CN102675960A - Nano copper-tin alloy conductive ink and preparation method and usage of nano copper-tin alloy conductive ink - Google Patents
Nano copper-tin alloy conductive ink and preparation method and usage of nano copper-tin alloy conductive ink Download PDFInfo
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Abstract
The invention belongs to the technical field of material chemistry, relates to conductive ink, and particularly relates to nano copper-tin alloy conductive ink and a preparation method and usage of the nano copper-tin alloy conductive ink. Nano copper-silver alloy is replaced by nano copper-tin alloy to be used as conductive filler in the conductive ink, sintering temperature of the conductive ink is lowered, and when the nano copper-tin alloy conductive ink is compared with nano copper-silver alloy conductive ink, antioxidant capacity of the conductive ink during sintering is improved, mechanical property and solderability of a conductive circuit formed after sintering of the conductive ink are improved, and the problem of silver ion migration is avoided. Further, since rare earth metal elements are doped in the nano copper-tin alloy, grain boundary of the nano copper-tin alloy is increased, electron scattering power is increased, and conductivity is improved as compared with that of nano copper alloy. On the other hand, tin is much cheaper than silver, so that raw material cost of the nano copper-tin alloy conductive ink is reduced.
Description
[technical field]
The invention belongs to material chemistry technical field, relate to a kind of electrically conductive ink, particularly a kind of nanometer gunmetal electrically conductive ink and preparation method thereof and method of use.
[background technology]
Electrically conductive ink is widely used in industries such as printed wiring and Electronic Packaging.Conduction is different according to conductive filler material wherein, can be divided into carbon slurry and metal, and from conductivity relatively, the electroconductibility of the conductive filler material of metal is best, and the carbon slurry secondly.Metal comprises gold system conduction, silver system conduction and copper system conduction, and the antioxidant property of gold system conduction is best, but price is higher relatively; Silver is that electrically conductive ink is compared gold system conduction price and wanted cheap; Electric conductivity is all higher than copper system and gold system, but silver is electrically conductive ink still to be compared copper to be that the electrically conductive ink price is wanted high, and silver system conduction exists valency to pick up height; The not high shortcoming of strength of joint; And under DC electric field and moisture condition, can produce silver-colored transport phenomena, electroconductibility is reduced, influence its work-ing life.Copper is that conductive phase is the low price of electrically conductive ink than silver, but because easy oxidation of copper and reunion, so cause the conductivity of copper system conduction unstable.Also be prone to oxidized though nano metal powder is compared the non-nano metal-powder; But nano metal powder has higher specific conductivity and lower sintering temperature than non-nano metal-powder; So; The relative merits of comprehensive various conductions more and more trend towards now selecting electrically conductive ink that nanometer copper system and nanometer silver the be printing material as base materials such as RFID label antenna or pcb board, touch-screens.
Ink jet printing mode printing RFID label antenna is the electrically conductive ink that contains nano-metal particle according to antenna pattern spray printing on base materials such as plastics, paper of design; Utilize the lower melting point characteristic of nano metal to carry out sintering processes then, obtain high-precision RFID antenna.Preparing this ink jet printing is under high molecular protection with the fairly simple method of electrically conductive ink; Adopt the mode of chemical reduction metals ion to obtain nano-metal particle; Obtain nano metal powder through centrifugal dispersion again; Through UW it is dispersed in water or the organic solution then, thereby obtains certain density electrically conductive ink, organic solvent in the printing ink and dispersion agent can remove in sintering process.Adopt the difficult point of this method to be to be difficult to obtain the electrically conductive ink of higher solids content and stably dispersing; Except dispersiveness; The electrically conductive ink that utilizes nano-metal particle to prepare need carry out the heat-agglomerating processing could be firm with substrate bondings such as PET, PI, PVC; Through after organic solvent and other auxiliary agents vapor away after the heating, electrically conductive ink could form more stable conductive effect simultaneously.General sintering temperature depends on the fusing point of nano-metal particle.In general, improve the electric conductivity that sintering temperature can improve residue fixing metal behind the sintering to a certain extent, because temperature is high more; Decomposition such as most of additive and solvent are fast more with evaporable speed, and the resistance owing to the defective generation between the metal nanoparticle is also more little, still; Qualitative change all takes place under the high temperature in most of flexible base materials more easily; Too high sintering temperature may make base material produce variations such as shape, color, snappiness, thereby production and use are impacted, if sintering temperature is above 300 ℃; Then electrically conductive ink can only be printed on what glass baseplate of PI, can not be applied on the base materials such as PET, PVC and paper.The sintering temperature of nanometer copper electrically conductive ink about 300 ℃, though and the sintering temperature of nano-silver conductive printing ink below 200 ℃, nano silver powder is compared copper nanoparticle body price and is wanted expensive; And nano-silver powder is known from experience the silver-colored transport phenomena of generation; So, to sum up, if the sintering temperature of nanometer copper electrically conductive ink is reduced; Sintering temperature is reduced; And can guarantee again additive and the solvent evaporates in the electrically conductive ink can prevent the oxidation of nanometer copper again simultaneously, will be that optimal nano metal is an electrically conductive ink.
