CN102675961A - Conductive ink, and preparation method and application method thereof - Google Patents
Conductive ink, and preparation method and application method thereof Download PDFInfo
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- CN102675961A CN102675961A CN2011100550262A CN201110055026A CN102675961A CN 102675961 A CN102675961 A CN 102675961A CN 2011100550262 A CN2011100550262 A CN 2011100550262A CN 201110055026 A CN201110055026 A CN 201110055026A CN 102675961 A CN102675961 A CN 102675961A
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Abstract
The invention discloses conductive ink. The conductive ink comprises the following materials by weight: 8%-60% of nanometer metal particle, 20%-90% of solvent and 2%-30% of assistant, wherein the solvent and the assistant are boiled or decomposed at 40-190 DEG C at normal pressure, and substances obtained by decomposing the solvent and the assistant is boiled at 40-190 DEG C at normal pressure. The conductive ink is characterized in that a temperature range of a melting point of the nanometer metal particle is 115-180 DEG C, the assistant comprises a reducing agent, the reducing agent can be boiled or decomposed at 120-190 DEG C at normal pressure, substance obtained by decomposing the reducing agent is boiled at 120-190 DEG C at normal pressure, and the melting point of the nanometer metal particle is 5-75 DEG C lower than the boiling/decomposing temperature of the reducing agent at normal pressure.
Description
[technical field]
The invention belongs to material chemistry technical field, relate to a kind of electrically conductive ink and preparation method thereof and method of use.
[background technology]
Inkjet technology is the printing technique of a kind of contactless, no pressure, no forme, widespread use at present in daily life, inkjet technology can be applied in the flexible solid substrate; For example on various films and rough base, produce electrical element etc.; So to the RFID tag (RFID) that is in high-speed development period at present, printed substrate (PCB), flexible display; Industries such as flexible solar photovoltaic cell, inkjet technology receives much attention.
Traditional P CB manufacturing process prepares through the etching subtractive process; Its shortcoming is that production process is many, high material consumption, discharging of waste liquid is high, environmental protection pressure is heavy; And the making of every laminar substrate all need realize the transfer of conductive pattern with the different masks of ready-formed, also wants the glass photoresist subsequently.With regard to multilayer and lamination PCB, it is very big to repeat labor content, and every layer all relate to tens procedures, thus efficient is low, the waste big, pollute weigh, cost is high.Ink-jet printing process is conductive particle to be scattered in solvent form electrically conductive ink, utilizes computer control, through printing type electrically conductive ink is accurately deposited to the needed position of substrate.Say that from technology ink-jet printing process is particluarly suitable for making on the flexible substrates electron device; Say that from material it can accomplish the almost utilization ratio of zero waste of raw metal; From the angle of environmental protection, it has avoided the desired a large amount of operations of etch process, thereby reduces discharging, reduces energy consumption.
The key of ink-jet printing process is the preparation of various printing ink, and wherein electrically conductive ink is basis wherein, and the essence of electrically conductive ink is the dispersion system of conductive particle, and common conductive particle has conductive polymer material, graphite-like, pottery and metal etc.Wherein conductive polymer material, graphite-like, the general conductivity of ceramic conductive particle are relatively poor, are not suitable for as the conducting wire.The metallic conduction particle has metal and their alloys such as gold and silver, copper, tin, zinc, nickel, iron, aluminium, lead.At present many to the research of fine silver particulate printing ink is stronger because fine silver has unreactiveness, is difficult for oxidized characteristics; Take all factors into consideration conductivity, production and transport cost, use cost etc., generally believe that silver is that the cost performance of electrically conductive ink is higher, in addition; The electrically conductive ink of fine copper also someone develops, but because the chemical property of copper is comparatively active, is difficult for preparation and use; The requirement of equipment also than higher, thereby has been increased the complexity of application cost and total system.
