CN101805574A - Sintered type conductive adhesive adopting silver filling with surfaces subjected to activating treatment and preparation method thereof - Google Patents
Sintered type conductive adhesive adopting silver filling with surfaces subjected to activating treatment and preparation method thereof Download PDFInfo
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- CN101805574A CN101805574A CN 201010121877 CN201010121877A CN101805574A CN 101805574 A CN101805574 A CN 101805574A CN 201010121877 CN201010121877 CN 201010121877 CN 201010121877 A CN201010121877 A CN 201010121877A CN 101805574 A CN101805574 A CN 101805574A
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- 229920005989 resin Polymers 0.000 description 82
- 239000011347 resin Substances 0.000 description 82
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 81
- 229910052709 silver Inorganic materials 0.000 description 44
- 239000004332 silver Substances 0.000 description 44
- 239000011159 matrix material Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000000945 filler Substances 0.000 description 14
- 238000001994 activation Methods 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
- 239000005357 flat glass Substances 0.000 description 12
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 12
- 239000000523 sample Substances 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 7
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000007520 diprotic acids Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000004304 visual acuity Effects 0.000 description 2
- 241000186216 Corynebacterium Species 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229940083025 silver preparation Drugs 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
本发明属于微电子封装互连材料技术领域，具体为一种采用表面活性处理的银填料的烧结型导电胶及其制备方法。本发明以有机二元酸对纳米银表面进行活化处理，二元酸可以去除纳米银表面微量的氧化层，并吸附在纳米银表面防止其进一步氧化和团聚，在导电胶固化过程中脱附，可促进纳米银粒子间的烧结，从而大大增加导电胶的电导率。将经过活化处理的纳米银和微米银混合填充到由环氧树脂、酸酐固化剂、活性稀释剂和固化促进剂组成的基体树脂中，制备得烧结型导电胶。该导电胶具有电导率高、工艺简单、使用方便、重复性好、与现有导电胶工艺完全兼容等特点，在电子封装等领域中具有广阔的应用前景和实用价值。
The invention belongs to the technical field of microelectronic packaging and interconnection materials, in particular to a sintered conductive adhesive using surface-active treated silver fillers and a preparation method thereof. The present invention uses an organic dibasic acid to activate the nano-silver surface. The dibasic acid can remove a small amount of oxide layer on the nano-silver surface, and adsorb on the nano-silver surface to prevent further oxidation and agglomeration. It desorbs during the curing process of the conductive adhesive. It can promote the sintering between nano-silver particles, thereby greatly increasing the conductivity of the conductive adhesive. The sintered conductive adhesive is prepared by mixing activated nano-silver and micro-silver into a matrix resin composed of epoxy resin, anhydride curing agent, reactive diluent and curing accelerator. The conductive adhesive has the characteristics of high electrical conductivity, simple process, convenient use, good repeatability, complete compatibility with the existing conductive adhesive process, etc., and has broad application prospects and practical value in the fields of electronic packaging and the like.
Description
Technical field
The invention belongs to microelectronics Packaging interconnection material technical field, be specifically related to a kind of nanometer silver surface treatment method and with the high conductivity sintered type conductive resin of its preparation, and the preparation method of this conductive resin.
Background technology
Along with the miniaturization and the high performance of modern micro-electronic device, the electronics package technique also develops towards the direction of microminiaturization, densification, high integration, thereby resolving power, the strength of joint of semiconductor packages connection material are had higher requirement.Simultaneously, along with the raising of people's environmental consciousness, low, the eco-friendly connection material of research and development energy consumption has caused people's great attention.As a kind of lead-free interconnection material, conductive resin is low with its solidification value, resolving power is high, thermomechanical property good, technology is simple and with advantages such as the material wettability is good, become the ideal substitute of traditional wiping solder and solder.
