CN115820181A - Underfill adhesive based on composite nano filler and preparation method and application thereof - Google Patents
Underfill adhesive based on composite nano filler and preparation method and application thereof Download PDFInfo
- Publication number
- CN115820181A CN115820181A CN202211565594.1A CN202211565594A CN115820181A CN 115820181 A CN115820181 A CN 115820181A CN 202211565594 A CN202211565594 A CN 202211565594A CN 115820181 A CN115820181 A CN 115820181A
- Authority
- CN
- China
- Prior art keywords
- underfill
- core
- parts
- epoxy resin
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 239000000945 filler Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000853 adhesive Substances 0.000 title claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 44
- 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 29
- 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
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 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
- 239000000377 silicon dioxide Substances 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 35
- 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 16
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000003292 glue Substances 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 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
- 150000001412 amines Chemical class 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
- 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
- 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
- 238000000034 method Methods 0.000 claims description 4
- 230000001681 protective effect Effects 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
- 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
- 150000005846 sugar alcohols Polymers 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
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 10
- 238000011049 filling Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 239000000243 solution Substances 0.000 description 12
- 150000002191 fatty alcohols Chemical class 0.000 description 8
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 239000004841 bisphenol A epoxy resin Substances 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000007789 gas 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 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
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 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
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 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
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
Abstract
The invention belongs to the technical field of filling adhesive preparation, and discloses a bottom filling adhesive based on a composite nano filler, and a preparation method and application thereof. The underfill adhesive 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, ferroferric oxide and silicon dioxide are combined to modify the epoxy resin, so that the ageing resistance, material strength and chemical corrosion resistance of the obtained underfill are further improved; meanwhile, the curing speed of the obtained underfill is moderate through the matching of the polyol, the curing agent and the curing accelerator, and the working performance of the underfill is improved. The preparation process is simple, and the required reaction conditions are mild. Meanwhile, the underfill adhesive obtained by the invention 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 adhesive preparation, in particular to a bottom filling adhesive based on composite nano filler and a preparation method and application thereof.
Background
With the fourth industrial revolution, human beings begin to step into the intelligent era, chip manufacturing is an indispensable product in the intelligent era, and with the development of the chip packaging industry, more rigorous requirements are put forward on chip packaging materials. Since the coefficient of thermal expansion of a wafer (die) made of a single crystalline silicon material is much lower than that of a substrate, underfill is widely used for a chip packaging material in order to protect the wafer (die) and bumps (bump) and enhance the reliability of a chip. In chip packaging, underfill is added to the wafer (die) and the substrate to improve the reliability and reduce the interface stress caused by the difference between the thermal expansion coefficients of the bump (bump) and the substrate. The underfill is usually made of epoxy resin, and has the advantages of high toughness, corrosion resistance, high viscosity, high insulation, etc., but the product of the epoxy resin cured by the common curing system has high brittleness, easy cracking, and poor moisture, heat and impact resistance. Therefore, in the prior art, the performance of the underfill is improved by various methods such as matrix modification, curing agent modification, filler introduction and the like so as to meet the requirements of practical application. Because the inorganic nano particles have surface effect and interface effect, the obtained product has great improvement in the aspects of strength, toughness, heat resistance and the like after the inorganic nano particles are added into an epoxy resin curing system.
However, most of the fillers adopted by the existing underfill are inorganic fillers, and the compatibility between the inorganic fillers and an epoxy resin system is poor, so that the flowability of the fillers and the resin of the underfill is inconsistent, the filling effect is affected, and the performance of the chip is further affected. In addition, the existing underfill is modified by adopting a single nano filler, and the mechanical property of the underfill cannot meet the application requirement of a high-quality chip. Therefore, the development of an underfill with good raw material compatibility and excellent mechanical properties is an urgent need in the field.
