CN102675963B - Continuous preparing method of nanometer particle conductive ink - Google Patents
Continuous preparing method of nanometer particle conductive ink Download PDFInfo
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Abstract
The invention relates to a continuous preparing method of nanometer particle conductive ink and belongs to the technical field of nanometer materials. The method includes the following steps: (1) preparing solution A containing solvents, surface active agents, organic protective agents and metal; and preparing reducing agent solution B containing viscosity modifier; and (2) leading the solution A and the solution B to be simultaneously connected with two constant flow pumps or injection pumps and continuously sending the solution A and the solution B to a tubular reactor with a heater device for reaction. Feeding lasting time ranges from 30 min to 180 min, the reaction temperature is controlled to range from 20 DEG C to 200 DEG C, and the nanometer particle conductive ink can be obtained. The particle diameter of nanometer particles in the nanometer particle conductive ink is 2-20 nm, particle dispersity is good, and mass content is 2-35%. Compared with the prior art, the method is simple in operation process, mild and controllable in reaction conditions, good in particle dispersity, low in cost and capable of achieving industrialization easily.
Description
Technical field
The invention belongs to technical field of nano material, especially relate to a kind of continuous production method of nanoparticle conductive ink.
Background technology
Along with electronic product is to miniaturization, flexibility future development, particularly adopt inkjet technology can make various electron devices and circuit, on flexible substrate, make various electronic circuits or device, make it have functions such as electric transmission, signal transmitting, electromagnetic shielding, opto-electronic conversion.As wireless frequency spectrum identification (RFID) label, Organic Light Emitting Diode (OLED)), thin film transistor (TFT), storer (Memory) etc., there is huge superiority than conventional photoetch method technology.But the conductive ink that traditional micron order electrocondution slurry or larger particle are prepared can not meet current electronic devices and components to more low processing temperature and the more requirement of small-feature-size.Nano-silver conductive slurry/ink that exploitation adapts to low thermal treatment temp, small size complete processing has become the inexorable trend that electrocondution slurry develops.
Conductive ink (clcctrically conductive ink) is a kind of being printed on various non-conductive objects, forms printed wiring, after dry also sintering, has the ink of good conduction current ability.Can be divided into gold and silver, copper, carbon etc. according to conductive filler material, silver powder becomes the focus of conductive ink research because having the factors such as good chemical stability, high specific conductivity.But the nano particle of current business-like conductive ink is excessive, and sintering temperature is too high, matrix range of choice is limited, seriously hinder the development of printed electronics technology, and nano particle spray ink Printing conductive ink is a kind of desirable solution.But existing spray ink Printing conductive ink, great majority only rest on intermittently preparatory phase of simple shaking flask, in intermittence preparation process, because mass transfer and the heat-transfer effect of macroscopical liquid in reactor are poor, to the potential disadvantageous effect of being prepared with of nano particle, and along with the increase of reactor volume, the homogeneity of temperature in the kettle and concentration is difficult to realize more.Utilize controlledly synthesis and extensive preparation that intermittently synthetic method is difficult to realize high-quality nano particle.Therefore, exploitation possesses homogeneous small particle size, sintering temperature and low, and the nanoparticle conductive ink of the continuous production of Heat stability is good is very necessary.
Summary of the invention
The technical problem to be solved in the present invention is the manual intermittent operation that overcomes existing preparation method, inefficient defect, and a kind of method of nanoparticle conductive ink continuous production is provided, and efficiency is high, steady quality, and particle dispersion is good.
In order to solve the problems of the technologies described above, the invention provides following technical scheme:
The method of nanoparticle conductive ink continuous production, comprises the following steps:
1) configuration solution A, described solution A is containing one of solvent, tensio-active agent, organic protective agent, metal or metallic compound salt; Configuration contains the reductant solution B of viscosity modifier:
In described solution A, B, solvent is one or the arbitrary combination in polar solvent or non-polar solvent; Described organic protective agent is the one or any combination in organic acid or organic amine;
Metal or metallic compound salt: organic protective agent: the mol ratio of tensio-active agent is 1:(1.5～5): (1.5～7); The mol ratio of metal or metallic compound and reductive agent is 1:1～1:7;
2) solution A, solution B simultaneously, are progressively delivered to the reactor that continues stirring, feeding time length 30～180min, controls 20～200 ℃ of temperature of reaction, obtains nanoparticle conductive ink.
