CN102676102B - Silver nanowire doped conductive silver colloid and preparation method thereof - Google Patents
Silver nanowire doped conductive silver colloid and preparation method thereof Download PDFInfo
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- CN102676102B CN102676102B CN201110063176.8A CN201110063176A CN102676102B CN 102676102 B CN102676102 B CN 102676102B CN 201110063176 A CN201110063176 A CN 201110063176A CN 102676102 B CN102676102 B CN 102676102B
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Abstract
The invention relates to the field of semiconductor electronic materials, and in particular relates to a silver nanowire doped conductive silver colloid and a preparation method thereof. The raw materials of the silver nanowire doped conductive silver colloid provided by the invention comprise the following components in percentage by weight: 25-60% of micrometer silver powder, 5-30% of silver nanowires, 20-50% of epoxy resin, 1.6-4% of curing agent, 5.8-9.2% of dissolvent, 0.4-1.6% of accelerant, 0.04-0.16% of toughening agent and 0.8-2.4% of additive. The conductive silver colloid is prepared by mixing and doping single-crystal silver nanowires and silver granules, thus, the total silver doping amount is reduced to 35-45%, and the conductive silver colloid has a favorable conductive effect, high shear strength, low working temperature and good ageing-resistant performance, and the cost of the conductive silver colloid is reduced. The silver nanowire doped conductive silver colloid can be widely applied to the fields of solar cell (film, crystal silicon) conductive colloids, conductive colloid LED (Light-Emitting Diode) package and the like.
Description
Technical field
The present invention relates to semiconductor electronic Material Field, be specifically related to a kind of conductive doped elargol of nano silver wire that is mainly used in the fields such as solar cell (film, crystal silicon) conductive resin, LED encapsulation and preparation method thereof.
Background technology
Recent two decades comes, and semiconductor electronic industry has obtained rapid progress.In traditional industrial production, use lead/tin (Pb/Sn) alloy to connect each built-up circuit as scolder, make each several part part can obtain the abundance support of electric power, stably transmission signal.Yet lead/tinsolder has exposed many shortcomings gradually in recent years.Plumbous have serious harm to human body and environment.Many countries, to the plumbous clearly regulation that proposes of used in electronic industry, forbid that the electronic goods of new production is used lead-containing materials; In addition, electronic product development trend is to miniaturization, portability development in recent years, the improving constantly of device integrated level.High I/O density requirements connecting material has high linear resolution, and the linear resolution of lead/tinsolder is too low, can only be applied in the connection of the following pitch of 0.065mm.Meanwhile, lead/tin-welding process temperature is up to 230 ℃, and the easy damage device of the thermal stresses of generation and substrate, cannot weld if contain the component of non-refractory in product.Therefore, the use of conductive resin becomes and in electronic industry industry, solves micro-nano connectivity problem effective ways.Conductive resin is mainly comprised of performed polymer and metallic stuffing.Mechanical property and the adhesiveproperties of conductive resin are mainly determined by polymeric matrix.Conductive filler material mostly is the metal-powders such as gold and silver that resistivity is lower, copper, nickel, has determined the electric property of conductive resin.Wherein, containing silver conductive adhesive, be that in conductive resin, people are frequent used a kind of.
In traditional silver conductive adhesive, filler silver is polycrystalline micro-silver powder particle, rely on being in contact with one another between silver particles to form conductive channel conduction, but because the contact area between silver powder particles is little, the node between particle and particle is more, and conductivity cannot promote; And in conventional conductive elargol, silver content is very high, weight percentage is generally 70-80%, the conductive effect that conductive rubber cannot obtain in the situation that silver powder doping is less, also just cannot reduce the cost of conductive resin, and its industrial application value has also been subject to certain restriction.
Summary of the invention
The object of the invention is for deficiency of the prior art, conductive doped elargol of a kind of nano silver wire and preparation method thereof is provided, and the conductive doped elargol of this nano silver wire is mainly used in the fields such as solar cell conductive glue, solar energy film conductive resin, solar cell crystal silicon conductive resin, conductive resin LED encapsulation.