Disclosure of Invention
The invention aims to provide an underfill based on composite nano-filler and a preparation method and application thereof, and aims to solve the problems that the existing underfill is poor in compatibility of inorganic filler and epoxy resin, so that the dispersibility of the inorganic filler is poor, and the working performance of the underfill is influenced, and the existing underfill is usually modified by using single nano-filler, so that the mechanical property of the underfill cannot be obviously improved, and the application requirement of a high-quality chip cannot be met.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a composite nano filler-based underfill adhesive, which comprises the following components in parts by weight:
40 to 80 parts of epoxy resin, 1 to 8 parts of polyol, 8 to 15 parts of curing agent, 1 to 2 parts of curing accelerator, 0.5 to 1 part of coupling agent, 30 to 50 parts of core-shell structure composite nano particles, 0.2 to 1 part of dispersing agent and 0.5 to 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 phenolic aldehyde amine curing agent and/or 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 amine ether and polyoxypropylene glycerol ether.
Preferably, in the core-shell structure composite nanoparticles, 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 core; mixing citric acid glue solution of a ferroferric oxide core body, a surfactant, an alkali liquor 2 and tetraethoxysilane for reaction to obtain the core-shell structure composite nano particles.
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 molar volume ratio of the ferric trichloride to the ferric dichloride to the solvent is 1-2 mmol: 0.5-1 mmol: 20-25 mL; the addition amount of the alkali liquor 1 is that the pH value of 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 to 65 portions; the concentration of the citric acid glue solution of the ferroferric oxide core body is 4-5 mg/mL; the volume ratio of the citric acid glue solution of the ferroferric oxide core, the surfactant, the alkali liquor 2 and the tetraethoxysilane is 1-1.2: 75-90: 0.5 to 0.8:1 to 1.5.
Preferably, the reaction is carried out under protective 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 nanoparticles, a dispersing agent and a defoaming agent, and then reacting to obtain the underfill based on the composite nanofiller.
Preferably, the vacuum degree of the reaction is-0.08 to-0.05 MPa, the temperature of the reaction is 20 to 30 ℃, and the reaction time is 2 to 3 hours.
The invention also provides application of the underfill adhesive based on the composite nano filler in electronic packaging chips.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) According to the underfill disclosed by the invention, the epoxy resin is modified by combining ferroferric oxide and silicon dioxide by adopting composite nano fillers, namely core-shell structure composite nano particles, so that the ageing resistance, material strength and chemical corrosion resistance of the underfill are further improved; compared with the nano particles obtained by combining the ferroferric oxide and the silicon dioxide and the single silicon dioxide nano particles, the nano particles obtained by combining the ferroferric oxide and the silicon dioxide have higher combining capacity with the epoxy resin, the dispersity of the nano particles in the epoxy resin can be improved, and the flowability of the obtained underfill is improved;
(2) 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;
(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 a composite nano filler-based underfill adhesive, which comprises the following components in parts by weight:
40 to 80 parts of epoxy resin, 1 to 8 parts of polyol, 8 to 15 parts of curing agent, 1 to 2 parts of curing accelerator, 0.5 to 1 part of coupling agent, 30 to 50 parts of core-shell structure composite nano particles, 0.2 to 1 part of dispersing agent and 0.5 to 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, and more preferably 50 to 70 parts; the amount of the polyol 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, and more preferably 10 to 11 parts; the amount of the curing accelerator is preferably 1.2 to 1.8 parts, and more preferably 1.3 to 1.7 parts; the amount of the coupling agent is preferably 0.6 to 0.9 part, and more preferably 0.7 to 0.8 part; the dosage of the core-shell structure composite nano particle 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, and more preferably 0.6 to 0.8 part; the amount of the defoaming agent is preferably 0.6 to 1.2 parts, and 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, and is more preferably a bisphenol a type epoxy resin; the bisphenol A type epoxy resin is preferably E-55 bisphenol A type epoxy resin, E-51 bisphenol A type epoxy resin and E-44 bisphenol A type epoxy resin, and more preferably E-55 bisphenol A type epoxy resin and/or 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 is more preferably pentaerythritol or sorbitol.
In the present invention, the curing agent is preferably a phenolic aldehyde amine curing agent and/or an acid anhydride curing agent, and more preferably a phenolic aldehyde amine curing agent; the phenolic aldehyde amine curing agent is preferably one or more of phenolic aldehyde amine curing agent KM-260, phenolic aldehyde amine curing agent T-33 and phenolic aldehyde amine curing agent T-31, and is further preferably phenolic aldehyde 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 is more preferably 2-ethyl-4-methylimidazole and/or 2-phenylimidazole.