The nano material that is in the nanoscale scope on one dimension, two dimension or the three-dimensional shows the unusual characteristic that is different from macro object or single isolated atom usually, has special physics, chemistry and mechanical property.Nano metal particles has the character of a lot of uniquenesses, and wherein one of the most noticeable feature is that its sintering temperature is lower than the metal scale fusing point widely, utilizes this specific character of nano metal can form the metal sinter of arbitrary shape at a lower temperature.Because its excellent electrical and thermal conductivity performance, add stable in properties, oxidation slowly and its oxide compound also have electroconductibility, argent becomes the most widely used conductive resin filler.Present commercially available conductive resin filler is mainly based on micro-silver powder (sheet), and the problem of existence comprises shortcomings such as unsettled contact resistance, low current density, low shock strength, and having restricted silver is the high-end applications of conductive resin.Relative nano-powder, nano silver wire has increased the one dimension size, more helps the contact between nanoparticle, can prepare the conductive resin of high conductance under the condition of low loading level.As publication number be CN 1948414A patent report adopt nano wire and nanoparticle as the ultraviolet light polymerization conductive resin of conductive filler material preparation, in loading level 56%, just can obtain 1.2 * 10
-4The high conductivity of Ω cm.Consider that from the angle that improves loading level nanometer is mixed filling with micron particle can improve filler content in the conductive resin, reduces resistivity.Publication number is that the patent of CN 101215450A adopts homemade corynebacterium nano-silver powder and commercially available micron silver mixing silver powder to prepare conductive resin as conductive filler material, improved conductivity, mechanical property and the ageing resistance of conductive resin, the total loading level of silver powder is that the volume specific resistance of 60% o'clock conductive resin reaches 2.0 * 10
-4Ω cm.If make nano-Ag particles (as the matrix resin solidification value) sintering and the conductive network that form to connect at a lower temperature in the conductive resin, not only can eliminate the contact resistance between nano silver particles, increase substantially the specific conductivity of conductive resin, and can improve the shock resistance of conductive resin.
Because the surfactivity of nano-metal particle is very high; so exist easy oxidation, easily form aggregate and in organism, be difficult to problems such as dispersion; therefore in the various preparation methods of nano metal; tend to use organism such as lipid acid, polyvinylpyrrolidone to protect its surface; prevent its oxidation and reunion; but the existence of these surface organic matters can hinder the formation of contact, sintering and the conductive network of nano metal in the conductive resin solidification process, is unfavorable for reducing the resistivity of conductive resin.Therefore, carry out suitable surface treatment for nano metal and adopt suitable technology to make that its sintering in organism is the key of preparation high conductivity conductive resin.
The present invention protects and activation treatment nanometer silver with organic dibasic acid; diprotic acid not only can be removed the zone of oxidation of nanometer silver surface trace; and can be adsorbed on the surface and prevent its further oxidation and reunion; and in the conductive resin solidification process desorption; produce the sintering between new life, activating surface promotion nano silver particles, thereby increased the specific conductivity of conductive resin greatly.Present method technology is simple, easy to use, good reproducibility, compatible fully with existing conductive resin technology, has broad application prospects in fields such as microelectronics Packaging.
Summary of the invention
The object of the present invention is to provide a kind of method of nano-Ag particles surface activation process, and adopt the high conductivity sintered type conductive resin of this surface-treated nanometer silver preparation and the preparation method of this conductive resin.
The method of the nanometer silver surface activation process that the present invention proposes, its step is as follows: at first prepare certain density organic dibasic acid solution as surface activation process reagent, organic acid concentration is 0.1-4mol/L, solvent can be conventional organic solvents such as ethanol, Virahol, organic dibasic acid can be propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid or senior diprotic acid etc., place surface activation process reagent ultrasonic or stirred 10-60 minute nanometer silver, the mol ratio of nanometer silver and surface activation process reagent is 1: 0.5-2; The supernatant liquid that inclines with a small amount of solvent drip washing nanometer silver, is removed unnecessary surface activation process agent.The nanometer silver here comprises nano-silver powder and/or nano-silver thread.
With above-mentioned same method micron silver is carried out surface activation process.