The present invention adopts the mixing and doping of monocrystal silver nano line and silver powder particles to prepare the conductive doped elargol of nano silver wire, because the contact area rate silver powder particles between nano silver wire is large, the node of etween the lines is less, conductivity is better than common silver powder, and this is just for the lifting of conductive resin electric property provides assurance; And under the series connection of nano silver wire, in conductive resin, can more easily form conductive channel, thereby the conductive effect that colloid also can obtain in the less situation of silver-colored doping, can greatly reduce (the silver content 70%-80% in conventional conductive elargol of silver content in conductive silver glue, in the present invention, silver content is at 35%-45%), thereby reduce the cost of conductive silver glue, reach the object of industrial applications.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme to realize:
The conductive doped elargol of nano silver wire of the present invention, its raw material comprises the component of following weight percentage:
Preferably, the conductive doped elargol of described nano silver wire, its raw material comprises the component of following weight percentage:
Preferably, described micro-silver powder is shaped as sheet or spherical; Diameter or particle diameter are 1-8 μ m, and specific surface area is 0.9-1.6m
2/ g.
Preferably, described nano silver wire is monocrystal silver nano line, and length is 20-200 μ m, and diameter is 20-100nm, and volume specific resistance is 0.3x10
5-0.35x10
5s/cm.
Preferably, described epoxy resin is selected from one or more in E-51 epoxy resin, bisphenol epoxy, glyceryl ether epoxy resin, modified glycerol ether ring epoxy resins, novolac epoxy and Modified phenolic epoxy resin.More excellent, described bisphenol epoxy is bisphenol-s epoxy resin, epoxy equivalent (weight) (g/mol) is 185～195 (blue star novel material Wuxi resin processing plants); Described glyceryl ether epoxy resin is glycidyl ether based epoxy resin, and oxirane value is 0.78～0.85 (Xinhua Resin Factory, Shanghai); Described modified glycerol ether ring epoxy resins is fluorinated modified glycidyl ether based epoxy resin (blue star novel material Wuxi resin processing plant); Described novolac epoxy is o-cresol formaldehyde epoxy resin, and the polymerization degree is 3-5; Described Modified phenolic epoxy resin is organic silicon modified phenolic epoxy resin, and the polymerization degree is 3-5.
Preferably, described solidifying agent is selected from one or more in benzene sulfone, Dyhard RU 100, organic acid hydrazides and trolamine.More excellent, described machine acid hydrazides is adipic dihydrazide.
Preferably, described solvent is selected from one or more in ethylene glycol, acetone, dimethyl phthalate, diethyl phthalate, phenylcarbinol, vinylbenzene and pimelinketone.
Preferably, described promotor is selected from one or more in organic urea, imidazoles and tertiary amine class.More excellent, described organic urea is Toluene-2,4-diisocyanate, 4-bis-[N, N-dimethylamino the third urea]; Described imidazoles is imidazoles; Described tertiary amine class is triethylamine.
Preferably, described toughner is selected from one or more in silicone resin, polysulfone resin, polyethers and urethane.More excellent, described silicone resin is SH-1053 silicone resin (Zaoyang Sihai Chemical Co., Ltd.); Described polysulfone resin is dihydroxyphenyl propane-4,4 '-sulfobenzide, and molecular weight is 1327; Described polyethers is polyether diols; Described urethane is AFCONA-4000 type polyurethane (Lan Ya trade Co., Ltd).
Epoxy resin of the present invention, solidifying agent, promotor and toughner are the common agents of this area in prior art.
Preferably, described additive comprises defoamer, coupling agent, thixotropic agent, anti-aging agent, flow agent and dispersion agent, and the weight ratio of described defoamer, coupling agent, thixotropic agent, anti-aging agent, flow agent and dispersion agent is 0.5-1.5: 1-3: 2-3: 0.1-0.5: 0.2-0.8: 0.5-1.5.Described defoamer, coupling agent, thixotropic agent, anti-aging agent, flow agent and dispersion agent are conventional reagent of the prior art.More excellent, described defoamer is that GPE20 type defoamer (Changzhou Shen Yun Chemical Co., Ltd.), coupling agent are that silane coupling agent (Yizheng Tian Yang Chemical Co., Ltd.), thixotropic agent are that organic thixotropic agent (Zhejiang clay chemistry company limited), anti-aging agent are that antioxidant 4020 (Jiangsu Hai'an Petrochemical Plant), flow agent are that flow agent SDS-306 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd) and dispersion agent are dispersion agent 1 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd).