Described metal or metallic compound salt: at least comprise following a kind of negatively charged ion or arbitrary combination: nitrate ion, carbanion, acetate ion, sulfate ion, oxalate denominationby, cyanic acid ion, nitrite ion, phosphate anion, thiocyanate ion, chloranion, perchlorate, tetrafluoroborate ion or methyl ethyl diketone radical ion, also comprise Cu, Ag, Au, Zn, Ni, Co, Pd, Pt, Ti, V, Mn, Fe, Mo, W, Ru, Cd, Ta, Al, Ga, Ge, In, Sn, at least one in Pb and Bi and their alloy or alloyed oxide or any combination.Wherein preferred Ag, Au, Cu, Zn, Ni, Fe, In, Sn metal or metallic compound salt.
Described organic acid is: caproic acid, enanthic acid, sad, isocaprylic acid, laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid, behenic acid or chain alkyl carboxylic acid and derivative thereof; Described organic amine is: n-Butyl Amine 99, isobutylamine, isobutylcarbylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, octodrine, nonyl amine, decyl amine, amino dodecane, tetradecy lamine, cetylamine, stearylamine or chain alkyl amine and derivative thereof.Preferably organic acid is palmitic acid, stearic acid, behenic acid, and preferably stating organic amine is cetylamine, stearylamine.
Described tensio-active agent is that tensio-active agent is: the one in tween, TX-10, AEO-9 or trolamine or arbitrary combination.
Described reductive agent is one or the arbitrary combination in sodium borohydride, Trisodium Citrate, citric acid, POTASSIUM BOROHYDRIDE, dimethyamine borane, hydrazine hydrate, phenylhydrazine, acethydrazide, methyldiethanolamine, xitix, glucose, inferior sodium phosphate or hydrogen peroxide.Preferably reductive agent is xitix, citric acid, hydrazine hydrate, glucose.
Described polar solvent is: water, methyl alcohol, ethanol, glycerine, ethylene glycol, polyoxyethylene glycol, Virahol, isopropylcarbinol or dimethyl sulfoxide (DMSO); Non-polar solvent is: hexanaphthene, methylcyclohexane, sherwood oil, benzene,toluene,xylene, trichloromethane or ethyl acetate.Preferably polar solvent is ethanol, ethylene glycol, polyoxyethylene glycol, and preferably non-polar solvent is hexanaphthene, toluene, dimethylbenzene.
The device of aforesaid method continuous production nano particle used, comprises solution bottle A, solution bottle B, its respectively by constant flow pump deliver to continuously be provided with the tubular reactor of heater assembly in react, reactor is also provided with nano particle and collects mouthful.
In the nanoparticle conductive ink making according to the inventive method, the particle diameter of nano particle is 2-20nm, mass content is 2-35%, can be directly by spray ink Printing on various base materials, be applied to wireless frequency spectrum identification (RFID) label, Organic Light Emitting Diode (OLED)), the field such as thin film transistor (TFT), flexible print circuit board or printed-wiring board (PWB).Compared with prior art, beneficial effect of the present invention is: 1, present method continuous production, and operating procedure is simple, and reaction conditions gentleness is controlled.2, product nano particle footpath homogeneous is less than 20nm, and particle dispersion is good.3, preparation cost is low, and environmental friendliness is easy to realize industrialization.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, for explaining the present invention, is not construed as limiting the invention together with embodiments of the present invention.In the accompanying drawings:
Fig. 1 is the setting drawing of the nano silver conductive ink of the embodiment of the present invention 1 continuous production;
Fig. 2 is the TEM figure of the silver-colored particle in the nano silver conductive ink of the embodiment of the present invention 1 continuous production.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein, only for description and interpretation the present invention, is not intended to limit the present invention.
As shown in Figure 1, the device of continuous production nano particle comprises 2 constant flow pumps 1, two interface tubular reactors 2, temp controlling heater 3.The entrance end of two interface tubular reactors 2, the other end that connects respectively 1,2 constant flow pump 1 of 2 constant flow pumps by silicone tube is in charge of and is received respectively in the solution bottle that solution A, solution B are housed by silica gel, and two interface tubular reactors 2 are placed in temp controlling heater interior 3.Constant flow pump, tubular reactor and well heater etc. all can adopt existing product.