The invention allows for a kind of sintered type conductive resin that mixes the filling preparation with nanometer silver and micron silver through above-mentioned surface activation process, its prescription weight share meter is as follows: 100 parts of Resins, epoxy, 10～15 parts of epoxy active diluents, 80～100 parts of anhydride curing agents and curing catalyst constitute matrix resin for 0.2～2 part, and the ratio of the mixed fillers of nanometer silver that matrix resin and surface activation process are crossed and micron silver is 1: 2.5-4; In the mixed fillers, the mass ratio of nanometer silver and micron silver is 0.2～1: 1.The concrete preparation method of this conductive resin is as follows: by above-mentioned conductive resin prescription, Resins, epoxy, epoxy active diluent and anhydride curing agent are mixed, add the mixed fillers of surface treated nanometer silver and micron silver then and mix, add curing catalyst at last, continue to be stirred to mixing of materials and evenly get final product.
The present invention gives the using method of surface treating nano silver sintered type conductive resin: described conductive resin is directly filmed in glass, silicon chip, printed circuit board or other dielectric surface, place under the 150-250 ℃ of temperature and reacted 0.5-1 hour, can make its completely solidified, realize the sintering between the nano-Ag particles simultaneously.And sintering degree and Nano silver grain size, solidification value are relevant, and nano-particles size is more little, and sintering at low temperatures is obvious more.
Nanometer silver surface treatment that the present invention provides and sintered type conductive resin preparation method, technology is simple, easy to use, good reproducibility, has broad application prospects in fields such as Electronic Packaging.
Description of drawings
Fig. 1 is thermogravimetric analysis (TGA) curve of nano-silver thread after pentanedioic acid is handled.
Fig. 2 is the stereoscan photograph before nano-silver thread sintered type conductive resin solidifies.
Fig. 3 is the stereoscan photograph after nano-silver thread sintered type conductive resin solidifies.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1 is an activation treatment nano-silver powder and micron preparation of silver strip conductive resin not: the ratio that according to mass ratio is 1: 0.15: 0.9 mixes bisphenol A type epoxy resin (Dow-332), epoxy active diluent and solidifying agent 4-methylhexahydrophthalic anhydride, makes the matrix resin of conductive resin; Nano-silver powder (diameter is about 50-60nm) and micron silver strip (diameter is about 6-9 μ m) that mass ratio is about 1: 3 mix as conductive filler material; According to 1: 4 ratio of mass ratio matrix resin and silver fillers are mixed then; At last, the 1-cyano ethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) that adds matrix resin consumption 1% is made catalyzer, mixes.Conductive resin is coated on the sheet glass of cleaning, the thickness of conductive resin is by the Kapton Tape control that is attached to the sheet glass two ends, put into 200 ℃ of baking ovens then and solidify after 1 hour, make the conductive coating sample 1 of thick 0.1mm, wide 10mm, long 25.4mm, resistivity is 2.3 * 10
-4Ω cm.
The preparation of embodiment 2 Ethanol Treatment nano-silver powders and micron silver strip conductive resin: it is centrifugal with it after 30 minutes that mass ratio is about in the ethanolic soln that 1: 3 nano-silver powder (diameter is about 50-60nm) and micron silver strip (diameter is about 6-9 μ m) join certain volume supersound process, incline behind the supernatant liquid, nano-silver powder and micron silver strip were placed the vacuum drying oven drying at room temperature 1 hour.The ratio that according to mass ratio is 1: 0.15: 0.9 mixes bisphenol A type epoxy resin (Dow-332), epoxy active diluent and solidifying agent 4-methylhexahydrophthalic anhydride, makes the matrix resin of conductive resin; And then according to 1: 4 mixed matrix resin of mass ratio and surface-treated nano-silver powder and micron silver strip filler; At last, the 1-cyano ethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) that adds matrix resin consumption 1% is made catalyzer, mixes.Conductive resin is coated on the sheet glass of cleaning, the thickness of conductive resin is by the Kapton Tape control that is attached to the sheet glass two ends, put into 200 ℃ of baking ovens then and solidify after 1 hour, make the conductive coating sample 2 of thick 0.1mm, wide 10mm, long 25.4mm, resistivity is 1.6 * 10
-4Ω cm.