The preparation method of the conductive doped elargol of nano silver wire of the present invention, comprises the steps:
(1) raw material epoxy resin of the conductive doped elargol of nano silver wire, solvent and promotor are taken by proportioning, first at 120-140 ℃ of temperature, stir pre-dispersed 15-30 minute, ultrasonic dispersion 10-20 minute again, after afterwards solidifying agent, toughner and additive being taken by proportioning, add in the mixture after ultrasonic dispersion, after mixing, obtain matrix.
(2) by proportioning, take nano silver wire and micro-silver powder, mix in the formalin that is placed on 2-5% and soak 10-15 minute, in the matrix that successively after filtration, adds step (1) to obtain after washing, fully stir, then put into three-roller and mix, obtain the conductive doped elargol of described nano silver wire.Preferably, described mixing adopts mechanically mixing; Till described washing is cleaned in principle.
Beneficial effect of the present invention is as follows:
The present invention adopts the mixing and doping of monocrystal silver nano line and silver powder particles to prepare the conductive doped elargol of nano silver wire, greatly reduced the doping of silver in conductive silver glue, the total doping of silver is reduced to 35%-45%, the conductive effect that can make conductive silver glue have simultaneously, good shearing resistance, the ageing-resistant performance that low working temperature is become reconciled, can not make conductive silver glue because silver-colored doping lost efficacy compared with little and then generation connectivity problem; Thereby reduced the cost of conductive silver glue, there is higher industrial application value, can be widely used in the fields such as solar cell conductive glue, solar energy film conductive resin, solar cell crystal silicon conductive resin, conductive resin LED encapsulation.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention, should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.
Embodiment 1
The conductive doped elargol of nano silver wire, its raw material comprises the component of following weight percentage:
Described micro-silver powder be shaped as sheet, diameter is 1-8 μ m, specific surface area is 0.9-1.6m
2/ g; Described nano silver wire is monocrystal silver nano line, and length is 20-200 μ m, and diameter is 20-100nm, and volume specific resistance is 0.3x10
5-0.35x10
5s/cm; Described epoxy resin is comprised of E-51 epoxy resin and bisphenol epoxy, and described bisphenol epoxy is bisphenol-s epoxy resin, and epoxy equivalent (weight) (g/mol) is 185～195 (blue star novel material Wuxi resin processing plants); Described solidifying agent is trolamine; Described solvent is comprised of ethylene glycol and acetone; Described promotor is imidazoles; Described toughner is urethane, and described urethane is AFCONA-4000 type polyurethane (Lan Ya trade Co., Ltd); Described additive comprises defoamer, coupling agent, thixotropic agent, anti-aging agent, flow agent, dispersion agent, and six weight ratios are 1: 2: 2.5: 0.3: 0.5: 1.Wherein defoamer is that GPE20 type defoamer (Changzhou Shen Yun Chemical Co., Ltd.), coupling agent are that silane coupling agent (Yizheng Tian Yang Chemical Co., Ltd.), thixotropic agent are that organic thixotropic agent (Zhejiang clay chemistry company limited), anti-aging agent are that antioxidant 4020 (Jiangsu Hai'an Petrochemical Plant), flow agent are that flow agent SDS-306 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd), dispersion agent are dispersion agent 1 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd).
The conductive doped elargol preparation method of nano silver wire of the present embodiment, comprises the steps:
1, extracting epoxy resin, solvent and promotor in proportion, first at 130 ℃ of temperature, stir within 25 minutes, carry out pre-dispersed, more ultrasonic dispersion 15 minutes; Get in proportion more afterwards solidifying agent, toughner and additive, add in the mixture after above-mentioned dispersion, after mixing, obtain matrix.
2, get in proportion nano silver wire and micro-silver powder, mechanically mixing is evenly placed in 2% formaldehyde solution soaks 10 minutes, filters and washes, more fully stir in the matrix that is added step 1 to obtain, and then puts into three-roller and mixes and get final product.
In the conductive silver glue of the nano silver wire doping of this example gained, have high electrical efficiency, its resistivity is 10
-4below Ω cm; Its silver-colored total content, between 35%-45%, is 35%, well below the silver content of 70%-80% in current industrial application conductive silver glue.Meanwhile, the conductive effect that the conductive silver glue of the present embodiment has had, good shearing resistance, the ageing-resistant performance that low working temperature is become reconciled, its performance data is as shown in table 1.