embodiment 1
By 22.7g(0.13mol) Silver Nitrate, 500ml deionized water, 70.2g(0.2mol) tensio-active agent tween 80,83.2g(0.4mol) stearic acid is placed in solution bottle A, keeping solution temperature is 50 ℃, and lasting stirring reaction obtains solution A after 20-180 minutes.22.8g(0.13mol) xitix, 100ml deionized water are mixed to get solution B in solution bottle B.By constant flow pump, solution A, B are continued to be transported to (internal diameter 0.05mm) reaction in two interface tubular reactors with the flow velocity of 0.05ml/min, continue approximately 140 minutes, controlling temperature of reaction is 100 C.Collect reaction liquid C in tubular reactor exit, gained reaction solution is Nano silver solution.Utilize particle diameter and the pattern of the nanometer silver of Electronic Speculum to gained to observe, it is subsphaeroidal that observations (referring to Fig. 2) shows that the nano-Ag particles of gained is, and evenly, particle diameter is mainly distributed in 5.3～12.7mm to size, and median size is 8.5mm.By regulating Nano silver solution can obtain stable nano silver conductive ink (l5wt%).After using printing of inkjet printer on film, 120 ℃ are heated 30 minutes, and can obtain this specific conductivity is 8.5 μ Ω .cm.
By 22.7g(0.13mol) Silver Nitrate, 500ml deionized water, 129.2g(0.2mol) tensio-active agent TX-10,57.8g(0.24mol) cetylamine is placed in solution bottle A, keeping solution temperature is 60 ℃, and lasting stirring reaction obtains solution A after 20-180 minutes.27.3g(0.13mol) deionized water of citric acid, 100ml obtains solution B in solution bottle B.By constant flow pump, these two kinds of solution are continued to be transported to (internal diameter 0.05mm) reaction in two interface tubular reactors with the flow velocity of 0.05ml/min, approximately 130 minutes, controlling temperature of reaction was 120 C.Collect reaction liquid C in tubular reactor exit, gained reaction solution is Nano silver solution.Utilize particle diameter and the pattern of the nanometer silver of Electronic Speculum to gained to observe, it is subsphaeroidal that observations shows that the nano-Ag particles of gained is, and evenly, particle diameter is mainly distributed in 15～30mm to size, and median size is 20.5mm.By regulating Nano silver solution can obtain stable nano silver conductive ink (l0wt%).After using printing of inkjet printer on film, 120 ℃ are heated 30 minutes, and can obtain this specific conductivity is 30.8 μ Ω .cm.
By 36.4g(0.2mol) nickelous nitrate, 1000ml ethylene glycol, 839g(1.4mol) surfactant A EO-9,80.7g(0.3mol) stearylamine is placed in solution bottle A, keeping solution temperature is 60 ℃, and lasting stirring reaction obtains solution A after 20-180 minutes.56.5g(0.9mol) ethylene glycol of sodium borohydride, 200ml obtains solution B in solution bottle B.By constant flow pump, these two kinds of solution are continued to be transported to (internal diameter 0.05mm) reaction in two interface tubular reactors with the flow velocity of 0.05ml/min, approximately 130 minutes, controlling temperature of reaction was 120 C.Collect reaction liquid C in tubular reactor exit, gained reaction solution is nano nickel solution.Utilize particle diameter and the pattern of the nano nickel of Electronic Speculum to gained to observe, it is subsphaeroidal that observations shows that the nano nickle granules of gained is, and evenly, particle diameter is mainly distributed in 15～30mm to size, and median size is 20.5mm.By regulating nano nickel solution can obtain stable nano nickel conductive ink (l0wt%).
embodiment 4
By 48.4g(0.2mol) iron nitrate, 1000ml hexanaphthene, 119.2g(0.8mol) trolamine, 340g(1.0mol) behenic acid is placed in solution bottle A, keeping solution temperature is 60 ℃, and lasting stirring reaction after 20-180 minutes solution A.70g(1.4mol) hydrazine hydrate, 200ml hexanaphthene obtain solution B in solution bottle B.By constant flow pump, these two kinds of solution are continued to be transported to (internal diameter 0.05mm) reaction in two interface tubular reactors with the flow velocity of 0.05ml/min, approximately 150 minutes, controlling temperature of reaction was 200 C.Collect reaction liquid C in tubular reactor exit, gained reaction solution is Nanoscale Iron solution.Utilize particle diameter and the pattern of the Nanoscale Iron of Electronic Speculum to gained to observe, it is subsphaeroidal that observations shows that the nano-Ag particles of gained is, and evenly, particle diameter is mainly distributed in 5～25mm to size, and median size is 10.5mm.By regulating Nanoscale Iron solution can obtain stable Nanoscale Iron conductive ink (l0wt%).