In the present invention, the coupling agent is preferably vinyltriethoxysilane and/or vinyltrimethoxysilane, and more preferably vinyltriethoxysilane or vinyltrimethoxysilane.
In the invention, the dispersing agent is preferably fatty alcohol-polyoxyethylene ether and/or fatty amine-polyoxyethylene ether, and is further 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 is 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 more preferably fatty amine polyoxyethylene ether AC-1860.
In the present invention, the antifoaming agent is preferably one or more of polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, and polyoxypropylene glycerol ether, and is more preferably polyoxyethylene polyoxypropylene pentaerythritol ether and/or polyoxyethylene polyoxypropylene amine ether.
The polyol, the curing agent and the curing accelerator are combined, wherein the polyol can be added to adjust the curing speed of an epoxy resin system, and the polyol can be combined with the curing agent and the curing accelerator to obtain the underfill with moderate curing speed, so that the working performance and the toughness of the underfill are improved.
In the invention, in the core-shell structure composite nanoparticles, 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 core; mixing citric acid glue solution of a ferroferric oxide core body, a surfactant, an alkali liquor 2 and tetraethoxysilane for reaction to obtain the core-shell structure composite nano particles.
In the invention, the concrete 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, stirring and mixing under the condition of introducing protective gas, and then adding citric acid for reaction;
the protective gas is preferably nitrogen or argon, and is further preferably nitrogen; the time of stirring and mixing is preferably 20-40 min, more preferably 25-35 min, and the temperature of stirring and mixing is preferably 70-85 ℃, more preferably 75-80 ℃; the stirring and mixing speed is preferably 500 to 800r/min, and more preferably 600 to 700r/min;
the reaction is carried out under the protection gas, and the protection gas is preferably nitrogen or argon, and is further preferably nitrogen; the reaction temperature is preferably 70-90 ℃, and more preferably 75-85 ℃; the reaction time is preferably 1 to 2 hours, more preferably 1.5 hours.
In the invention, the post-treatment is specifically as follows: performing centrifugal separation, washing and drying on products obtained by the reaction in sequence;
the rotation speed of the centrifugal separation is preferably 1000-2000 r/min, and more preferably 1200-1800 r/min; the time for centrifugal separation is preferably 10 to 30min, and more preferably 15 to 25min; the washing reagent is preferably water, and the number of washing is preferably 2 to 4, and more preferably 3; the drying temperature is preferably 60-70 ℃, and more preferably 65-68 ℃; the drying time is preferably 10 to 30min, and more preferably 15 to 25min.
In the invention, the specific steps of mixing and reacting the citric acid glue solution of the ferroferric oxide nucleus, the surfactant, the alkali liquor 2 and the tetraethoxysilane are as follows: mixing citric acid glue solution of a ferroferric oxide core, a surfactant and alkali liquor 2, and then dropwise adding tetraethoxysilane for mixing reaction;
the dripping 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, and 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 is further preferably polyethylene glycol octyl phenyl ether; the mol volume ratio of the ferric trichloride to the ferric dichloride to the solvent is preferably 1-2 mmol: 0.5-1 mmol:20 to 25mL, more preferably 1.2 to 1.5mmol: 0.6-0.8 mmol: 21-24 mL; the addition amount of the alkali liquor 1 is preferably 8.5 to 10 of the pH value of a mixed solution obtained by mixing ferric trichloride, ferric dichloride and a solvent, and is further preferably 9 of the pH value of a mixed solution obtained by mixing ferric trichloride, ferric dichloride and a solvent; the volume ratio of the citric acid to the solvent is preferably 1:55 to 65, more preferably 1:60 to 62 percent; the concentration of the citric acid glue solution of the ferroferric oxide core is preferably 4-5 mg/mL, and further preferably 4.2-4.5 mg/mL; the volume ratio of the citric acid glue solution of the ferroferric oxide core, the surfactant, the alkali liquor 2 and the tetraethoxysilane 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 core-shell structure composite nanoparticles to modify epoxy resin, so that the ageing resistance, material strength and chemical corrosion resistance of the obtained underfill are further improved; the core-shell structure composite nanoparticles have respective performances of ferroferric oxide and silicon dioxide, and have higher binding capacity with epoxy resin compared with the existing single silicon dioxide nanoparticles due to the action of the ferroferric oxide and the epoxy resin, so that the dispersibility of the core-shell structure composite nanoparticles in the epoxy resin can be improved, and the flowability of the underfill can be 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 nanoparticles, a dispersing agent and a defoaming agent, and then reacting to obtain the underfill based on the composite nanofiller.