Embodiment 2
The conductive doped elargol of nano silver wire, its raw material comprises the component of following weight percentage:
Described micro-silver powder be shaped as sheet, diameter is 1-8 μ m, specific surface area is 0.9-1.6m
2/ g; Described nano silver wire is monocrystal silver nano line, and length is 20-200 μ m, and diameter is 20-100nm, and volume specific resistance is 0.3x10
5-0.35x10
5s/cm; Described epoxy resin is comprised of bisphenol epoxy and glyceryl ether epoxy resin, wherein bisphenol epoxy is bisphenol-s epoxy resin, epoxy equivalent (weight) (g/mol) is 185～195 (blue star novel material Wuxi resin processing plants), glyceryl ether epoxy resin is glycidyl ether based epoxy resin, and oxirane value is 0.78～0.85 (Xinhua Resin Factory, Shanghai); Described solidifying agent is trolamine; Described solvent is comprised of ethylene glycol, acetone and dimethyl phthalate; Described promotor is tertiary amine class, and described tertiary amine class is triethylamine; Described toughner is silicone resin, and described silicone resin is SH-1053 silicone resin (Zaoyang Sihai Chemical Co., Ltd.); Described additive comprises defoamer, coupling agent, thixotropic agent, anti-aging agent, flow agent, dispersion agent, and six weight ratios are 1: 2: 2.5: 0.3: 0.5: 1.Wherein defoamer is that GPE20 type defoamer (Changzhou Shen Yun Chemical Co., Ltd.), coupling agent are that silane coupling agent (Yizheng Tian Yang Chemical Co., Ltd.), thixotropic agent are that organic thixotropic agent (Zhejiang clay chemistry company limited), anti-aging agent are that antioxidant 4020 (Jiangsu Hai'an Petrochemical Plant), flow agent are that flow agent SDS-306 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd), dispersion agent are dispersion agent 1 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd).
The conductive doped elargol preparation method of nano silver wire of the present embodiment, comprises the steps:
1, extracting epoxy resin, solvent and promotor in proportion, first at 130 ℃ of temperature, stir within 25 minutes, carry out pre-dispersed, more ultrasonic dispersion 15 minutes; Get in proportion more afterwards solidifying agent, toughner and additive, add in the mixture after above-mentioned dispersion, after mixing, obtain matrix.
2, get in proportion nano silver wire and micro-silver powder, mechanically mixing is evenly placed in 2.5% formaldehyde solution soaks 12 minutes, filters and washes, more fully stir in the matrix that is added step 1 to obtain, and then puts into three-roller and mixes and get final product.
In the conductive silver glue of the nano silver wire doping of this example gained, have high electrical efficiency, its resistivity is 10
-4below Ω cm; Its silver-colored total content, between 35%-45%, is 40%, well below the silver content of 70%-80% in current industrial application conductive silver glue.Meanwhile, the conductive effect that the conductive silver glue of the present embodiment has had, good shearing resistance, the ageing-resistant performance that low working temperature is become reconciled, its performance data is as shown in table 1.
Embodiment 3
The conductive doped elargol of nano silver wire, its raw material comprises the component of following weight percentage:
Described micro-silver powder be shaped as sheet, diameter is 1-8 μ m, specific surface area is 0.9-1.6m
2/ g; Described nano silver wire is monocrystal silver nano line, and length is 20-200 μ m, and diameter is 20-100nm, and volume specific resistance is 0.3x10
5-0.35x10
5s/cm; Described epoxy resin is comprised of E-51 epoxy resin and glyceryl ether epoxy resin, and wherein glyceryl ether epoxy resin is glycidyl ether based epoxy resin, and oxirane value is 0.78～0.85; Described solidifying agent is comprised of Dyhard RU 100 and organic acid hydrazides, and described machine acid hydrazides is adipic dihydrazide; Described solvent is comprised of acetone and dimethyl phthalate; Described promotor is imidazoles; Described toughner is silicone resin, and described silicone resin is SH-1053 silicone resin; Described additive comprises defoamer, coupling agent, thixotropic agent, anti-aging agent, flow agent, dispersion agent, and six weight ratios are 1: 2: 2.5: 0.3: 0.5: 1.Wherein defoamer is that GPE20 type defoamer (Changzhou Shen Yun Chemical Co., Ltd.), coupling agent are that silane coupling agent (Yizheng Tian Yang Chemical Co., Ltd.), thixotropic agent are that organic thixotropic agent (Zhejiang clay chemistry company limited), anti-aging agent are that antioxidant 4020 (Jiangsu Hai'an Petrochemical Plant), flow agent are that flow agent SDS-306 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd), dispersion agent are dispersion agent 1 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd).
