CN104672991A - Preparation method of copper conductive ink - Google Patents
Preparation method of copper conductive ink Download PDFInfo
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- CN104672991A CN104672991A CN201310606012.4A CN201310606012A CN104672991A CN 104672991 A CN104672991 A CN 104672991A CN 201310606012 A CN201310606012 A CN 201310606012A CN 104672991 A CN104672991 A CN 104672991A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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Abstract
The invention provides a preparation method of a copper conductive ink; the method includes the following steps: S1, heating a copper salt aqueous solution to 78-82 DEG C, then simultaneously dropwise adding an ascorbic acid aqueous solution and an inositol hexaphosphate aqueous solution, maintaining the temperature at 78-82 DEG C until a reaction is finished, and thus obtaining a copper nanoparticle dispersion liquid; S2, carrying out centrifugal separation of the copper nanoparticle dispersion liquid, washing, drying, and thus obtaining copper particles; and S3, mixing the copper nanoparticles with a solvent to obtain the copper conductive ink. The conductive copper ink prepared by the method has high dispersion of the metallic copper nanoparticle conductive ink, has concentrated particle size distribution, and can be aerobically stored for a long time. The preparation method is green and environmentally friendly, raw materials are cheap and easy to obtain, and the copper conductive ink has no chemical toxicity and can be prepared in large scale.
Description
Technical field
The invention belongs to conductive ink field, particularly relate to a kind of preparation method of copper conductive ink.
Background technology
At present, along with RF identification and RFID(Radio Frequency IDentification) technology fast universal, promote also more and more coming into one's own of the electrically conductive ink of one of key factor of progressively leading to success in RFID market.
Electrically conductive ink is dispersed in by metallic conducting particle (silver, copper, carbon are generally silver) a kind of conductive composite material formed in low-melting ink vehicle, after being printed onto on stock, plays the effect of wire, antenna and resistance.This ink printing can be made into printed wiring in flexibility or mechanically resistant material (paper, PVC, PE etc.).After electrically conductive ink drying, because the distance between conducting particles diminishes, unbound electron moves formation electric current along extra electric field direction, has good conductivity, can receive the radio frequency signal that RFID is special.For printing RFID label tag built-in aerial, a good conducting ink formulation, require to have good printability, the layer of ink after printing has the features such as strong adhesion, resistivity is low, solidification value is low, conductivity is stable.
Electrically conductive ink is made up of electroconductive stuffing, solvent and additive.The silver powder that electroconductive stuffing uses electroconductibility best and copper powder, also use bronze, graphite, carbon black (now existing special graphitized carbon black), carbon fibre, nickel powder etc. sometimes.At present, general using the organic-or-inorganic salt of noble metal as starting material, with organic reductive agent organic amine and aldehyde compound, add dispersion agent and tensio-active agent simultaneously, obtain the mixed solution of metal nanoparticle in the mode of chemical reduction, obtain metal nano powder by centrifugation, drying.Divide ultrasonic disperse in organic solvent metal nano, obtain metal nanoparticle conductive ink.
Publication number is the preparation method that CN101608077A discloses a kind of nano-copper conductive ink, concrete steps are: A: be dissolved in solvent by mantoquita and organic protection, be warming up to 30-100 DEG C gradually, reductive agent is added in reaction system simultaneously, Keep agitation reaction afterwards, after 20-30 minute, cools gradually; B: the solution of cooling is carried out electrodialysis desalination process, and adopt the mode of underpressure distillation to carry out concentration, stable nano-copper conductive ink can be obtained; Wherein, described reductive agent is one or several in sodium borohydride, hydrazine hydrate, inferior sodium phosphate and vitamins C; The mol ratio of reductive agent and mantoquita is 1-3:1.The metallic particles bad dispersibility that this obtains, particle size distribution is very wide.The metallic particles simultaneously obtained is unstable, is easy to oxidized, not easily preserves and use.In addition, the reduzate of use and reductive agent and reaction solvent are easy to environment, very not environmentally.
Summary of the invention
The present invention is that the copper particle size distribution solved in existing copper conductive ink is wide, the technical problem of copper particle instability, provides a kind of preparation method of the copper conductive ink that copper particle size distribution is concentrated, copper is particle stabilized.
The invention provides a kind of preparation method of copper conductive ink, the method comprises the following steps:
S1, copper salt solution is heated to 78-82 DEG C, then drips aqueous ascorbic acid and the phytinic acid aqueous solution simultaneously, keep temperature be 78-82 DEG C to reacting end, obtain copper nano particles dispersion liquid;
S2, copper nano particles dispersion liquid carried out centrifugation and carry out washing, dry, obtain copper particle;
S3, namely copper nano particles and solvent are obtained copper conductive ink.