Patent publication No. is: the Chinese invention patent of CN 1783355A discloses a kind of copper-silver alloy conductor size and preparation method thereof; The component concentration of slurry is respectively in this patent: Kufil nanoparticle 35～50Wt%; Terpineol 350 30～45Wt%; Glass powder 5～25Wt%, TKK 021 1～5Wt%, absolute ethyl alcohol 2～5Wt%.The median size of said Kufil nanoparticle is 80～100 nanometers, and silver content is 5～20Wt% in the particle.It is that the purpose of the conductor paste of main raw material is in order to reduce the sintering temperature of slurry that the present invention adopts the Kufil nanoparticle; And the gas that do not need protection during sintering; Nanometer copper-silver alloy resistance of oxidation is higher than copper nanoparticle, so the conductive stability of conductor paste is higher than the copper powder slurry.
But the contriver finds through experiment; The sintering temperature of this nanometer copper-silver alloy conductive slurry still maintains 210 ℃～220 ℃; Still higher to some extent; Because the fusing point of PET and PVC all is lower than 200 ℃, and still the silver ions transport phenomena be can occur in the nanometer copper-silver alloy, circuit card short circuit or inefficacy caused.
The Chinese patent publication number is: but the patent of invention of CN 101805538A discloses the conductive ink of a kind of low-temperature sintering (sintering temperature is 130 ℃～150 ℃); Comprise that in this conductive ink massfraction is respectively 0.1%～10%, 25%～98% and 0.01%～36% dispersion agent, solvent and additive; Comprise that also massfraction is 1%～70% nano-metal particle, said nano-metal particle is metal and their alloys such as the metal of making conductor commonly used such as gold and silver, copper and iron, nickel, zinc, lead.In fact; No matter described nano-metal particle is pure metal or alloy; Its fusing point is all greater than 180 ℃, is that the sintering temperature of the electrically conductive ink of conductive filler material must could will make the nano-metal particle fusing form conduction favorable conductive circuit more than 200 ℃ so adopt above-mentioned nano-metal particle.
[summary of the invention]
In order to solve above-mentioned technical problem; The present invention proposes a kind of new nanometer gunmetal electrically conductive ink and preparation method thereof and method of use; The sintering temperature of the nanometer gunmetal electrically conductive ink that the present invention proposes is reduced to below 150 ℃; This kind nanometer gunmetal resistance of oxidation, mechanical property and weldability phase ratio nano copper, nanometer silver and nanometer copper-silver alloy are all obviously promoted simultaneously, the problem of silver ions migration also can not occur.
And nanometer gunmetal electrically conductive ink of the present invention forms the electric conductivity that the gunmetal electric conductivity is higher than copper behind sintering.