The conductive doped elargol preparation method of nano silver wire of the present embodiment, comprises the steps:
1, extracting epoxy resin, solvent and promotor in proportion, first at 130 ℃ of temperature, stir within 30 minutes, carry out pre-dispersed, more ultrasonic dispersion 15 minutes; Get in proportion more afterwards solidifying agent, toughner and additive, add in the mixture after above-mentioned dispersion, after mixing, obtain matrix.
2, get in proportion nano silver wire and micro-silver powder, mechanically mixing is evenly placed in 3% formaldehyde solution soaks 12 minutes, filters and washes, more fully stir in the matrix that is added step 1 to obtain, and then puts into three-roller and mixes and get final product.
In the conductive silver glue of the nano silver wire doping of this example gained, have high electrical efficiency, its resistivity is 10
-4below Ω cm; Its silver-colored total content, between 35%-45%, is 40%, well below the silver content of 70%-80% in current industrial application conductive silver glue.Meanwhile, the conductive effect that the conductive silver glue of the present embodiment has had, good shearing resistance, the ageing-resistant performance that low working temperature is become reconciled, its performance data is as shown in table 1.
Embodiment 4
The conductive doped elargol of nano silver wire, its raw material comprises the component of following weight percentage:
Described micro-silver powder be shaped as sheet, diameter is 1-8 μ m, specific surface area is 0.9-1.6m
2/ g; Described nano silver wire is monocrystal silver nano line, and length is 20-200 μ m, and diameter is 20-100nm, and volume specific resistance is 0.3x10
5-0.35x10
5s/cm; Described epoxy resin is comprised of E-51 epoxy resin, modified glycerol ether ring epoxy resins, and wherein modified glycerol ether ring epoxy resins is fluorinated modified glycidyl ether based epoxy resin (blue star novel material Wuxi resin processing plant); Described solidifying agent is comprised of Dyhard RU 100 and organic acid hydrazides, and wherein organic acid hydrazides is adipic dihydrazide; Described solvent is comprised of ethylene glycol, dimethyl phthalate; Described promotor is that tertiary amine class and imidazoles form; Described toughner is that silicone resin, polyethers form, and wherein polyethers is polyether diols; Described additive comprises defoamer, coupling agent, thixotropic agent, anti-aging agent, flow agent, dispersion agent, and six weight ratios are 1: 2: 2.5: 0.3: 0.5: 1.Wherein defoamer is that GPE20 type defoamer (Changzhou Shen Yun Chemical Co., Ltd.), coupling agent are that silane coupling agent (Yizheng Tian Yang Chemical Co., Ltd.), thixotropic agent are that organic thixotropic agent (Zhejiang clay chemistry company limited), anti-aging agent are that antioxidant 4020 (Jiangsu Hai'an Petrochemical Plant), flow agent are that flow agent SDS-306 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd), dispersion agent are dispersion agent 1 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd).
The conductive doped elargol preparation method of nano silver wire of the present embodiment, comprises the steps:
1, extracting epoxy resin, solvent and promotor in proportion, first at 140 ℃ of temperature, stir within 30 minutes, carry out pre-dispersed, more ultrasonic dispersion 20 minutes; Get in proportion more afterwards solidifying agent, toughner and additive, add in the mixture after above-mentioned dispersion, after mixing, obtain matrix.
2, get in proportion nano silver wire and micro-silver powder, mechanically mixing is evenly placed in 5% formaldehyde solution soaks 12 minutes, filters and washes, more fully stir in the matrix that is added step 1 to obtain, and then puts into three-roller and mixes and get final product.
In the conductive silver glue of the nano silver wire doping of this example gained, have high electrical efficiency, its resistivity is 10
-4below Ω cm; Its silver-colored total content, between 35%-45%, is 45%, well below the silver content of 70%-80% in current industrial application conductive silver glue.Meanwhile, the conductive effect that the conductive silver glue of the present embodiment has had, good shearing resistance, the ageing-resistant performance that low working temperature is become reconciled, its performance data is as shown in table 1.