In the preparation method of copper conductive ink of the present invention, metallic copper nanoparticle conductive ink dispersiveness is high, and size-grade distribution is concentrated, and can deposit by prolonged aerobic.Preparation method's environmental protection, starting material are cheap and easy to get, do not have chemical toxicity, can prepare in a large number.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of preparation method of copper conductive ink, the method comprises the following steps:
S1, copper salt solution is heated to 78-82 DEG C, then drips aqueous ascorbic acid and the phytinic acid aqueous solution simultaneously, keep temperature be 78-82 DEG C to reacting end, obtain copper nano particles dispersion liquid;
S2, copper nano particles dispersion liquid carried out centrifugation and carry out washing, dry, obtain copper particle;
S3, namely copper nano particles and solvent are obtained copper conductive ink.
In the preparation method of copper conductive ink of the present invention, using xitix simultaneously as reductive agent and modifier, first xitix provides an active hydrogen cupric ion of divalence to be reduced into the copper of zeroth order, generates the xitix of water and half dehydrogenation.Half L-dehydroascorbic acid can be combined with the phytinic acid added; the copper of reduction is played a protective role; when copper is again oxidized time; the xitix of half dehydrogenation can discharge an active hydrogen; again oxidized cupric ion is reduced into the copper of zeroth order; generate L-dehydroascorbic acid and water, phytinic acid is also as antioxidant simultaneously.The copper nano particles dispersion liquid that the present invention obtains has high dispersing stability, can standing storage, when application by its centrifugation and carry out washing, dry, be prepared into copper conductive ink after obtaining copper particle.
According to the preparation method of copper conductive ink provided by the present invention, preferably, the mol ratio of described mantoquita, xitix and phytinic acid is 1:0.5-1:0.005-0.5.Phytinic acid once at most can in conjunction with six and half L-dehydroascorbic acid molecules, and different phytinic acids can combine same half L-dehydroascorbic acid molecule simultaneously, so just can form the cross-linked network being similar to sponge structure in a space.The copper be reduced can enter the cross-linked network space of sponge structure, forms stable dispersion liquid.Meanwhile, effectively preventing copper is oxidized, ensures that dispersion liquid is preserved for a long time.
According to the preparation method of copper conductive ink provided by the present invention, preferably, in described copper salt solution, the concentration of mantoquita is 0.05-0.2mol/L.The excessive concentration of mantoquita can cause reaction product to be reunited, and affects the size of material and the distribution of particle diameter.
According to the preparation method of copper conductive ink provided by the present invention, in order to better control the size range of copper particle, preferably, in described aqueous ascorbic acid, the concentration of described left xitix is 0.025-0.1mol/L.
According to the preparation method of copper conductive ink provided by the present invention, in order to better protect copper particle not oxidized, preferably, in the described phytinic acid aqueous solution, the concentration of described phytinic acid is 0.0125-0.1mol/L.
According to the preparation method of copper conductive ink provided by the present invention, in order to make reaction more abundant, preferably, after described reaction terminates, continue insulation 30-50min.
According to the preparation method of copper conductive ink provided by the present invention, preferably, the time of described dropping is 40-60min.If drip too fast, easily cause that copper grain diameter is excessive and size-grade distribution is wide; Too slow, make whole reaction process need the more time, lose time.
According to the preparation method of copper conductive ink provided by the present invention, described mantoquita has no particular limits, the various solvable mantoquita can commonly used for this area, as at least one in Copper dichloride dihydrate, copper sulfate, cupric nitrate, venus crystals, Salzburg vitriol and succsinic acid copper.
According to the preparation method of copper conductive ink provided by the present invention, described solvent has no particular limits, and all kinds of SOLVENTS can commonly used for this area, as at least one in diethylene glycol monobutyl ether, dibutyl ethylene glycol ether, pimelinketone, hexalin and isobutyl ester.
According to the preparation method of copper conductive ink provided by the present invention, in order to increase the conductivity of copper conductive ink, preferably, with the gross weight of described copper conductive ink for benchmark, the content of described copper particle is 20-50wt%.
According to the preparation method of copper conductive ink provided by the present invention, in order to increase the conductivity of copper conductive ink, preferably, the median size of described copper particle is 1.0-2.5nm.
In the present invention, reaction uses oil bath heating or other devices that strictly can control temperature of reaction to heat, and reacts without the need to protection of inert gas.Temperature of reaction is too low or too highly can reduce productive rate.
Copper conductive ink of the present invention, metallic copper nanoparticle conductive ink dispersiveness is high, and size-grade distribution is concentrated, and can deposit by prolonged aerobic.Preparation method's environmental protection, starting material are cheap and easy to get, do not have chemical toxicity, can prepare in a large number.