Concrete technical scheme of the present invention is following:
The present invention provides a kind of nanometer gunmetal electrically conductive ink, it is characterized in that, by mass percentage, this nanometer gunmetal electrically conductive ink comprises following component:
Nanometer gunmetal particle: 8%～60%;
Solvent: 20%～90%;
Auxiliary agent: 2%～20%.
Said nanometer gunmetal particle grain size distribution scope is 1nm～100nm.
By mass percentage, the content of copper and tin is respectively in the said nanometer gunmetal particle:
Copper: 70%～99.5%;
Tin: 0.5%～30%.
More excellent, by mass percentage, the content of said nanometer gunmetal particulate copper and tin is respectively: 95% and 5%.
Also include REE in the said nanometer gunmetal particle, by mass percentage, the content of said copper, tin and REE is respectively:
Copper: 71%～99.4%;
Tin: 0.5%～28%;
Rare earth: 0.01%～5%.
More excellent, by mass percentage, the content of said copper, tin and REE is respectively: 95%, 4.9% and 0.1%.
Said auxiliary agent comprises one or more in tensio-active agent, dispersion agent, coupling agent, reductive agent, adhesion promoter, the anti-settling agent.
Said tensio-active agent comprises but is not limited in the following component one or more: Triple Pressed Stearic Acid, oleic acid, LAURIC ACID 99 MIN, X 2073, trolamine, sodium laurylsulfate, sodium laurylsulfonate, quaternary ammonium compound, hydroxypropylcellulose, sodiun alginate, pectic acid sodium, Walocel MT 20.000PV, hydroxymethyl starch, methacrylic propylhomoserin graft starch, shell gather acid, vinylpyridine copolymer.
Said dispersion agent includes but not limited to one or more in the following component: alkyl sulfhydryl, alkyl acid, alkylamine, alkylphosphonic acid carboxylic acid, contain the micromolecular compound of ring texture.
Said coupling agent includes but not limited to one or more in the following component: KH550 coupling agent, KH560 coupling agent and KBM1003 coupling agent that Japan XINYUE produces.
Said reductive agent includes but not limited to one or more in the following component: xitix, Hydrazine Hydrate 80, formic acid and formaldehyde.
Said adhesion promoter includes but not limited to one or more in the following component: modified phenolic resins, modified epoxy, X 050, styrene-butadiene rubber(SBR) and Zylox.
Said anti-settling agent includes but not limited to one or more in the following component: the N-Methyl pyrrolidone of polyolefine, polymeric amide, modification polyureas.
Said solvent comprises one or more of water, alcohols, ethers and ester class, and said alcohols, ethers and ester class are liquid at normal temperatures.
Said alcohols includes but not limited to one or more in the following component: ethanol, Virahol, butanols, terepthaloyl moietie, phenylcarbinol, diacetone alcohol.
Said ethers includes but not limited to one or more in the following component: butyl glycol ether, ethylene glycol ethyl ether, Diethylene Glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol ether.
Said ester class includes but not limited to one or more in the following component: N-BUTYL ACETATE, vinyl acetic monomer, ethylene glycol ether acetate.
Said ketone includes but not limited to one or more in the following component: acetone, isophorone, MIBK, butanone, metacetone.
The present invention also provides a kind of preparation method of the gunmetal of nanometer as stated electrically conductive ink, it is characterized in that this method comprises the steps:
By weight, 8～60 parts of nanometer gunmetal powders are joined in 20～90 parts of solvents and 2～20 parts of auxiliary agents behind the thorough mixing, homodisperse 10～50 minutes obtains electrically conductive ink.
The present invention provides a kind of employing method of nanometer gunmetal electrically conductive ink printing conducting wire as stated in addition, it is characterized in that this method comprises the steps:
Electrically conductive ink is joined in ink-jet printer or the gravure printing machine; Through ink-jet printer or gravure printing machine electrically conductive ink is printed in the circuit board; The wiring board that is printed with electrically conductive ink is placed under the environment of vacuum or rare gas element; Attemperation is 120 ℃～150 ℃ sintering 5～50 minutes, treat that the volatilization of solvent and auxiliary agent is accomplished after, with the wiring board naturally cooling.