Table 1
| Embodiment | Resistivity (Ω cm) | Shearing resistance (psi) | Working temperature (℃) |
| 1 | 10 -4 | 1450 | 130 |
| 2 | 7×10 -5 | 1380 | 140 |
| 3 | 8×10 -5 | 1390 | 140 |
| 4 | 5×10 -5 | 1320 | 145 |
Embodiment 5
The conductive doped elargol of nano silver wire, its raw material comprises the component of following weight percentage:
Being shaped as of described micro-silver powder is spherical, and particle diameter is 1-8 μ m, and specific surface area is 0.9-1.6m
2/ g; Described nano silver wire is monocrystal silver nano line, and length is 20-200 μ m, and diameter is 20-100nm, and volume specific resistance is 0.3x10
5-0.35x10
5s/cm; Described epoxy resin is comprised of E-51 epoxy resin, bisphenol epoxy; Described solidifying agent is trolamine; Described solvent comprises by ethylene glycol and acetone and forming; Described promotor is imidazoles; Described toughner is urethane; Described additive comprises defoamer, coupling agent, thixotropic agent, anti-aging agent, flow agent, dispersion agent, and six weight ratios are 1.5: 1: 2: 0.5: 0.2: 1.5.Wherein defoamer is that GPE20 type defoamer (Changzhou Shen Yun Chemical Co., Ltd.), coupling agent are that silane coupling agent (Yizheng Tian Yang Chemical Co., Ltd.), thixotropic agent are that organic thixotropic agent (Zhejiang clay chemistry company limited), anti-aging agent are that antioxidant 4020 (Jiangsu Hai'an Petrochemical Plant), flow agent are that flow agent SDS-306 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd), dispersion agent are dispersion agent 1 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd).
The conductive doped elargol preparation method of nano silver wire of the present embodiment, comprises the steps:
1, extracting epoxy resin, solvent and promotor in proportion, first at 120 ℃ of temperature, stir within 20 minutes, carry out pre-dispersed, more ultrasonic dispersion 15 minutes; Get in proportion more afterwards solidifying agent, toughner and additive, add in the mixture after above-mentioned dispersion, after mixing, obtain matrix.
2, get in proportion nano silver wire and micro-silver powder, mechanically mixing is evenly placed in 2% formaldehyde solution soaks 10 minutes, filters and washes, more fully stir in the matrix that is added step 1 to obtain, and then puts into three-roller and mixes and get final product.
In the conductive silver glue of the nano silver wire doping of this example gained, have high electrical efficiency, its resistivity is 10
-4below Ω cm; Its silver-colored total content, between 35%-45%, is 36%, well below the silver content of 70%-80% in current industrial application conductive silver glue.Meanwhile, the conductive effect that the conductive silver glue of the present embodiment has had, good shearing resistance, the ageing-resistant performance that low working temperature is become reconciled.
Embodiment 6
The conductive doped elargol of nano silver wire, its raw material comprises the component of following weight percentage:
Described micro-silver powder be shaped as sheet, diameter is 1-8 μ m, specific surface area is 0.9-1.6m
2/ g; Described nano silver wire is monocrystal silver nano line, and length is 20-200 μ m, and diameter is 20-100nm, and volume specific resistance is 0.3x10
5-0.35x10
5s/cm; Described epoxy resin is comprised of E-51 epoxy resin, bisphenol epoxy; Described solidifying agent is trolamine; Described solvent comprises by ethylene glycol and acetone and forming; Described promotor is imidazoles; Described toughner is urethane; Described additive comprises defoamer, coupling agent, thixotropic agent, anti-aging agent, flow agent, dispersion agent, and six weight ratios are 0.5: 3: 3: 0.1: 0.8: 0.5.Wherein defoamer is that GPE20 type defoamer (Changzhou Shen Yun Chemical Co., Ltd.), coupling agent are that silane coupling agent (Yizheng Tian Yang Chemical Co., Ltd.), thixotropic agent are that organic thixotropic agent (Zhejiang clay chemistry company limited), anti-aging agent are that antioxidant 4020 (Jiangsu Hai'an Petrochemical Plant), flow agent are that flow agent SDS-306 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd), dispersion agent are dispersion agent 1 (Hangzhou Sheng Dishi Chemical Industry Science Co., Ltd).