The preparation of embodiment 3 nano-silver powder sintered type conductive resins: the nano-silver powder (diameter is about 50-60nm) and the micron silver strip (diameter is about 6-9 μ m) that mass ratio are about 1: 3 join in the pentane two acid alcohol solution of 0.5mol/L of certain volume, the mol ratio of silver and pentanedioic acid is 1: 1, supersound process is centrifugal with it after 30 minutes, incline behind the supernatant liquid, nano-silver powder and micron silver strip were placed the vacuum drying oven drying at room temperature 1 hour.The ratio that according to mass ratio is 1: 0.15: 0.9 mixes bisphenol A type epoxy resin (Dow-332), epoxy active diluent and solidifying agent 4-methylhexahydrophthalic anhydride, makes the matrix resin of conductive resin; And then according to 1: 4 mixed matrix resin of mass ratio and surface-treated nano-silver powder and micron silver strip filler; At last, the 1-cyano ethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) that adds matrix resin consumption 1% is made catalyzer, mixes.Conductive resin is coated on the sheet glass of cleaning, the thickness of conductive resin is by the Kapton Tape control that is attached to the sheet glass two ends, put into 200 ℃ of baking ovens then and solidify after 1 hour, make the conductive coating sample 3 of thick 0.1mm, wide 10mm, long 25.4mm, resistivity is 4.2 * 10
-5Ω cm.
The preparation of embodiment 4 nano-silver powder sintered type conductive resins: the nano-silver powder (diameter is about 50-60nm) and the micron silver strip (diameter is about 6-9 μ m) that mass ratio are about 2: 3 join in the hexanodioic acid ethanolic soln of 0.4mol/L of certain volume, the mol ratio of silver and pentanedioic acid is 1: 1, supersound process is centrifugal with it after 30 minutes, incline behind the supernatant liquid, nano-silver powder and micron silver strip were placed the vacuum drying oven drying at room temperature 1 hour.The ratio that according to mass ratio is 1: 0.85 mixes bisphenol A type epoxy resin (Dow-332) and solidifying agent 4-methylhexahydrophthalic anhydride, makes the matrix resin of conductive resin; And then according to 1: 4 mixed matrix resin of mass ratio and surface-treated nano-silver powder and micron silver strip filler; At last, the 1-cyano ethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) that adds matrix resin consumption 1% is made catalyzer, mixes.Conductive resin is coated on the sheet glass of cleaning, the thickness of conductive resin is by the Kapton Tape control that is attached to the sheet glass two ends, put into 200 ℃ of baking ovens then and solidify after 1 hour, make the conductive coating sample 4 of thick 0.1mm, wide 10mm, long 25.4mm, resistivity is 7.0 * 10
-5Ω cm.
The preparation of embodiment 5 nano-silver thread sintered type conductive resins: mass ratio is about 2: 3 nano-silver thread, and (diameter is about 50-60nm, length is about 2-3 μ m) and micron silver strip (diameter is about 6-9 μ m) join in the pentane two acid alcohol solution of 0.5mol/L of certain volume, the mol ratio of silver and pentanedioic acid is 1: 1, supersound process is centrifugal with it after 30 minutes, incline behind the supernatant liquid, nano-silver thread and micron silver strip were placed the vacuum drying oven drying at room temperature 1 hour.The ratio that according to mass ratio is 1: 0.15: 0.9 mixes bisphenol A type epoxy resin (Dow-332), epoxy active diluent and solidifying agent 4-methylhexahydrophthalic anhydride, makes the matrix resin of conductive resin; And then according to 1: 3 mixed matrix resin of mass ratio and surface-treated nano-silver thread and micron silver strip filler; At last, the 1-cyano ethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) that adds matrix resin consumption 1% is made catalyzer, mixes.Conductive resin is coated on the sheet glass of cleaning, the thickness of conductive resin is by the Kapton Tape control that is attached to the sheet glass two ends, then respectively at after solidifying 1 hour in 200 and 300 ℃ of baking ovens, make the conductive coating sample 5 and 6 of thick 0.1mm, wide 10mm, long 25.4mm, resistivity is respectively 8.3 * 10
-5With 6.4 * 10
-5Ω cm.