Finally it should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. the method for nanoparticle conductive ink continuous production, is characterized in that, comprises the following steps:
1) configuration solution A, described solution A is containing solvent, tensio-active agent, organic protective agent, metal or metallic compound salt; Configuration contains the reductant solution B of viscosity modifier:
In described solution A, B, solvent is one or the arbitrary combination in polar solvent or non-polar solvent; Described organic protective agent is the one or any combination in organic acid or organic amine;
Metal or metallic compound salt: organic protective agent: the mol ratio of tensio-active agent is 1:(1.5～5): (1.5～7); The mol ratio of metal and reductive agent is 1:(1～7);
2) by solution A, solution B simultaneously, deliver in the tubular reactor that is provided with heater assembly and react continuously, obtain nanoparticle conductive ink;
Wherein, described metal or metallic compound salt at least comprise following a kind of negatively charged ion or arbitrary combination: nitrate ion, carbanion, acetate ion, sulfate ion, oxalate denominationby, cyanic acid ion, nitrite ion, phosphate anion, thiocyanate ion, chloranion, perchlorate, tetrafluoroborate ion or methyl ethyl diketone radical ion; Also comprise at least one or any combination in Cu, Ag, Au, Zn, Ni, Co, Pd, Pt, Ti, V, Mn, Fe, Mo, W, Ru, Cd, Ta, Al, Ga, Ge, In, Sn, Pb and Bi and their alloy or alloyed oxide; Described step 2) in, feeding time length 30～180min, controls 20～200 ℃ of temperature of reaction.
2. the method for nanoparticle conductive ink continuous production according to claim 1, is characterized in that: described metal or metallic compound salt are Ag, Au, Cu, Zn, Ni, Fe, In, Sn metal or metallic compound salt.
3. the method for nanoparticle conductive ink continuous production according to claim 1, is characterized in that: described organic acid is: chain alkyl carboxylic acid and derivative thereof; And/or described organic amine is: chain alkyl amine and derivative thereof.
4. according to the method for the nanoparticle conductive ink continuous production described in claim 1 or 3, it is characterized in that: described organic acid is palmitic acid, stearic acid, behenic acid, and/or described organic amine is cetylamine, stearylamine.
5. the method for nanoparticle conductive ink continuous production according to claim 1, is characterized in that: described tensio-active agent is that tensio-active agent is: the one in tween, TX-10, AEO-9 or trolamine or arbitrary combination.
6. the method for nanoparticle conductive ink continuous production according to claim 1, is characterized in that: described reductive agent is one or the arbitrary combination in sodium borohydride, Trisodium Citrate, citric acid, POTASSIUM BOROHYDRIDE, dimethyamine borane, hydrazine hydrate, phenylhydrazine, acethydrazide, methyldiethanolamine, xitix, glucose, inferior sodium phosphate or hydrogen peroxide.
7. according to the method for the nanoparticle conductive ink continuous production described in claim 1 or 6, it is characterized in that: described reductive agent is xitix, citric acid, hydrazine hydrate, glucose.
8. nanoparticle conductive ink continuous production method according to claim 1, is characterized in that: described polar solvent is: water, methyl alcohol, ethanol, glycerine, ethylene glycol, polyoxyethylene glycol, Virahol, isopropylcarbinol or dimethyl sulfoxide (DMSO); And/or described non-polar solvent is: hexanaphthene, methylcyclohexane, sherwood oil, benzene,toluene,xylene, trichloromethane or ethyl acetate.
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| CN107690710A (en) * | 2015-05-29 | 2018-02-13 | 默克专利股份有限公司 | Solution methods for InSb nano particles and the application for infrared detector |
| IL247113B (en) * | 2016-08-04 | 2018-02-28 | Copprint Tech Ltd | Formulations and processes for producing highly conductive copper patterns |
| US10800938B2 (en) * | 2017-09-16 | 2020-10-13 | Xerox Corporation | Molecular organic reactive inks for conductive metal printing using photoinitiators |
| CN108250845A (en) * | 2018-01-17 | 2018-07-06 | 厦门卡拉风娱乐有限公司 | A kind of nanometer conductive ink and preparation method thereof |
| CN113560562B (en) * | 2021-06-17 | 2022-06-14 | 佛山华智新材料有限公司 | Nano silver particles, preparation method thereof, nano silver paste and welding joint |
| CN115322623B (en) * | 2022-07-01 | 2023-08-11 | 湖南兴威新材料有限公司 | Reactive ink-jet printing silver ink and preparation method and application thereof |
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