The performance index of electrically conductive ink mainly are: (1) electric conductivity: the printing ink that contains conductive particle generally will pass through solvent boils and sintering process after depositing to substrate with inkjet printing methods; Form the successive electrical conductor; Owing to have unavoidable impurities and space; And bigger resistance between particle, its electric conductivity is not as good as the pure metal conductor; (2) printability: the droplet volume that ejects during spray ink Printing is generally below ten skins rise; So require electrically conductive ink to have good flowability, particle size, solids content and continuity; And the effect that guarantees printing, the printing ink that requires simultaneously to be printed on the printing plate has certain stability, viscosity, surface tension, rate of drying etc.; (3) sintering characteristic: need after electrically conductive ink is printed through heat treated; To remove or to reduce the content of solvent and other non-conductive additives; Sinter metallic particles into continuous solid body simultaneously, sintering temperature, heat-up time and whether to need the special gas environment be the index of weighing sintering characteristic.In general; Improve the electric conductivity that sintering temperature can improve remaining solid metal behind the sintering to a certain extent; Because temperature is high more, decomposition such as most of additive and solvent and ebullient speed are fast more, between the metal nanoparticle because the resistance that defective produces is also more little.But qualitative change at high temperature all takes place in the base material of most of wiring boards easily, and too high sintering temperature may make base material damage, thereby impacts to use.If but sintering temperature is low excessively, the solvent and the auxiliary agent that are present in the electrically conductive ink are difficult to seethe with excitement away, cause electrically conductive ink behind the sintering because of remaining have too much impurity to cause the electrically conductive ink sintering after the conducting wire electric conductivity descend.
The Chinese patent publication number is: but the patent of invention of CN 101805538A discloses the electrically conductive ink of a kind of low-temperature sintering (sintering temperature is 130 ℃～150 ℃); Comprise that in this electrically conductive ink massfraction is respectively 0.1%～10%, 25%～98% and 0.01%～36% dispersion agent, solvent and additive; Said additive is a kind of or two or more combinations in tensio-active agent, reductive agent, skimmer, tackiness agent, sanitas, the wetting Agent for Printing Inks; And also pointed out some concrete dispersion agents, solvent, tensio-active agent, reductive agent, skimmer, tackiness agent, sanitas and wetting Agent for Printing Inks in the application documents, some material is that some material of organism is an inorganics in these dispersion agents, solvent, tensio-active agent, skimmer, tackiness agent, sanitas and the wetting Agent for Printing Inks that provides, and some material is a small organic molecule; Some material is a macromolecule organic; The boiling point of some material is lower than 150 ℃ under normal pressure, the boiling of some material or decomposition temperature are higher than 150 ℃ under normal pressure, even is higher than 200 ℃; When the boiling temperature of these auxiliary agents is higher than 150 ℃; Sintering temperature is below 150 ℃ the time under normal pressure, and these things are difficult to from electrically conductive ink boiling and come out, thereby influence the electroconductibility behind the sintering; So the material that must select for use can seethe with excitement away, otherwise can influence the conductivity behind the electrically conductive ink sintering when sintering.Described additive comprises reductive agent; Reductive agent is used for protecting the nano-metal particle at production, transportation and use electrically conductive ink not oxidized; To guarantee the electric conductivity of the finished product; And reductive agent can also protect nano-metal particle nano-metal particle in sintering process not oxidized or the nonmetallic impurity in the nano-metal particle of oxidation removed, and the nano-metal-oxide that perhaps oxidation is generated is reduced to nano metal, thereby improves sintering effect; Reduce sintering temperature, improve electroconductibility.And reductive agent seethes with excitement away after being preferably in the nano-metal particle fusing; With electric conductivity behind the assurance electrically conductive ink sintering; Be the boiling of reductive agent or the fusing point that decomposition temperature will be higher than nano-metal particle; And the boiling of reductive agent or decomposition temperature also will be lower than the damage temperature of base material, and promptly reductive agent is elevated in sintering temperature and seethe with excitement away before damaging base material, and the assurance base material is not damaged.
In this patent, the boiling of cited Peng Qinghuana, sodium hypophosphite, xitix, S-WAT and methyl sodium hydrosulfite or decomposition temperature are higher than 200 ℃, if the sintering temperature that adopts is for being lower than 200 ℃; Then these reductive agents are difficult to seethe with excitement away; Can still remain in the electrically conductive ink behind the sintering, influence its electric conductivity, and the boiling temperature of Hydrazine Hydrate 80, formic acid and formaldehyde be lower than 120 ℃; If the sintering temperature that adopts is 120 ℃; Be that reductive agent does not also promptly seethe with excitement before the sintering fusing at nano-metal particle, then can make nano-metal particle oxidized in sintering process, thereby influence its electric conductivity; And still can remain in after zinc powder and the iron powder oxidation by air in the electrically conductive ink behind the sintering, thereby influence the electric conductivity of conducting wire.