Beneficial technical effects of the present invention is:
The present invention adopts the nanometer gunmetal to replace the nanometer copper-silver alloy as the conductive filler material in the electrically conductive ink; Both reduced the sintering temperature of electrically conductive ink; Compare nanometer copper-silver alloy conductive printing ink simultaneously; Improve the resistance of oxidation of electrically conductive ink when sintering, improved mechanical property and the weldability of the conducting wire that electrically conductive ink forms behind sintering, and avoided occurring the problem of silver ions migration.
In metal alloy; The fusing point of tin alloy is minimum; But tin alloy shortcoming such as the ubiquity electric conductivity is low again; To adopt tin alloy be the problem of the conducting wire electric conductivity that behind sintering, forms of the electrically conductive ink of conductive filler material so how in the sintering temperature that reduces the tin alloy electrically conductive ink, can improve again, also is another technical problem to be solved by this invention.In the present invention, be doped with thulium in the nanometer gunmetal, the crystal boundary of nanometer gunmetal is increased, the electron scattering rate increases, and causes specific conductivity phase ratio nano copper alloy to increase.
On the other hand, all want cheap many, adopt other nano-metal particles or nano metal alloy particle as conductive filler material, reduced the raw materials cost of electrically conductive ink of the present invention so compare because the price of copper, tin is compared silver.
[embodiment]
The present invention relates to a kind of nanometer gunmetal electrically conductive ink, also relate to the preparation method and the method for use of this nanometer gunmetal electrically conductive ink.Adopt the nanometer gunmetal can reduce the sintering temperature of electrically conductive ink, the antioxidant property when having improved the electrically conductive ink sintering simultaneously as the conductive filler material in the electrically conductive ink.And the mechanical property of the conducting wire that forms behind the sintering and weldability all are improved.
Below in conjunction with specific embodiment the present invention is done further to set forth and explanation:
Embodiment 1
A kind of nanometer gunmetal electrically conductive ink; Adopt following method to be prepared from: by weight; The auxiliary agent of the nanometer gunmetal powder that to take by weighing 8 parts of median sizes be 50nm, 90 parts of solvents and 2 parts; The mass percent that comprises copper and tin in the said nanometer gunmetal powder is respectively 70% and 30%; Comprise 15 parts of water, 50 parts of Virahols, 13 parts of ethylene glycol ethyl ethers and 12 parts of butanone in said 90 parts of solvents, said 2 parts of auxiliary agents comprise 0.5 part of tensio-active agent-LAURIC ACID 99 MIN, 0.5 part of dispersion agent-alkyl sulfhydryl and 1 part of adhesion promoter-modified phenolic resins.15 parts of water, 50 parts of Virahols, 13 parts of ethylene glycol ethyl ethers, 12 parts of butanone are mixed and make 90 parts of solvents; 8 parts of nanometer gunmetal powders are joined in 90 parts the solvent, add 0.5 part of LAURIC ACID 99 MIN and 0.5 part of alkyl sulfhydryl simultaneously, vibration is ground and was disperseed 10 minutes in ultrasound environments; After disperseing to accomplish; Add 1 part of modified phenolic resins, continuing vibrates to grind under ultrasound environments disperseed 5 minutes, made nanometer gunmetal electrically conductive ink.
The above-mentioned nanometer gunmetal electrically conductive ink that makes is formed certain wiring diagram through ink-jet printer on paper; The paper that is printed with electrically conductive ink is positioned under the environment of vacuum and 120 ℃; Sintering 50 minutes; Obtain sintered product, under electron microscope, observe sintered product and find that the nanometer gunmetal particle in this nanometer gunmetal conductive ink has all sintered the gunmetal line into.Using the resistivity of this copper-tin alloy conducting wire of four probe method side tool is 1 * 10
-6Ω m.