In the invention, the concrete steps of mixing the epoxy resin, the polyol, the curing agent, the curing accelerator, the coupling agent, the core-shell structure composite nano particles, the dispersing agent and the defoaming agent are as follows: firstly, mixing epoxy resin, polyol, a coupling agent, core-shell structure composite nanoparticles, a dispersing agent and a defoaming agent, and then adding a curing agent and a curing accelerator for reaction.
In the present invention, the degree of vacuum 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 20-30 ℃, and more preferably 25-28 ℃; the reaction time is preferably 2 to 3 hours, and more preferably 2.5 hours.
The invention also provides application of the underfill adhesive based on the composite nano filler in electronic packaging chips.
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 the core-shell structure composite nano particles:
putting 4mmol of ferric trichloride, 2mmol of ferric dichloride and 80mL of water into a reaction kettle for mixing, then introducing nitrogen into the reaction kettle and heating, adding ammonia water with the mass concentration of 30% under the conditions of 75 ℃ and nitrogen protection to adjust the pH value of the mixed solution in the reaction kettle to 9, then stirring and mixing at the speed of 600r/min for 30min, then adding 480mL of citric acid, and reacting at the temperature of 80 ℃ for 1h; placing the obtained reaction solution in a centrifuge, centrifuging at 1500r/min for 20min, filtering to obtain solid matter, washing the solid matter with water for 3 times, and drying in a drying oven at 60 deg.C for 20min to obtain ferroferric oxide core;
mixing a ferroferric oxide core body with citric acid to obtain glue solution with the concentration of 4 mg/mL; and mixing 10mL of glue solution with 800mL of polyethylene glycol octyl phenyl ether and 6mL of ammonia water with the mass concentration of 25% to obtain a mixture, dropwise adding 12mL of ethyl orthosilicate into the mixture at the speed of 1.2mL/min, mixing and reacting for 16h, and drying a product obtained by the mixed reaction at 60 ℃ to obtain the core-shell structure composite nanoparticles.
Example 2
Preparing the underfill based on the composite nano filler:
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 aldehyde amine curing agent KM-26010 parts, 1 part of 2-ethyl-4-methylimidazole, 0.5 part of vinyl triethoxysilane, 30 parts of core-shell structure composite nanoparticles 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: mixing E-55 bisphenol A epoxy resin, pentaerythritol, vinyl triethoxysilane, the core-shell structure composite nanoparticles obtained in example 1, fatty alcohol polyoxyethylene ether AEO-9 and polyoxyethylene polyoxypropylene pentaerythritol ether, adding phenolic aldehyde amine curing agent KM-260 and 2-ethyl-4-methylimidazole, and reacting for 2h under the conditions that the vacuum degree is-0.08 MPa and the temperature is 25 ℃ to obtain the underfill.
Example 3
Preparing the underfill based on the composite nano filler:
the raw materials and the dosage are as follows: 50 parts of E-51 bisphenol A 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 nanoparticles 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: mixing E-51 bisphenol A epoxy resin, pentaerythritol, vinyl trimethoxy silane, the core-shell structure composite nanoparticles obtained in example 1, fatty alcohol polyoxyethylene ether AEO-9 and polyoxyethylene polyoxypropylene pentaerythritol ether, adding phthalic anhydride and 2-ethyl-4-methylimidazole, and reacting for 2 hours at 25 ℃ under the conditions of vacuum degree of-0.06 MPa to obtain the underfill.