The preparation of embodiment 6 nano-silver thread sintered type conductive resins: mass ratio is about 2: 3 nano-silver thread, and (diameter is about 50-60nm, length is about 2-3 μ m) and micron silver strip (diameter is about 6-9 μ m) join in the pentane two acid alcohol solution of 0.5mol/L of certain volume, the mol ratio of silver and pentanedioic acid is 1: 1, supersound process is centrifugal with it after 30 minutes, incline behind the supernatant liquid, nano-silver thread and micron silver strip were placed the vacuum drying oven drying at room temperature 1 hour.The ratio that according to mass ratio is 1: 0.15: 0.9 mixes bisphenol A type epoxy resin (Dow-332), epoxy active diluent and solidifying agent 4-methylhexahydrophthalic anhydride, makes the matrix resin of conductive resin; And then according to 1: 3 mixed matrix resin of mass ratio and surface-treated nano-silver thread and micron silver strip filler; At last, the acetylacetone cobalt (Co (acac) that adds matrix resin consumption 1%
2) make catalyzer, mix.Conductive resin is coated on the sheet glass of cleaning, the thickness of conductive resin is by the Kapton Tape control that is attached to the sheet glass two ends, putting into 150,200,250,300 ℃ of baking ovens then respectively solidified after 1 hour, make the conductive coating sample 7-10 of thick 0.1mm, wide 10mm, long 25.4mm, it is 6.5 * 10 that resistivity is respectively
-5, 7.1 * 10
-5, 4.5 * 10
-5, 1.3 * 10
-5Ω cm.
The resistance of all samples is by the test of the Shanghai Qian Feng SB100A/2 of Electron equipment Co., Ltd type four point probe conductor/semiconductor resistivity tester, and the sample resistivity values summarized is in table 1.By sample resistivity value in the table 1 as can be seen, tangible sintering has taken place in surface active nano-silver conductive glue in solidification process, thereby has reduced the contact resistance between the conductive resin filler, has improved the conductivity of conductive resin greatly.
The resistivity of conductive resin sample among table 1 embodiment
Claims (3)
1. sintered type conductive resin is characterized in that the moiety weight share meter of this conductive resin is as follows:
Matrix resin 1,
Silver fillers 2.5～4,
Wherein, the component of matrix resin weight share meter is:
Resins, epoxy 100,
Reactive thinner 10～15,
Anhydride curing agent 80～100,
Curing catalyst 0.2～2;
Silver fillers is made up of nanometer silver and micron silver through surface activation process, and the mass ratio of nanometer silver and micron silver is 0.2～1: 1;
The step of described surface activation process is as follows:
With organic dibasic acid solution as the surface activation process agent, organic dibasic acid is propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid or senior diprotic acid, the organic dibasic acid strength of solution is 0.1-4mol/L, nanometer silver or micron silver are 1: 0.5～2 with the mol ratio of surface activation process agent, and nanometer silver or micron silver are ultrasonic or stirred 10-60 minute in the surface activation process agent.
2. the preparation method of a sintered type conductive resin as claimed in claim 1, it is characterized in that concrete steps are as follows: Resins, epoxy, reactive thinner and anhydride curing agent are mixed by compositing formula, add the mixed fillers of surface treated nanometer silver and micron silver then and mix, add curing catalyst at last, it is even to continue to be stirred to mixing of materials.
3. the using method of a sintered type conductive resin as claimed in claim 1, it is characterized in that concrete steps are as follows: described conductive resin is directly filmed in glass, silicon chip, printed circuit board or other dielectric surface, place under the 150-250 ℃ of temperature and reacted 0.5-1 hour, can make its completely solidified, realize the sintering between the nano-Ag particles simultaneously.