So the selection of reductive agent is all extremely important in storage, transportation and sintering process for electrically conductive ink, and the boiling of reductive agent or decomposition temperature must be the fusing point that is higher than nano-metal particle, and be lower than the damage temperature of base material.
[summary of the invention]
In order to solve above-mentioned technical problem; The present invention proposes a kind of new electrically conductive ink and preparation method thereof and method of use; In this electrically conductive ink, include reductive agent; And the boiling of said reductive agent or decomposition temperature both be lower than the damage temperature of base material, were higher than the sintering temperature of nano-metal particle simultaneously again, had guaranteed the electric conductivity of electrically conductive ink behind sintering.
Concrete technical scheme of the present invention is following:
The present invention provides a kind of electrically conductive ink; By mass percentage; Include 8%～60% nano-metal particle, 20%～90% solvent and 2%～30% auxiliary agent in this electrically conductive ink, said solvent and auxiliary agent be boiling or decompose 40 ℃～190 ℃ the time under normal pressure, and the material after said solvent decomposes with auxiliary agent seethes with excitement 40 ℃～190 ℃ the time under normal pressure; It is characterized in that; The melting temperature scope of said nano-metal particle is 115 ℃～180 ℃, and said auxiliary agent comprises reductive agent, 120 ℃～190 ℃ time boilings or decompose under normal pressure of said reductive agent; Material after said reductive agent decomposes is boiling 120 ℃～190 ℃ the time under normal pressure, and the fusing point of said nano-metal particle is than low 5 ℃～70 ℃ of the boiling/decomposition temperature of said reductive agent under normal pressure.
Said reductive agent accounts for 1.5%～7% of electrically conductive ink total mass.
Said reductive agent is that the benzene series thing is or/and the verivate of benzene series thing.
Said benzene series thing is one or more in aniline, phenol, phenylcarbinol, phenyl aldehyde, the phenylformic acid.
Said nano-metal particle is the Nanoalloy particle.
More excellent, said Nanoalloy particle is a nanometer gunmetal particle.
Said Nanoalloy particulate median size is 10nm～75nm.
Said nanometer copper alloy particle is a nanometer gunmetal particle, and by mass percentage, the content of copper and tin is respectively in the said nanometer gunmetal particle:
Copper: 70%～99.9%;
Tin: 0.1%～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 also comprises one or more in tensio-active agent, dispersion agent, coupling agent, the anti-settling agent.
Boiling temperature or decomposition temperature scope are that 40 ℃～190 ℃ tensio-active agent comprises having under the normal pressure: X 2073, Walocel MT 20.000PV, shell gather acid, vinylpyridine copolymer, polyvinyl butyral acetal and N vinyl pyrrolidone, and said tensio-active agent comprises one or more of above-mentioned substance.
Boiling temperature or decomposition temperature scope are that 40 ℃～190 ℃ said dispersion agent includes under the normal pressure: alkyl sulfhydryl, alkyl acid, alkylamine, alkylphosphonic acid carboxylic acid and contain the micromolecular compound of ring texture, said dispersion agent comprises one or more of above-mentioned substance.
Boiling temperature or decomposition temperature scope are that 40 ℃～190 ℃ said coupling agent is under the normal pressure: the KBM1003 coupling agent that Japan XINYUE produces.
Boiling temperature or decomposition temperature scope are that 40 ℃～190 ℃ said anti-settling agent is: the N-Methyl pyrrolidone of modification polyureas under the normal pressure.
Boiling temperature or decomposition temperature scope are that 40 ℃～190 ℃ said solvent comprises: one or more of water, alcohols, ethers and ester class under the normal pressure.
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 aforesaid 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 method that adopts aforesaid electrically conductive ink to print the conducting wire 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 electrocondution slurry is placed air; Regulate sintering temperature to 125 ℃～195 ℃ gradually, and guarantee that sintering temperature is higher than 5 ℃～75 ℃ of said solvent and the boiling/decomposition temperature of auxiliary agent under normal pressure; Sintering 5 minutes～90 minutes treats that solvent and the auxiliary agent back of having seethed with excitement forms the circuit of high conductivity.