Example 4
Preparing the underfill based on the composite nano filler:
the raw materials and the dosage are as follows: alicyclic epoxy resin S-2170 parts, sorbitol 7 parts, phenolic aldehyde amine curing agent T-33 parts, 2-methylimidazole 1 part, vinyl triethoxysilane 0.8 part, core-shell structure composite nanoparticles 40 parts obtained in example 1, fatty alcohol polyoxyethylene ether AEO-90.5 parts and polyoxyethylene polyoxypropylene pentaerythritol ether 1.2 parts;
the preparation process comprises the following steps: firstly, alicyclic epoxy resin S-21, sorbitol, vinyl triethoxysilane, the core-shell structure composite nanoparticles obtained in example 1, fatty alcohol polyoxyethylene ether AEO-9 and polyoxyethylene polyoxypropylene pentaerythritol ether are mixed, then phenolic aldehyde amine curing agents T-33 and 2-methylimidazole are added, and the mixture is reacted for 2 hours under the conditions that the vacuum degree is-0.05 MPa and the temperature is 25 ℃ to obtain the underfill.
Example 5
Preparing the underfill based on the composite nano filler:
the raw materials and the dosage are as follows: 80 parts of E-51 bisphenol A 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 nanoparticles 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: mixing E-51 bisphenol A epoxy resin, sorbitol, vinyl triethoxysilane, the core-shell structure composite nanoparticles obtained in example 1, fatty alcohol polyoxyethylene ether AEO-9 and polyoxyethylene polyoxypropylene pentaerythritol ether, adding dodecyl succinic anhydride and 2-phenylimidazole, and reacting for 2.5h under the conditions of vacuum degree of-0.07 MPa and temperature of 30 ℃ to obtain the underfill.
The properties of the underfill obtained in examples 2 to 5 were measured, and 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 of performance test and method used
TABLE 2 Performance test results for underfill obtained in examples 2 to 5
As can be seen from Table 2, the curing time of the underfill obtained by the present invention is higher than that of the existing two-stage underfill (the curing time is usually 20-25 min), and the flow property is excellent, which indicates that the underfill of the present invention has excellent working performance; the thermal expansion coefficient and the elastic modulus of the underfill are both superior to those of common underfill (the thermal expansion coefficient is 50-53 mu m/m ℃, and the elastic modulus is 10-11 GPa). Therefore, the underfill has excellent mechanical properties while having excellent working performance, and ensures higher reliability of packaged components.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The underfill adhesive based on the composite nano filler is characterized by comprising the following components in parts by weight:
40 to 80 parts of epoxy resin, 1 to 8 parts of polyol, 8 to 15 parts of curing agent, 1 to 2 parts of curing accelerator, 0.5 to 1 part of coupling agent, 30 to 50 parts of core-shell structure composite nano particles, 0.2 to 1 part of dispersing agent and 0.5 to 1.5 parts of defoaming agent.
2. The composite nanofiller-based underfill according to claim 1, wherein said epoxy resin is a bisphenol a type epoxy resin and/or a cycloaliphatic epoxy resin; the polyhydric alcohol is one or more of pentaerythritol, xylitol and sorbitol; the curing agent is phenolic aldehyde amine curing agent and/or anhydride curing agent; the curing accelerator is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
3. The composite nanofiller-based underfill according to claim 2, wherein said 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 amine ether and polyoxypropylene glycerol ether.
4. The underfill according to any one of claims 1 to 3, wherein the core-shell structure composite nanoparticles comprise ferroferric oxide as a core and silica as a shell.
5. The underfill based on composite nanofillers according to claim 4, wherein the preparation of the core-shell structured composite nanoparticles 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 core; mixing citric acid glue solution of a ferroferric oxide core body, a surfactant, an alkali liquor 2 and tetraethoxysilane for reaction to obtain the core-shell structure composite nano particles.
6. The underfill according to claim 5, wherein said lye 1 and 2 are ammonia; the surfactant is polyethylene glycol octyl phenyl ether and/or cyclohexane; the molar volume ratio of the ferric trichloride to the ferric dichloride to the solvent is 1-2 mmol: 0.5-1 mmol: 20-25 mL; the addition amount of the alkali liquor 1 is that the pH value of 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 to 65 portions; the concentration of the citric acid glue solution of the ferroferric oxide core body is 4-5 mg/mL; the volume ratio of the citric acid glue solution of the ferroferric oxide core, the surfactant, the alkali liquor 2 and the tetraethoxysilane is 1-1.2: 75-90: 0.5-0.8: 1 to 1.5.
7. The underfill based on composite nanofillers according to claim 5 or 6, wherein the reaction is carried out under a protective gas at a temperature of 70-90 ℃ for 1-2 h; the mixing reaction time is 15-20 h.