Below by specific embodiment, the present invention is described in further detail.
embodiment 1
By the CuCl of 10mmol
22H
2o is dissolved in 50ml deionized water, uses magnetic agitation solution, and is heated to 80 DEG C with oil bath; Simultaneously to CuCl
22H
2evenly drip 50ml in O solution, the aqueous ascorbic acid of 0.1mol/L and the phytinic acid aqueous solution of 5ml, 0.05mol/L, time for adding 40min to 60min, control both rate of addition well.Reacted insulation 30min, naturally cooling, namely obtains the copper nano particles dispersion liquid A1 with high dispersing stability.
embodiment 2
Prepare copper nano particles dispersion liquid A2 according to the method for embodiment 1, difference is: mantoquita is cupric nitrate, and concentration is 0.05mol/L, and volume is 200ml; The concentration of aqueous ascorbic acid is 0.025mol/L, and volume is 40ml, and the concentration of the phytinic acid aqueous solution is 0.0125mol/L.
embodiment 3
Prepare copper nano particles dispersion liquid A3 according to the method for embodiment 1, difference is: mantoquita is copper sulfate, and concentration is 0.06mol/L, and volume is 100ml; The concentration of aqueous ascorbic acid is 0.05mol/L, and volume is 120ml; The concentration of the phytinic acid aqueous solution is 0.04mol/L, and volume is 30ml.
embodiment 4
Prepare copper nano particles dispersion liquid A4 according to the method for embodiment 1, difference is: mantoquita is venus crystals, and concentration is 0.08mol/L, and volume is 125ml; The concentration of aqueous ascorbic acid is 0.06mol/L, and volume is 120ml; The concentration of the phytinic acid aqueous solution is 0.06mol/L.
embodiment 5
Prepare copper nano particles dispersion liquid A5 according to the method for embodiment 1, difference is: mantoquita is Salzburg vitriol, and concentration is 0.1mol/L, and volume is 100ml; The concentration of aqueous ascorbic acid is 0.08mol/L, and volume is 90ml, and the concentration of the phytinic acid aqueous solution is 0.1mol/L.
embodiment 6
Prepare copper copper nano particles dispersion liquid A6 according to the method for embodiment 1, difference is: mantoquita is succsinic acid copper, and concentration is 0.15mol/L, and volume is 100ml, and the concentration of aqueous ascorbic acid is 0.03mol/L, and volume is 80ml.
comparative example 1
Copper nano particles dispersion liquid CA1 is prepared by the method that traditional method makes.
comparative example 2
Copper nano particles dispersion liquid CA2 is prepared according to the method for CN101608077A embodiment 1.
comparative example 3
Prepare copper nano particles dispersion liquid CA3 according to the method for embodiment 1, difference is: not containing phytinic acid.
performance test
1, particle diameter and size distribution test
The laser particle size analyzer Zetasizer nano ZS of Malvern company of Britain is adopted to analyze the size and distribution of nano particle.Instrument range 0.3nm-10 μm, ensures that accuracy is (p-poly-phenyl ethene standard particle) within ± 0.6%; Ensure that circulation ratio precision is within 0.1%.
Respectively by copper nano particles dispersion liquid A1-A6 and CA1-CA3 centrifugal 15min under the rotating speed of 8000rad/min, use deionized water and absolute ethanol washing twice respectively, then at room temperature vacuum-drying 2h, obtain nano copper particle.Get 0.2g nano copper particle ultrasonic disperse in 10ml dehydrated alcohol, jitter time 10min, obtains sample B1-B6 and CB1-CB3.
Sample B1-B6 and CB1-CB3 is put into Zetasizer nano ZS laser particle size analyzer and carry out size and distribution test.Test result is in table 1.
Table 1
2, print circuit specific conductivity test
1) sample preparation
Respectively get copper nano particles dispersion liquid A1-A6 and CA1-CA3 100ml, respectively dispersion liquid is divided into 5 grades and divides 20ml, place 1h, 24h, 36h, 72h and 100h respectively, then make the ink that can be used for spray ink Printing.
Ink making method: by the copper dispersion liquid centrifugal 15min under the rotating speed of 8000rad/min obtained, use deionized water and absolute ethanol washing twice respectively, then at room temperature vacuum-drying 2h, obtain in nano copper particle diethylene glycol monobutyl ether, after ultrasonic 15 min, obtain nano-copper conductive ink.
2) specific conductivity test
The Dimatix DMP-2800 ink-jet printer of Japanese Fujifilm company is adopted to print on polyimide film by nano-copper conductive ink, vacuum sintering 30min at 150 DEG C, then the specific conductivity of the metal copper nano granules of the AutoSigma300 conductivity measurement test printing of GE company of the U.S. is used, test frequency 500kHz, test result is in table 2.