Embodiment 2
A kind of nanometer gunmetal electrically conductive ink; Adopt following method to be prepared from: by weight; The auxiliary agent of the nanometer gunmetal powder that to take by weighing 60 parts of median sizes be 10nm, 20 parts of solvents and 20 parts; The mass percent that comprises copper and tin in the said nanometer gunmetal powder is respectively 99.5% and 0.5%; Comprise 5 parts of water, 13 parts of Virahols and 2 parts of N-BUTYL ACETATEs in said 20 parts of solvents, said 20 parts of auxiliary agents comprise 3 parts of tensio-active agent-X 2073es, 5 parts of dispersion agent-alkyl acids, 5 parts of KH550 coupling agent, 3 parts of reductive agent-formic acid and 4 parts of adhesion promoter-modified epoxies that coupling agent-Japan XINYUE produces.5 parts of water, 13 parts of Virahols and 2 parts of N-BUTYL ACETATEs are mixed make 20 parts of solvents; 60 parts of nanometer gunmetal powders are joined in 20 parts the solvent; Add 3 parts of tensio-active agent-X 2073es, 5 parts of dispersion agent-alkyl acids, 5 parts of KH550 coupling agents that coupling agent-Japan XINYUE produces simultaneously; Vibration is ground and was disperseed 25 minutes in ultrasound environments, after disperseing to accomplish, adds 3 parts of formic acid and 4 parts of modified epoxies; Continuation is vibrated to grind under ultrasound environments and was disperseed 5 minutes, makes nanometer gunmetal electrically conductive ink.
The above-mentioned nanometer gunmetal electrically conductive ink that makes is formed certain wiring diagram through ink-jet printer on PVC; The PVC that is printed with electrically conductive ink is positioned under the environment of vacuum and 130 ℃; Sintering 40 minutes; Obtain sintered product, under electron microscope, observe sintered product and find that the nanometer gunmetal particle in this nanometer gunmetal conductive ink has all sintered the gunmetal line into.Using the resistivity of this copper-tin alloy conducting wire of four probe method side tool is 5 * 10
-6Ω m.
Embodiment 3
A kind of nanometer gunmetal electrically conductive ink; Adopt following method to be prepared from: by weight; The auxiliary agent of the nanometer gunmetal powder that to take by weighing 60 parts of median sizes be 20nm, 38 parts of solvents and 2 parts; The mass percent that comprises copper and tin in the said nanometer gunmetal powder is respectively 99.4% and 0.59%; Comprise that also mass percent is 0.01% Rare Earth Lanthanum element, comprise 10 parts of water, 23 parts of ethanol and 5 parts of diethylene glycol ethers in said 38 parts of solvents, said 2 parts of auxiliary agents are dispersion agent-alkyl acid.10 parts of water, 23 parts of ethanol and 5 parts of diethylene glycol ethers are mixed make 38 parts of solvents; 60 parts of nanometer gunmetal powders are joined in 38 parts the solvent; Add 2 parts of dispersion agent-alkyl acids simultaneously; Vibration is ground and was disperseed 10 minutes in ultrasound environments, after disperseing to accomplish, makes nanometer gunmetal electrically conductive ink.
The above-mentioned nanometer gunmetal electrically conductive ink that makes is formed certain wiring diagram through ink-jet printer on the PE plastics; The PE that is printed with electrically conductive ink is positioned under the environment of vacuum and 150 ℃; Sintering 5 minutes; Obtain sintered product, under electron microscope, observe sintered product and find that the nanometer gunmetal particle in this nanometer gunmetal conductive ink has all sintered the gunmetal line into.Using the resistivity of this copper-tin alloy conducting wire of four probe method side tool is 3 * 10
-6Ω m.