The conductive doped elargol preparation method of nano silver wire of the present embodiment, comprises the steps:
1, extracting epoxy resin, solvent and promotor in proportion, first at 130 ℃ of temperature, stir within 15 minutes, carry out pre-dispersed, more ultrasonic dispersion 10 minutes; Get in proportion more afterwards solidifying agent, toughner and additive, add in the mixture after above-mentioned dispersion, after mixing, obtain matrix.
2, get in proportion nano silver wire and micro-silver powder, mechanically mixing is evenly placed in 3% formaldehyde solution soaks 15 minutes, filters and washes, more fully stir in the matrix that is added step 1 to obtain, and then puts into three-roller and mixes and get final product.
In the conductive silver glue of the nano silver wire doping of this example gained, have high electrical efficiency, its resistivity is 10
-4below Ω cm; Its silver-colored total content, between 35%-45%, is 35%, well below the silver content of 70%-80% in current industrial application conductive silver glue.Meanwhile, the conductive effect that the conductive silver glue of the present embodiment has had, good shearing resistance, the ageing-resistant performance that low working temperature is become reconciled.
Claims (8)
1. the conductive doped elargol of nano silver wire, its raw material comprises the component of following weight percentage:
Described nano silver wire is monocrystal silver nano line, and length is 20-200 μ m, and diameter is 20-100nm, and volume specific resistance is 0.3x10
5-0.35x10
5s/cm; And the conductive doped elargol of described nano silver wire adopts following steps to prepare:
1) raw material epoxy resin of the conductive doped elargol of nano silver wire, solvent and promotor are taken by proportioning, first at 120-140 ℃, stir pre-dispersed 15-30 minute, ultrasonic dispersion 10-20 minute again, after afterwards solidifying agent, toughner and additive being taken by proportioning, add in the mixture after ultrasonic dispersion, after mixing, obtain matrix;
2) by proportioning, take nano silver wire and micro-silver powder, mix in the formalin that is placed on 2-5% and soak 10-15 minute, in the matrix that successively after filtration, adds step 1) to obtain after washing, fully stir, then put into three-roller and mix, obtain the conductive doped elargol of described nano silver wire.
2. the conductive doped elargol of nano silver wire as claimed in claim 1, is characterized in that, described micro-silver powder be shaped as sheet or spherical; Diameter or particle diameter are 1-8 μ m, and specific surface area is 0.9-1.6m
2/ g.
3. the conductive doped elargol of nano silver wire as claimed in claim 1, it is characterized in that, described epoxy resin is selected from one or more in bisphenol epoxy, glyceryl ether epoxy resin, modified glycerol ether ring epoxy resins, novolac epoxy and Modified phenolic epoxy resin.
4. the conductive doped elargol of nano silver wire as claimed in claim 1, is characterized in that, described solidifying agent is selected from one or more in benzene sulfone, Dyhard RU 100, organic acid hydrazides and trolamine.
5. the conductive doped elargol of nano silver wire as claimed in claim 1, is characterized in that, described solvent is selected from one or more in ethylene glycol, acetone, dimethyl phthalate, diethyl phthalate, phenylcarbinol, vinylbenzene and pimelinketone.
6. the conductive doped elargol of nano silver wire as claimed in claim 1, is characterized in that, described promotor is selected from one or more in organic urea, imidazoles and tertiary amine class; Described toughner is selected from one or more in silicone resin, polysulfone resin, polyethers and urethane.
7. the conductive doped elargol of nano silver wire as claimed in claim 1, it is characterized in that, described additive comprises defoamer, coupling agent, thixotropic agent, anti-aging agent, flow agent and dispersion agent, and the weight ratio of described defoamer, coupling agent, thixotropic agent, anti-aging agent, flow agent and dispersion agent is 0.5-1.5:1-3:2-3:0.1-0.5:0.2-0.8:0.5-1.5.
8. the application of the conductive doped elargol of nano silver wire as described in as arbitrary in claim 1-7 in solar cell conductive glue, solar energy film conductive resin, solar cell crystal silicon conductive resin and conductive resin LED encapsulation field.
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