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|---|---|---|---|
| CN 201010121877 CN101805574A (en) | 2010-03-11 | 2010-03-11 | Sintered type conductive adhesive adopting silver filling with surfaces subjected to activating treatment and preparation method thereof |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174306A (en) * | 2011-01-26 | 2011-09-07 | 烟台德邦电子材料有限公司 | Conductive adhesive for LED (light emitting diode) packaging and preparation method of conductive adhesive |
| CN102373029A (en) * | 2010-08-26 | 2012-03-14 | 上海亿金纳米科技有限公司 | Preparation method of rapid curing of flexible conductive adhesive under room temperature |
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| CN102373029A (en) * | 2010-08-26 | 2012-03-14 | 上海亿金纳米科技有限公司 | Preparation method of rapid curing of flexible conductive adhesive under room temperature |
| CN102443370A (en) * | 2010-10-15 | 2012-05-09 | 深圳市道尔科技有限公司 | Low-halogen high-conductivity single-component silver conductive adhesive |
| CN102174306B (en) * | 2011-01-26 | 2013-09-04 | 烟台德邦科技有限公司 | Conductive adhesive for LED (light emitting diode) packaging and preparation method of conductive adhesive |
| CN102174306A (en) * | 2011-01-26 | 2011-09-07 | 烟台德邦电子材料有限公司 | Conductive adhesive for LED (light emitting diode) packaging and preparation method of conductive adhesive |
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| CN102655030B (en) * | 2011-03-02 | 2015-07-15 | 韩国电子通信研究院 | Conductive composition, silicon solar cell including the same, and manufacturing method thereof |
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| CN102990056A (en) * | 2012-10-15 | 2013-03-27 | 宁波广博纳米新材料股份有限公司 | Surface processing method of submicron silver powder |
| CN104968746A (en) * | 2012-12-27 | 2015-10-07 | 学校法人关西大学 | Thermally Conductive Conductive Adhesive Composition |
| CN104751940B (en) * | 2013-12-30 | 2017-04-12 | 财团法人工业技术研究院 | transparent conductive film composition and transparent conductive film |
| CN105733470B (en) * | 2014-12-11 | 2018-04-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of denatured conductive filler, its preparation method and application |
| CN105733470A (en) * | 2014-12-11 | 2016-07-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Modified conductive filling material, preparation method thereof and application |
| CN105618734A (en) * | 2016-01-12 | 2016-06-01 | 昆明理工大学 | Method for surface modification of flaky silver powder |
| CN106833428A (en) * | 2017-01-10 | 2017-06-13 | 金陵科技学院 | A kind of conducting resinl suitable for flexible electrode bonding |
| CN108165209A (en) * | 2018-01-31 | 2018-06-15 | 深圳名飞远科技有限公司 | Low form power battery based on conducting resinl, the conducting resinl preparation method and application |
| CN108165209B (en) * | 2018-01-31 | 2018-11-27 | 深圳名飞远科技有限公司 | Low form power battery, the conducting resinl preparation method and application based on conducting resinl |
| CN109247003A (en) * | 2018-04-12 | 2019-01-18 | 庆鼎精密电子（淮安）有限公司 | Electromagnetic shielding film and preparation method thereof |
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| CN114429830B (en) * | 2022-02-22 | 2023-02-03 | 中南大学 | Metal slurry with good fluidity and uniformity and preparation method thereof |
| CN114907805A (en) * | 2022-03-29 | 2022-08-16 | 苏州博濬新材料科技有限公司 | Low-temperature sintering conductive adhesive based on hybrid filler modification and preparation method thereof |
| CN114806476A (en) * | 2022-06-01 | 2022-07-29 | 罗卫中 | Epoxy resin conductive adhesive containing composite conductive filler and preparation method thereof |
| CN114806476B (en) * | 2022-06-01 | 2023-09-01 | 山东大福粘合剂股份有限公司 | Epoxy resin conductive adhesive containing composite conductive filler and preparation method thereof |
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