Embodiment 4
A kind of nanometer gunmetal electrically conductive ink; Adopt following method to be prepared from: by weight; The auxiliary agent of the nanometer gunmetal powder that to take by weighing 8 parts of median sizes be 25nm, 72 parts of solvents and 20 parts; The mass percent that comprises copper and tin in the said nanometer gunmetal powder is respectively 67% and 28%; Comprise that also mass percent is 5% rare earth actinium element; Comprise 10 parts of water, 56 parts of diacetone alcohols, 2 parts of Diethylene Glycol butyl ether, 2 parts of N-BUTYL ACETATEs and 2 parts of acetone in said 72 parts of solvents, said 20 parts of auxiliary agents comprise the N-Methyl pyrrolidone of KBM1003 coupling agent, 3 parts of reductive agent-methyl sodium hydrosulfites, 3 parts of adhesion promoter-modified epoxies and 3 parts of anti-settling agent-modification polyureas of 5 parts of tensio-active agent-Walocel MT 20.000PVs, 3 parts of dispersion agent-alkylamines, 3 parts of coupling agent-Japan XINYUE's productions.10 parts of water, 56 parts of diacetone alcohols, 2 parts of Diethylene Glycol butyl ether, 2 parts of N-BUTYL ACETATEs and 2 parts of acetone are mixed make 72 parts of solvents; 8 parts of nanometer gunmetal powders are joined in 72 parts the solvent; Add 5 parts of tensio-active agent-Walocel MT 20.000PVs, 3 parts of dispersion agent-Z 150PH, 5 parts of KBM1003 coupling agents that coupling agent-Japan XINYUE produces simultaneously; Vibration is ground and was disperseed 35 minutes in ultrasound environments; After disperseing to accomplish; The N-Methyl pyrrolidone that adds 3 parts of reductive agent-methyl sodium hydrosulfites, 3 parts of adhesion promoter-modified epoxies and 3 parts of anti-settling agent-modification polyureas, continuing vibrates to grind under ultrasound environments disperseed 15 minutes, made nanometer gunmetal electrically conductive ink.
The above-mentioned nanometer gunmetal electrically conductive ink that makes is formed certain wiring diagram through ink-jet printer on PI; The PI that is printed with electrically conductive ink is positioned under the environment of vacuum and 135 ℃; Sintering 30 minutes; Obtain sintered product, under electron microscope, observe sintered product and find that the nanometer gunmetal particle in this nanometer gunmetal conductive ink has all sintered the gunmetal line into.Using the resistivity of this copper-tin alloy conducting wire of four probe method side tool is 5 * 10
-6Ω m.
Embodiment 5
A kind of nanometer gunmetal electrically conductive ink; Adopt following method to be prepared from: by weight; The auxiliary agent of the nanometer gunmetal powder that to take by weighing 36 parts of median sizes be 25nm, 50 parts of solvents and 14 parts; The mass percent that comprises copper and tin in the said nanometer gunmetal powder is respectively 95% and 0.49%; Comprise that also mass percent is 0.1% Rare Earth Lanthanum element; Comprise 6 parts of water, 36 parts of diacetone alcohols, 6 parts of Diethylene Glycol butyl ether, 1 part of N-BUTYL ACETATE and 1 part of acetone in said 50 parts of solvents, said 14 parts of auxiliary agents comprise the N-Methyl pyrrolidone of KBM550 coupling agent, 4 parts of reductive agent-methyl sodium hydrosulfites, 2 parts of adhesion promoter-modified epoxies and 2 parts of anti-settling agent-modification polyureas of 2 parts of tensio-active agent-Walocel MT 20.000PVs, 2 parts of dispersion agent-alkylphosphonic acid carboxylic acids, 2 parts of coupling agent-Japan XINYUE's productions.6 parts of water, 36 parts of diacetone alcohols, 6 parts of Diethylene Glycol butyl ether, 1 part of N-BUTYL ACETATE and 1 part of acetone mixed make 50 parts of solvents; 36 parts of nanometer gunmetal powders are joined in 50 parts the solvent; Add 2 parts of tensio-active agent-Walocel MT 20.000PVs, 2 parts of dispersion agent-alkylphosphonic acid carboxylic acids, 2 parts of KBM550 coupling agents that coupling agent-Japan XINYUE produces simultaneously; Vibration is ground and was disperseed 30 minutes in ultrasound environments; After disperseing to accomplish; The N-Methyl pyrrolidone that adds 4 parts of reductive agent-methyl sodium hydrosulfites, 2 parts of adhesion promoter-modified epoxies and 2 parts of anti-settling agent-modification polyureas, continuing vibrates to grind under ultrasound environments disperseed 10 minutes, made nanometer gunmetal electrically conductive ink.