Beneficial technical effects of the present invention is:
Owing to adopted boiling temperature or decomposition temperature to be in the reductive agent between nano-metal particle fusing point and the printing substrate material damage temperature; Make reductive agent can either protect nano-metal particle when sintering, to be unlikely to oxidized; Simultaneously; Can guarantee that again reductive agent can seethe with excitement away after sintering, make that electrically conductive ink remaining impurities after sintering is less, thereby improved the electric conductivity of conducting wire.
The present invention adopts one or more in aniline, phenol, phenylcarbinol, phenyl aldehyde, the phenylformic acid; Because the boiling temperature of reductive agent under normal pressure of these benzene series things is 120 ℃～190 ℃; So can guarantee electrically conductive ink under normal pressure 125 ℃～195 ℃ the time sintering also can seethe with excitement away; And in the time of 125 ℃～195 ℃, during sintering, can not damage the printing substrate material yet.Simultaneously because had reductive agent when sintering as protection, make that electrically conductive ink need not to be under vacuum or the rare gas element, has saved production cost when sintering.
Choosing low-melting tin alloy is that low solvent and the auxiliary agent of can making again simultaneously of sintering temperature is in the prerequisite of seething with excitement away behind the sintering and not damaging base material during at sintering as the conductive filler material of electrically conductive ink.The nanometer gunmetal that the present invention selects for use is as the conductive filler material of electrically conductive ink; The sintering temperature that can guarantee electrically conductive ink is lower; Simultaneously can guarantee that electrically conductive ink sintering in air is unlikely to oxidized, the gunmetal conducting wire that forms behind the sintering simultaneously is also high to also than copper metallographic phase because of being doped with its electric conductivity of REE.
[embodiment]
The present invention relates to a kind of electrically conductive ink, also relate to the preparation method and the method for use of this electrically conductive ink.A kind of electrically conductive ink; By mass percentage; Include 8%～60% nano-metal particle, 20%～90% solvent and 2%～30% auxiliary agent in this electrically conductive ink, said solvent and auxiliary agent be boiling or decompose 40 ℃～190 ℃ the time under normal pressure, and the material after said solvent decomposes with auxiliary agent seethes with excitement 40 ℃～190 ℃ the time under normal pressure; It is characterized in that; The melting temperature scope of said nano-metal particle is 115 ℃～180 ℃, and said auxiliary agent comprises reductive agent, 120 ℃～190 ℃ time boilings or decompose under normal pressure of said reductive agent; Material after said reductive agent decomposes is boiling 120 ℃～190 ℃ the time under normal pressure, and the fusing point of said nano-metal particle is than low 5 ℃～75 ℃ of the boiling/decomposition temperature of said reductive agent under normal pressure.Adopt normal pressure down boiling/decomposition temperature be in the reductive agent between the damage temperature of fusing point and printing substrate material of nano-metal particle; Make reductive agent can either protect nano-metal particle when sintering, to be unlikely to oxidation by air; Simultaneously; Can guarantee that again reductive agent can seethe with excitement away after sintering, make that electrically conductive ink remaining impurities after sintering is less, thereby improved the electric conductivity of conducting wire.
Below in conjunction with specific embodiment the present invention is done further to set forth and explanation:
Embodiment 1
A kind of 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 75nm, 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-X 2073,1.5 parts of reductive agent-aniline.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 X 2073, vibration is ground and was disperseed 10 minutes in ultrasound environments; After disperseing to accomplish; In filtered liq, add 1.5 parts of aniline, continuing vibrates to grind under ultrasound environments disperseed 5 minutes, made nanometer gunmetal electrically conductive ink.
The above-mentioned 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 150 ℃ the environment; Sintering 50 minutes; Obtain sintered product, under electron microscope, observe sintered product and find that the nanometer gunmetal particle in this nanometer gunmetal electrically 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 9 * 10
-7Ω m.
Embodiment 2
A kind of 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 99.9% and 0.1%; 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-vinylpyridine copolymers, 5 parts of dispersion agent-alkyl acids, 5 parts of KBM1003 coupling agent, 7 parts of reductive agent-phenol 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-vinylpyridine copolymers, 5 parts of dispersion agent-alkyl acids, 5 parts of KBM1003 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 7 parts of phenol; 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; With the PVC that is printed with electrically conductive ink be positioned in the air, under 195 ℃ the environment; Sintering 5 minutes; Obtain sintered product, under electron microscope, observe sintered product and find that the nanometer gunmetal particle in this nanometer gunmetal electrically 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
-7Ω m.