8. The process for the preparation of underfill based on composite nanofillers according to any one of claims 1 to 7, characterized by comprising the steps of:
mixing epoxy resin, polyol, a curing agent, a curing accelerator, a coupling agent, core-shell structure composite nanoparticles, a dispersing agent and a defoaming agent, and then reacting to obtain the underfill based on the composite nanofiller.
9. The preparation method of underfill according to claim 8, wherein the degree of vacuum of the reaction is-0.08 to-0.05 MPa, the temperature of the reaction is 20 to 30 ℃, and the reaction time is 2 to 3 hours.
10. Use of the composite nanofiller-based underfill according to any one of claims 1 to 7 in an electronic packaging chip.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211565594.1A CN115820181A (en) | 2022-12-07 | 2022-12-07 | Underfill adhesive based on composite nano filler and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211565594.1A CN115820181A (en) | 2022-12-07 | 2022-12-07 | Underfill adhesive based on composite nano filler and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115820181A true CN115820181A (en) | 2023-03-21 |
Family
ID=85544507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211565594.1A Pending CN115820181A (en) | 2022-12-07 | 2022-12-07 | Underfill adhesive based on composite nano filler and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115820181A (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348713A (en) * | 2007-07-20 | 2009-01-21 | 同济大学 | Magnetic composite nano microsphere capable of emitting fluorescence and preparation thereof |
| CN102010686A (en) * | 2010-09-30 | 2011-04-13 | 烟台德邦电子材料有限公司 | Double-solidification system fast-flowing underfill and preparation method thereof |
| CN102504745A (en) * | 2011-11-09 | 2012-06-20 | 烟台德邦科技有限公司 | Double curing encapsulating adhesive and preparation method thereof |
| CN102965074A (en) * | 2012-11-30 | 2013-03-13 | 钢铁研究总院 | Nanoparticle for absorbing microwave and synthesis method thereof |
| CN103331142A (en) * | 2013-07-11 | 2013-10-02 | 南京工业大学 | Magnetic adsorbent, preparation method and application of magnetic adsorbent in desulfurization of fuel oil |
| CN103436211A (en) * | 2013-09-10 | 2013-12-11 | 烟台德邦科技有限公司 | Underfill adhesive with good compatibility and preparation method thereof |
| CN103725240A (en) * | 2013-12-27 | 2014-04-16 | 烟台德邦科技有限公司 | Underfill adhesive with storage stability and fast mobility and preparation method of underfill adhesive |
| CN104086720A (en) * | 2014-07-29 | 2014-10-08 | 齐鲁工业大学 | Preparation method of double-shell core-shell structured composite nanoparticle with with cavity |
| CN105655078A (en) * | 2014-11-14 | 2016-06-08 | 神华集团有限责任公司 | Magnetic composite material with core-shell structure and preparation method thereof |
| CN105802563A (en) * | 2016-04-20 | 2016-07-27 | 烟台德邦科技有限公司 | Flowing type chip-grade bottom filling adhesive and preparation method thereof |
| CN106590494A (en) * | 2016-12-01 | 2017-04-26 | 烟台信友新材料股份有限公司 | Low-thermal expansion coefficient low-viscosity rapid-penetration bottom filling glue and preparation method thereof |
| CN109294499A (en) * | 2018-09-20 | 2019-02-01 | 王景硕 | A kind of electronic device bottom filling glue |
| CN109401706A (en) * | 2018-10-31 | 2019-03-01 | 深圳广恒威科技有限公司 | One kind can quick-setting high reliability filling glue |
-
2022
- 2022-12-07 CN CN202211565594.1A patent/CN115820181A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348713A (en) * | 2007-07-20 | 2009-01-21 | 同济大学 | Magnetic composite nano microsphere capable of emitting fluorescence and preparation thereof |
| CN102010686A (en) * | 2010-09-30 | 2011-04-13 | 烟台德邦电子材料有限公司 | Double-solidification system fast-flowing underfill and preparation method thereof |
| CN102504745A (en) * | 2011-11-09 | 2012-06-20 | 烟台德邦科技有限公司 | Double curing encapsulating adhesive and preparation method thereof |
