8.5-10; the volume ratio of the citric acid to the solvent is 1: 55-65; the concentration of the citric acid glue solution of the ferroferric oxide nucleus body is 4-5 mg/mL; the volume ratio of the citric acid glue solution, the surfactant, the alkali liquor 2 and the tetraethoxysilane of the ferroferric oxide nucleus body is 1-1.2: 75-90: 0.5 to 0.8:1 to 1.5.
5. The underfill based on composite nanofillers according to claim 1 or 4, wherein the reaction is carried out under a protective gas at a temperature of 70 to 90 ℃ for a time of 1 to 2 hours; the mixing reaction time is 15-20 h.
6. The method for preparing underfill based on composite nanofiller according to any one of claims 1 to 5, comprising the steps of:
Mixing epoxy resin, polyol, a curing agent, a curing accelerator, a coupling agent, core-shell structure composite nano particles, a dispersing agent and a defoaming agent, and then reacting to obtain the underfill based on the composite nano filler.
7. The method for preparing underfill based on composite nano-filler according to claim 6, wherein the vacuum degree of the reaction is-0.08 to-0.05 MPa, the reaction temperature is 20-30 ℃, and the reaction time is 2-3 h.
8. Use of the underfill based on composite nanofillers according to any one of claims 1 to 5 in electronic packaging chips.
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