The above-mentioned nanometer gunmetal electrically conductive ink that makes is formed certain wiring diagram through ink-jet printer on paper; The paper that is printed with electrically conductive ink is positioned under the environment of vacuum and 140 ℃; Sintering 15 minutes; Obtain sintered product, under electron microscope, observe sintered product and find that the nanometer gunmetal particle in this nanometer gunmetal conductive ink has all sintered the gunmetal line into.Using the resistivity of this copper-tin alloy conducting wire of four probe method side tool is 1 * 10
-6Ω m.
Need to prove that those skilled in the art can also very simply expect other embodiment to the above embodiments, and through simply repeatedly experiment, just can access some improvement.But no matter how to improve,, belong to the protection domain of this patent as long as these technical schemes in concept of the present invention, should be equal to the technical scheme of this patent.
Claims (10)
1. a nanometer gunmetal electrically conductive ink is characterized in that, by mass percentage, this nanometer gunmetal electrically conductive ink comprises following component:
Nanometer gunmetal powder: 8%～60%;
Solvent: 20%～90%;
Auxiliary agent: 2%～20%.
2. a kind of nanometer gunmetal electrically conductive ink according to claim 1 is characterized in that the particle size distribution range of said nanometer gunmetal powder is 1nm～100nm.
3. a kind of nanometer gunmetal electrically conductive ink according to claim 1 is characterized in that, by mass percentage, the content of copper and tin is respectively in the said nanometer gunmetal powder:
Copper: 70%～99.5%;
Tin: 0.5%～30%.
4. a kind of nanometer gunmetal electrically conductive ink according to claim 3 is characterized in that, and is more excellent, and by mass percentage, the copper of said nanometer gunmetal powder and the content of tin are respectively: 95% and 5%.
5. a kind of nanometer gunmetal electrically conductive ink according to claim 3 is characterized in that, also includes REE in the said nanometer gunmetal powder, and by mass percentage, the content of said copper, tin and REE is respectively:
Copper: 71%～99.4%;
Tin: 0.5%～28%;
Rare earth: 0.01%～5%.
6. a kind of nanometer gunmetal electrically conductive ink according to claim 5 is characterized in that more excellent, by mass percentage, the content of said copper, tin and REE is respectively: 95%, 4.9% and 0.1%.
7. a kind of nanometer gunmetal electrically conductive ink according to claim 1 is characterized in that said auxiliary agent comprises one or more in tensio-active agent, dispersion agent, coupling agent, reductive agent, adhesion promoter, the anti-settling agent.
8. a kind of nanometer gunmetal electrically conductive ink according to claim 7 is characterized in that said solvent comprises one or more of water, alcohols, ethers and ester class, and said alcohols, ethers and ester class are liquid at normal temperatures.
9. the preparation method like the arbitrary said nanometer gunmetal electrically conductive ink of claim 1-8 is characterized in that this method comprises the steps:
By weight, 8～60 parts of nanometer gunmetal powders are joined in 20～90 parts of solvents and 2～20 parts of auxiliary agents behind the thorough mixing, homodisperse 10～50 minutes obtains electrically conductive ink.
10. a method that adopts the arbitrary said nanometer gunmetal electrically conductive ink of claim 1-8 to print the conducting wire is characterized in that this method comprises the steps:
Electrically conductive ink is joined in ink-jet printer or the gravure printing machine; Through ink-jet printer or gravure printing machine electrically conductive ink is printed in the circuit board; The wiring board that is printed with electrically conductive ink is placed under the environment of vacuum or rare gas element; Attemperation is 120 ℃～150 ℃ sintering 5～50 minutes, treat that the volatilization of solvent and auxiliary agent is accomplished after, with the wiring board naturally cooling.
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