Table 2
As can be seen from Table 1, the nano copper particle uniform particle sizes prepared by method of the present invention, distribution is concentrated.As can be seen from Table 2, the conductive copper ink prepared by method of the present invention can be placed for a long time, little to its performance impact, but the conductive copper ink of comparative example is after long-time existence, and its degradation is larger.Illustrate that the conductive copper ink metallic copper nanoparticle conductive ink dispersiveness prepared by method of the present invention is high, size-grade distribution is concentrated, and can deposit by prolonged aerobic.Preparation method's environmental protection, starting material are cheap and easy to get, do not have chemical toxicity, can prepare in a large number.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (11)
1. a preparation method for copper conductive ink, is characterized in that, the method comprises the following steps:
S1, copper salt solution is heated to 78-82 DEG C, then drips aqueous ascorbic acid and the phytinic acid aqueous solution simultaneously, keep temperature be 78-82 DEG C to reacting end, obtain copper nano particles dispersion liquid;
S2, copper nano particles dispersion liquid carried out centrifugation and carry out washing, dry, obtain copper particle;
S3, namely copper nano particles and solvent are obtained copper conductive ink.
2. the preparation method of copper conductive ink according to claim 1, is characterized in that, the mol ratio of described mantoquita, xitix and phytinic acid is 1:0.5-1:0.005-0.5.
3. the preparation method of copper conductive ink according to claim 1, is characterized in that, in described copper salt solution, the concentration of mantoquita is 0.05-0.2mol/L.
4. the preparation method of copper conductive ink according to claim 1, is characterized in that, in described aqueous ascorbic acid, the concentration of described xitix is 0.025-0.1mol/L.
5. the preparation method of copper conductive ink according to claim 1, is characterized in that, in the described phytinic acid aqueous solution, the concentration of described phytinic acid is 0.0125-0.1mol/L.
6. the preparation method of copper conductive ink according to claim 1, is characterized in that, after described reaction terminates, continues insulation 30-50min.
7. the preparation method of copper conductive ink according to claim 1, is characterized in that, the time of described dropping is 40-60min.
8. the preparation method of copper conductive ink according to claim 1, is characterized in that, described mantoquita be Copper dichloride dihydrate, copper sulfate, cupric nitrate, venus crystals, Salzburg vitriol and, at least one in succsinic acid copper.
9. the preparation method of copper conductive ink according to claim 1, is characterized in that, described solvent is at least one in diethylene glycol monobutyl ether, dibutyl ethylene glycol ether, pimelinketone, hexalin and isobutyl ester.
10. the preparation method of copper conductive ink according to claim 1, is characterized in that, with the gross weight of described copper conductive ink for benchmark, the content of described copper particle is 20-50wt%.
The preparation method of 11. copper conductive inks according to claim 1, is characterized in that, the median size of described copper particle is 1.0-2.5nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997604A (en) * | 2018-09-08 | 2018-12-14 | 佛山市禅城区诺高环保科技有限公司 | The preparation method of iron film is covered in a kind of anticorrosion |
| CN111421143A (en) * | 2020-04-01 | 2020-07-17 | 中国人民解放军陆军军医大学第一附属医院 | Preparation method of nano-copper particles for treating inflammatory diseases |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1696006A1 (en) * | 2005-02-28 | 2006-08-30 | Samsung SDI Germany GmbH | metal ink and substrate for a display and method for manufacturing the same |
| CN103087582A (en) * | 2013-01-25 | 2013-05-08 | 天津理工大学 | Preparation method of low-temperature sintering nano copper conductive ink |
-
2013
- 2013-11-26 CN CN201310606012.4A patent/CN104672991B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1696006A1 (en) * | 2005-02-28 | 2006-08-30 | Samsung SDI Germany GmbH | metal ink and substrate for a display and method for manufacturing the same |
| CN103087582A (en) * | 2013-01-25 | 2013-05-08 | 天津理工大学 | Preparation method of low-temperature sintering nano copper conductive ink |
Non-Patent Citations (1)
| Title |
|---|
| 熊皓平等: "天然植物抗氧化剂的研究进展", 《天然产物研究与开发》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997604A (en) * | 2018-09-08 | 2018-12-14 | 佛山市禅城区诺高环保科技有限公司 | The preparation method of iron film is covered in a kind of anticorrosion |
| CN111421143A (en) * | 2020-04-01 | 2020-07-17 | 中国人民解放军陆军军医大学第一附属医院 | Preparation method of nano-copper particles for treating inflammatory diseases |
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| CN104672991B (en) | 2017-07-04 |
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