Embodiment 3
A kind of 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%, comprises 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 reductive agent-phenyl aldehyde.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; Vibration is ground and was disperseed 5 minutes in ultrasound environments, after disperseing to accomplish, adds 2 parts of phenyl aldehydes; 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 PE; The PE that is printed with electrically conductive ink is positioned in the air under the environment with 125 ℃; Sintering 90 minutes; Obtain sintered product, under electron microscope, observe sintered product and find that the nanometer gunmetal particle in this nanometer gunmetal electrically 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
-7Ω m.
Embodiment 4
A kind of 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 16 parts of water, 36 parts of diacetone alcohols, 20 parts of acetone in said 72 parts of solvents, said 20 parts of auxiliary agents comprise the N-Methyl pyrrolidone of KBM1003 coupling agent, 8 parts of reductive agent-phenylformic acid and 3 parts of anti-settling agent-modification polyureas of 3 parts of tensio-active agent-Walocel MT 20.000PVs, 3 parts of dispersion agent-alkylamines, 3 parts of coupling agent-Japan XINYUE's productions.16 parts of water, 36 parts of diacetone alcohols, 20 parts of acetone are mixed and make 72 parts of solvents; 8 parts of nanometer gunmetal powders are joined in 72 parts the solvent; Add 3 parts of tensio-active agent-Walocel MT 20.000PVs, 3 parts of dispersion agent-alkylamines, 3 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, adds the N-Methyl pyrrolidone of 8 parts of reductive agent-phenylformic acid and 3 parts of anti-settling agent-modification polyureas; Continuation is vibrated to grind under ultrasound environments and was disperseed 8 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 PI; The PI that is printed with electrically conductive ink is positioned under the environment of vacuum and 155 ℃; Sintering 30 minutes; Obtain sintered product, under electron microscope, observe sintered product and find that the nanometer gunmetal particle in this nanometer gunmetal electrically 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
-7Ω 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, 7 parts of Diethylene Glycol butyl ether and 1 part of acetone in said 50 parts of solvents, said 14 parts of auxiliary agents comprise the N-Methyl pyrrolidone of KBM1003 coupling agent, 6 parts of reductive agent-phenylcarbinols 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, 7 parts of Diethylene Glycol butyl ether 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 KBM1003 coupling agents that coupling agent-Japan XINYUE produces simultaneously; Vibration is ground and was disperseed 30 minutes in ultrasound environments, after disperseing to accomplish, adds 6 parts of reductive agent-phenylcarbinols; Continuation is vibrated to grind under ultrasound environments and was disperseed 20 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 paper; The paper that is printed with electrically conductive ink is positioned in the air under the environment with 185 ℃; Sintering 35 minutes; Obtain sintered product, under electron microscope, observe sintered product and find that the nanometer gunmetal particle in this nanometer gunmetal electrically 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
-7Ω 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. electrically conductive ink; By mass percentage; Include 8%～60% nano-metal particle, 20%～90% solvent and 2%～30% auxiliary agent in this electrically conductive ink, said solvent and auxiliary agent be boiling or decompose 40 ℃～190 ℃ the time under normal pressure, and the material after said solvent decomposes with auxiliary agent seethes with excitement 40 ℃～190 ℃ the time under normal pressure; It is characterized in that; The melting temperature scope of said nano-metal particle is 115 ℃～180 ℃, and said auxiliary agent comprises reductive agent, 120 ℃～190 ℃ time boilings or decompose under normal pressure of said reductive agent; Material after said reductive agent decomposes is boiling 120 ℃～190 ℃ the time under normal pressure, and the fusing point of said nano-metal particle is than low 5 ℃～75 ℃ of the boiling/decomposition temperature of said reductive agent under normal pressure.
2. electrically conductive ink according to claim 1 is characterized in that, said reductive agent is that the benzene series thing is or/and the verivate of benzene series thing.
3. a kind of electrically conductive ink according to claim 2 is characterized in that, said benzene series thing is one or more in aniline, phenol, phenylcarbinol, phenyl aldehyde, the phenylformic acid.
4. according to the arbitrary described a kind of electrically conductive ink of claim 1-3, it is characterized in that said nano metal gold grain is the Nanoalloy particle, said Nanoalloy particulate median size is 10nm～75nm.
5. a kind of electrically conductive ink according to claim 4 is characterized in that, said nanometer copper alloy particle is a nanometer gunmetal particle, and by mass percentage, the content of copper and tin is respectively in the said nanometer gunmetal particle:
Copper: 70%～99.9%;
Tin: 0.1%～30%.
6. a kind of electrically conductive ink according to claim 5 is characterized in that, and is more excellent, and by mass percentage, the content of said nanometer gunmetal particulate copper and tin is respectively: 95% and 5%.
7. a kind of electrically conductive ink according to claim 5 is characterized in that, also includes REE in the said nanometer gunmetal particle, 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%.
8. a kind of electrically conductive ink according to claim 7 is characterized in that, and is more excellent, and by mass percentage, the content of said copper, tin and REE is respectively: 95%, 4.9% and 0.1%.
9. one kind prepares arbitrary described electrically conductive ink like claim 1-8, 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.
10. the arbitrary described electrically conductive ink of employing such as claim 1-8 is printed the method for conducting wire, 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 electrocondution slurry is placed air; Regulate sintering temperature to 125 ℃～195 ℃ gradually, and guarantee that sintering temperature is higher than 5 ℃～75 ℃ of said solvent and the boiling/decomposition temperature of auxiliary agent under normal pressure; Sintering 5～90 minutes treats that solvent and the auxiliary agent back of having seethed with excitement forms the circuit of high conductivity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110055026.2A CN102675961B (en) | 2011-03-08 | 2011-03-08 | A kind of electrically conductive ink and preparation method thereof and using method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110055026.2A CN102675961B (en) | 2011-03-08 | 2011-03-08 | A kind of electrically conductive ink and preparation method thereof and using method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102675961A true CN102675961A (en) | 2012-09-19 |
| CN102675961B CN102675961B (en) | 2015-08-19 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146249A (en) * | 2013-03-01 | 2013-06-12 | 溧阳市新力机械铸造有限公司 | Nano gold-tin-copper alloy conductive ink |
| CN103160166A (en) * | 2013-03-01 | 2013-06-19 | 溧阳市新力机械铸造有限公司 | Nano-silver tin-copper alloy conductive ink |
| CN103228109A (en) * | 2013-03-01 | 2013-07-31 | 溧阳市新力机械铸造有限公司 | Line resistance welding process for printed circuit board |
| CN104962113A (en) * | 2015-06-27 | 2015-10-07 | 铜陵铜基粉体科技有限公司 | Spherical copper powder with radiation protection function and preparation method for spherical copper powder |
| CN105017817A (en) * | 2015-06-27 | 2015-11-04 | 铜陵铜基粉体科技有限公司 | Flame retardant copper-tin alloy powder and making method thereof |
| CN105038334A (en) * | 2015-06-27 | 2015-11-11 | 铜陵铜基粉体科技有限公司 | Corrosion-resisting water-based copper-zinc alloy powder and production method thereof |
| CN108441927A (en) * | 2018-02-27 | 2018-08-24 | 德阳利源节能科技有限公司 | A kind of hot dip film liquid |
| CN108893044A (en) * | 2018-06-29 | 2018-11-27 | 南京信息工程大学 | A kind of high-peeling strength coating and the preparation method and application thereof |
| CN109943150A (en) * | 2019-02-01 | 2019-06-28 | 广东华祐新材料有限公司 | A kind of electrically conductive ink and its preparation method and application |
| CN112437706A (en) * | 2018-08-08 | 2021-03-02 | 三井金属矿业株式会社 | Composition for bonding, bonded structure of electrical conductor, and method for producing same |
| CN115947543A (en) * | 2022-12-20 | 2023-04-11 | 重庆永信科技有限公司 | Etching method of flexible glass single-sided pattern |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009091634A (en) * | 2007-10-10 | 2009-04-30 | Dowa Electronics Materials Co Ltd | Method for producing silver fine powder |
| JP2009102716A (en) * | 2007-10-25 | 2009-05-14 | Dowa Electronics Materials Co Ltd | Method for producing silver nanoparticle |
| WO2009111393A2 (en) * | 2008-03-05 | 2009-09-11 | Applied Nanotech Holdings, Inc. | Additives and modifiers for solvent- and water-based metallic conductive inks |
| CN101569936A (en) * | 2009-06-05 | 2009-11-04 | 中国乐凯胶片集团公司 | Preparation method for flaky micro-aluminum powder |
| CN101583449A (en) * | 2007-01-09 | 2009-11-18 | 同和电子科技有限公司 | Silver fine powder, method for producing the same, and ink |
| CN101805538A (en) * | 2010-04-08 | 2010-08-18 | 中国科学院宁波材料技术与工程研究所 | Lower-temperature sintered conductive ink |
| CN101880493A (en) * | 2010-07-01 | 2010-11-10 | 中国科学院宁波材料技术与工程研究所 | Method for preparing nano copper conductive ink |
-
2011
- 2011-03-08 CN CN201110055026.2A patent/CN102675961B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101583449A (en) * | 2007-01-09 | 2009-11-18 | 同和电子科技有限公司 | Silver fine powder, method for producing the same, and ink |
| JP2009091634A (en) * | 2007-10-10 | 2009-04-30 | Dowa Electronics Materials Co Ltd | Method for producing silver fine powder |
| JP2009102716A (en) * | 2007-10-25 | 2009-05-14 | Dowa Electronics Materials Co Ltd | Method for producing silver nanoparticle |
| WO2009111393A2 (en) * | 2008-03-05 | 2009-09-11 | Applied Nanotech Holdings, Inc. | Additives and modifiers for solvent- and water-based metallic conductive inks |
| CN101569936A (en) * | 2009-06-05 | 2009-11-04 | 中国乐凯胶片集团公司 | Preparation method for flaky micro-aluminum powder |
| CN101805538A (en) * | 2010-04-08 | 2010-08-18 | 中国科学院宁波材料技术与工程研究所 | Lower-temperature sintered conductive ink |
| CN101880493A (en) * | 2010-07-01 | 2010-11-10 | 中国科学院宁波材料技术与工程研究所 | Method for preparing nano copper conductive ink |
Cited By (14)
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|---|---|---|---|---|
| CN103146249A (en) * | 2013-03-01 | 2013-06-12 | 溧阳市新力机械铸造有限公司 | Nano gold-tin-copper alloy conductive ink |
| CN103160166A (en) * | 2013-03-01 | 2013-06-19 | 溧阳市新力机械铸造有限公司 | Nano-silver tin-copper alloy conductive ink |
| CN103228109A (en) * | 2013-03-01 | 2013-07-31 | 溧阳市新力机械铸造有限公司 | Line resistance welding process for printed circuit board |
| CN103160166B (en) * | 2013-03-01 | 2014-10-29 | 溧阳市新力机械铸造有限公司 | Nano-silver tin-copper alloy conductive ink |
| CN103228109B (en) * | 2013-03-01 | 2015-11-25 | 溧阳市新力机械铸造有限公司 | The circuit welding resistance technique of printed circuit board (PCB) |
| CN105038334A (en) * | 2015-06-27 | 2015-11-11 | 铜陵铜基粉体科技有限公司 | Corrosion-resisting water-based copper-zinc alloy powder and production method thereof |
| CN105017817A (en) * | 2015-06-27 | 2015-11-04 | 铜陵铜基粉体科技有限公司 | Flame retardant copper-tin alloy powder and making method thereof |
| CN104962113A (en) * | 2015-06-27 | 2015-10-07 | 铜陵铜基粉体科技有限公司 | Spherical copper powder with radiation protection function and preparation method for spherical copper powder |
| CN108441927A (en) * | 2018-02-27 | 2018-08-24 | 德阳利源节能科技有限公司 | A kind of hot dip film liquid |
| CN108893044A (en) * | 2018-06-29 | 2018-11-27 | 南京信息工程大学 | A kind of high-peeling strength coating and the preparation method and application thereof |
| CN112437706A (en) * | 2018-08-08 | 2021-03-02 | 三井金属矿业株式会社 | Composition for bonding, bonded structure of electrical conductor, and method for producing same |
| CN112437706B (en) * | 2018-08-08 | 2024-01-02 | 三井金属矿业株式会社 | Bonding composition, conductive body bonding structure, and method for manufacturing same |
| CN109943150A (en) * | 2019-02-01 | 2019-06-28 | 广东华祐新材料有限公司 | A kind of electrically conductive ink and its preparation method and application |
| CN115947543A (en) * | 2022-12-20 | 2023-04-11 | 重庆永信科技有限公司 | Etching method of flexible glass single-sided pattern |
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