| CN102965074A (en) * | 2012-11-30 | 2013-03-13 | 钢铁研究总院 | Nanoparticle for absorbing microwave and synthesis method thereof |
| CN103331142A (en) * | 2013-07-11 | 2013-10-02 | 南京工业大学 | Magnetic adsorbent, preparation method and application of magnetic adsorbent in desulfurization of fuel oil |
| CN103436211A (en) * | 2013-09-10 | 2013-12-11 | 烟台德邦科技有限公司 | Underfill adhesive with good compatibility and preparation method thereof |
| CN103725240A (en) * | 2013-12-27 | 2014-04-16 | 烟台德邦科技有限公司 | Underfill adhesive with storage stability and fast mobility and preparation method of underfill adhesive |
| CN104086720A (en) * | 2014-07-29 | 2014-10-08 | 齐鲁工业大学 | Preparation method of double-shell core-shell structured composite nanoparticle with with cavity |
| CN105655078A (en) * | 2014-11-14 | 2016-06-08 | 神华集团有限责任公司 | Magnetic composite material with core-shell structure and preparation method thereof |
| CN105802563A (en) * | 2016-04-20 | 2016-07-27 | 烟台德邦科技有限公司 | Flowing type chip-grade bottom filling adhesive and preparation method thereof |
| CN106590494A (en) * | 2016-12-01 | 2017-04-26 | 烟台信友新材料股份有限公司 | Low-thermal expansion coefficient low-viscosity rapid-penetration bottom filling glue and preparation method thereof |
| CN109294499A (en) * | 2018-09-20 | 2019-02-01 | 王景硕 | A kind of electronic device bottom filling glue |
| CN109401706A (en) * | 2018-10-31 | 2019-03-01 | 深圳广恒威科技有限公司 | One kind can quick-setting high reliability filling glue |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3469446B2 (en) | Resin composition and method of manufacturing resin-encapsulated semiconductor device using the same | |
| CN104672785B (en) | A kind of epoxy-plastic packaging material and preparation method thereof | |
| CN112409971B (en) | Liquid mold sealing adhesive for protecting five sides of semiconductor chip and preparation method | |
| JPH05235212A (en) | Resin composition with improved heat resistance property for sealing semiconductor device | |
| CN115820181A (en) | Underfill adhesive based on composite nano filler and preparation method and application thereof | |
| US7224050B2 (en) | Plastic materials including dendrimers or hyperbranched polymers for integrated circuit packaging | |
| CN113948481A (en) | Semiconductor device, epoxy resin, preparation method of epoxy resin, packaging material and terminal | |
| CN106280254A (en) | Filler and preparation method thereof and purposes at the bottom of a kind of low-k moulding type epoxy | |
| JP2002274834A (en) | Surface-modified silica for epoxy molding material, method for producing the same, apparatus therefor and epoxy molding material for semiconductor package | |
| JPS62290720A (en) | Epoxy resin molding material for sealing electronic component | |
| JP2002226675A (en) | Insulating paste | |
| JPH0211654A (en) | Epoxy resin composition for semiconductor sealing | |
| KR100458274B1 (en) | Epoxy resin composition for semiconductor device sealing | |
| CN107880829A (en) | A kind of high-performance epoxy structural rubber and preparation method thereof | |
| JP3200251B2 (en) | Semiconductor device and epoxy resin composition used therefor | |
| CN112063362A (en) | Bi-component organic silicon pouring sealant and preparation method thereof | |
| JPH0535175B2 (en) | ||
| JPS63349A (en) | Epoxy resin composition for use in sealing semiconductor | |
| JPS6361017A (en) | Liquid epoxy sealant | |
| JPH1192549A (en) | Liquid epoxy resin composition | |
| CN114456771B (en) | LED insulation condensation type die bonding adhesive and preparation method thereof | |
| CN114989759B (en) | Modified epoxy resin with low shrinkage, high toughness and low stress and preparation method thereof | |
| CN108641647A (en) | A kind of membrane module sealing end double-component epoxy adhesive | |
| JPS6317926A (en) | Epoxy resin composition for semiconductor sealing | |
| CN117050383A (en) | Application of amino modifier with triphenylphosphine, amino modified silica micropowder, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |