CN106433316A - Preparation method of nano silver wire ink-jet conductive ink - Google Patents

Preparation method of nano silver wire ink-jet conductive ink Download PDF

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Publication number
CN106433316A
CN106433316A CN201510486451.5A CN201510486451A CN106433316A CN 106433316 A CN106433316 A CN 106433316A CN 201510486451 A CN201510486451 A CN 201510486451A CN 106433316 A CN106433316 A CN 106433316A
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nano
silver thread
conductive ink
silver
solution
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CN106433316B (en
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王悦辉
谢辉
赵玉珍
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University of Electronic Science and Technology of China Zhongshan Institute
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Abstract

The invention discloses a preparation method of nano silver wire ink-jet conductive ink, which is characterized in that a nano silver wire with the diameter of 30-60 nm and the length of 2-4 mu m is obtained by adopting a method of combining ultrasonic oscillation and centrifugal separation. By adopting the nano silver wire as a conductive component, high conductivity under the condition of low conductive component content can be realized, and good stability and rheological behavior can be realized, thereby being beneficial to ink-jet printing of conductive circuits. The nano silver wire ink-jet conductive ink comprises, by mass, 0.8-2% of a nano silver wire, 0.01-0.08% of polyvinylpyrrolidone K90, 78-87% of isopropanol, 8-15% of diethylene glycol and 3-6% of diethylene glycol monobutyl ether, wherein the sum of the mass percentages of the components is 100%.

Description

A kind of preparation method of nano-silver thread jet conductive ink
Technical field
The present invention relates to a kind of preparation method of nano-silver thread jet conductive ink.This conductive ink belongs to printed electronic slurry, is applied to ink-jet printed electronic technology field.
Background technology
Ink-jet printed refer to by computer come the technology of assist control ink-jet printing apparatus, be a kind of contactless, printing technology that need not make a plate.Compared with conditional electronic Manufacturing Method of Products, Printing techniques have and accurately can connect up in the relevant position of base material, need not make a plate, the advantages of directly obtain target conductive pattern.Ink-jet printed electronic technology has unrivaled advantage at aspects such as large area, flexibility, transparence, low cost and environmental protections.With the fast development of ink-jet printed electronic technology, associated printed electronics material causes the extensive concern of people, and especially its core component conductive ink has even more at home and abroad started research and development upsurge.Conductive ink, as the basic material of conductive pattern, is the bottleneck of printed electronics technology development, directly affects performance and the quality of electronic product.Conventional conductive component has nano metal, conducting polymer, material with carbon element etc..Because nano metal has, size is little, fusing point is low, and after sintering, electric conductivity is excellent waits outstanding advantages it is ensured that smooth from the micron order diameter nozzle of ink-jet printer spray, so nano metal can be widely used in conductive ink-jet as conductive filler.
Silver has higher conductivity and thermal conductivity, excellent physical and chemical performance, acceptable price, easy processing and its oxide are widely used as the conductive component of conductive ink the features such as also having certain electric conductivity.Conventional nanoscale silver is mainly spherical particle.The content of conductive component directly affects the electric conductivity of conductive ink.Conductive component content is very few, can not effectively contact, conductivity is relatively low between conducting particles;Content is excessive, and conductive ink is easy to sedimentation, situations such as particle packing and blocking shower nozzle.Compared to spherical nanoparticle, nano wire/nanometer rods of high aspect ratio etc. can significantly reduce the percolation threshold of conductive ink, so that conductive component content reduces, and is obtained in that good stability and mechanical property.However, nano-silver thread has two key issues to need to solve as the conductive component of jet conductive ink, i.e. the effective control of nano-silver thread size and nano-silver thread dispersion stabilization in a solvent.As conductive component, the size of nano-silver thread is longer, and in conducting wire, contact point is fewer, and contact resistance is lower, and electric conductivity is better.But, long nano-silver thread is not only difficult to disperse in a solvent, and is also easy to crosslinked sedimentation of reuniting between nano wire, blocks shower nozzle.Theoretical research shows, the length of inkjet printing conductive component is less than a/50(A is the diameter of shower nozzle)When, ink can print glibly.However, nano-silver thread in spray printing is long often because situation about aligning in liquor stream induction.Accordingly, it is considered to the impact to electric conductivity etc. for the conductive component pattern, the length of actual nano-silver thread conductive component may be greater than a/50's.Research shows, only the nano-silver thread of appropriate size, not only can achieve the high conductivity in the case of low content, and is also easy to obtain high dispersion stabilization and reduces cost.Therefore, developing a kind of nano-silver thread conductive ink being adapted to inkjet printing becomes the art difficult problem urgently to be resolved hurrily.
Content of the invention
In order to overcome the deficiencies in the prior art, present invention offer is a kind of to be suitable for ink-jet printed nano-silver thread conductive ink, and this ink is applied to the base materials such as papery, PI and PET, through 100-300 DEG C of heat treatment, has good electric conductivity.
The technical solution adopted for the present invention to solve the technical problems is:
The preparation process of nano-silver thread jet conductive ink is as follows: (1)0.04-0.06 mol L is prepared under room temperature-1Silver nitrate glycerin solution 100 mL, stir 10 minutes, prepare 0.23-0.35 mol L-1PVP K30 glycerin solution 100 mL.PVP K30 solution is added in silver nitrate solution, stirs 10 minutes, be uniformly dispersed.Prepare 0.4-0.6 mol L-1The glycerol of sodium chloride and water(Volume ratio 10:1)11 mL solution, then in 100-150 rpm min-1Under mixing speed, sodium chloride solution is added in silver nitrate and Polyvinylpyrrolidone mixed solution, solution is warming up to 205 DEG C simultaneously.Then it is naturally cooling to room temperature.By the nano-silver thread of preparation, respectively deionized water and ethanol, with the rotating speed centrifuge washing 30 minutes of 7000 rpm, and respectively wash 2 times, obtain purified nanotubes silver wire.
(2)By step(1)The nano-silver thread of preparation is added in isopropanol, ultrasonic vibration 90-180 minute, then is centrifuged 30 minutes with the rotating speed of 10000 rpm, obtains the nano-silver thread refining.
(3)PVP K90 is dissolved in isopropanol, diethylene glycol and diethylene glycol monobutyl ether mixed solution, then by step(2)In nano-silver thread be added in mixed solution, ultrasonic disperse is after 10 minutes, then in 1200-1800 rpm min-1Under the conditions of mechanical agitation 30-60 minute, obtain ink-jet nano silver wire conductive ink.
The present invention adopts above-mentioned steps(1)The nano-silver thread diameter 20-60 nm, length 2-15 m of middle preparation.
The present invention adopts above-mentioned steps(1)In the molecular weight of PVP K30 be 58000.
The present invention adopts above-mentioned steps(2)To step(1)The nano-silver thread of preparation, through ultrasonic vibration micronization processes, needs the rotating speed centrifugation through 10000 rpm again to remove undersized nano-silver thread in 30 minutes, obtains the diameter 30-60 nm, length 2-4 m of nano-silver thread.
The present invention adopts above-mentioned steps(2)The condition of ultrasonic vibration micronization processes is supersonic frequency 40 KHz, ultrasonic power 70-100W.
The present invention adopts and introduces PVP K90 in above-mentioned steps (3) as dispersant, and the molecular weight of K90 is 130000.
The present invention adopts above-mentioned steps(3)The nano-silver thread jet conductive ink of preparation is made up of the material of following weight/mass percentage composition:Nano-silver thread is 0.8-2%, and PVP K90 is 0.01-0.08%, and isopropanol is 78-87%, and diethylene glycol is 8-15%, diethylene glycol monobutyl ether 3-6%, and the mass percentage content sum of above-mentioned each component is 100%.
The invention has the beneficial effects as follows:The present invention adopts nano-silver thread as the conductive component of conductive ink, it is possible to decrease conductive component content, and conducting wire has good electric conductivity;Ultrasonic vibration method refines nano-silver thread, thus obtaining the nano-silver thread being adapted to inkjet printing, and is also beneficial to obtain the nano-silver thread conductive ink of high stability;Using K90 as dispersant, not only can effectively disperse nano-silver thread, and be also beneficial to improve nano-silver thread rheological behavior in a solvent;Using isopropanol, diethylene glycol and diethylene glycol monobutyl ether mixture as solvent, can effectively adjust viscosity and the rate of drying of ink, it is to avoid particle packing causes spray nozzle clogging, also can effectively reduce " coffee ring " effect of ink droplet simultaneously.
Specific embodiment
In order that the object, technical solutions and advantages of the present invention are clearer, with reference to the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described.Described embodiment is a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained under the premise of not making creative work, broadly fall into the scope of protection of the invention.
Embodiment 1
A kind of described nano-silver thread jet conductive ink, prepares according to following mass percent:Nano-silver thread is 1%, and PVP K90 is 0.02%, and isopropanol is 80.98%, and diethylene glycol is 15%, diethylene glycol monobutyl ether 3%, and the mass percentage content sum of above-mentioned each component is 100%.
0.04 mol L is prepared under room temperature-1Silver nitrate glycerin solution 100 mL, stir 10 minutes, prepare 0.23 mol L-1PVP K30 glycerin solution 100 mL.PVP K30 solution is added in silver nitrate solution, stirs 10 minutes, be uniformly dispersed.Prepare 0.4 mol L-1The glycerol of sodium chloride and water(Volume ratio 10:1)11 mL solution, then in 120 rpm min-1Under mixing speed, sodium chloride solution is added in silver nitrate and Polyvinylpyrrolidone mixed solution, solution is warming up to 205 DEG C simultaneously.Then it is naturally cooling to room temperature.By the nano-silver thread of preparation, respectively deionized water and ethanol, with the rotating speed centrifuge washing 30 minutes of 7000 rpm, and respectively wash 2 times, obtain purified nanotubes silver wire.
The nano-silver thread of above-mentioned preparation is added in isopropanol, in supersonic frequency 40 KHz, under the conditions of ultrasonic power 100W, ultrasonic vibration 180 minutes, then be centrifuged 30 minutes with the rotating speed of 10000 rpm, obtain the nano-silver thread refining.
It is 80.98% that 0.02% PVP K90 is dissolved into isopropanol, and diethylene glycol is 15%, in diethylene glycol monobutyl ether 3% mixed solution, is subsequently adding 1% nano-silver thread, and ultrasonic disperse is after 10 minutes, then in 1500 rpm min-1Under the conditions of mechanical agitation 30 minutes, obtain ink-jet nano silver wire conductive ink.
Embodiment 2
A kind of described nano-silver thread jet conductive ink, prepares according to following mass percent:Nano-silver thread is 1.2%, and PVP K90 is 0.02%, and isopropanol is 85.78%, and diethylene glycol is 10%, diethylene glycol monobutyl ether 3%, and the mass percentage content sum of above-mentioned each component is 100%.
Nano-silver thread prepare long as embodiment 1.
It is 85.78% that 0.02% PVP K90 is dissolved into isopropanol, and diethylene glycol is 10%, in diethylene glycol monobutyl ether 3% mixed solution, is subsequently adding 1.2% nano-silver thread, and ultrasonic disperse is after 10 minutes, then in 1500 rpm min-1Under the conditions of mechanical agitation 30 minutes, obtain ink-jet nano silver wire conductive ink.
Embodiment 3
A kind of described nano-silver thread jet conductive ink, prepares according to following mass percent:Nano-silver thread is 0.9%, and PVP K90 is 0.01%, and isopropanol is 79.09%, and diethylene glycol is 15%, diethylene glycol monobutyl ether 5%, and the mass percentage content sum of above-mentioned each component is 100%.
0.05 mol L is prepared under room temperature-1Silver nitrate glycerin solution 100 mL, stir 10 minutes, prepare 0.35 mol L-1PVP K30 glycerin solution 100 mL.PVP K30 solution is added in silver nitrate solution, stirs 10 minutes, be uniformly dispersed.Prepare 0.6 mol L-1The glycerol of sodium chloride and water(Volume ratio 10:1)11 mL solution, then in 120 rpm min-1Under mixing speed, sodium chloride solution is added in silver nitrate and Polyvinylpyrrolidone mixed solution, solution is warming up to 205 DEG C simultaneously.Then it is naturally cooling to room temperature.By the nano-silver thread of preparation, respectively deionized water and ethanol, with the rotating speed centrifuge washing 30 minutes of 7000 rpm, and respectively wash 2 times, obtain purified nanotubes silver wire.
The nano-silver thread of above-mentioned preparation is added in isopropanol, in supersonic frequency 40 KHz, under the conditions of ultrasonic power 70W, ultrasonic vibration 180 minutes, then be centrifuged 30 minutes with the rotating speed of 10000 rpm, obtain the nano-silver thread refining.
It is 79.09% that 0.01% PVP K90 is dissolved into isopropanol, and diethylene glycol is 15%, in diethylene glycol monobutyl ether 5% mixed solution, is subsequently adding 0.9% nano-silver thread, and ultrasonic disperse is after 10 minutes, then in 1500 rpm min-1Under the conditions of mechanical agitation 30 minutes, obtain ink-jet nano silver wire conductive ink.

Claims (7)

1. a kind of preparation method of nano-silver thread spray printing conductive ink is it is characterised in that the preparation process of this spray printing conductive ink is as follows: (1)0.04-0.06 is prepared under room temperature mol·L-1Silver nitrate glycerin solution 100 mL, stir 10 minutes, prepare 0.23-0.35 mol L-1PVP K30 glycerin solution 100 mL;PVP K30 solution is added in silver nitrate solution, stirs 10 minutes, be uniformly dispersed;Prepare 0.4-0.6 mol L-1The glycerol of sodium chloride and water(Volume ratio 10:1)11 mL solution, then in 100-150 rpm min-1Under mixing speed, sodium chloride solution is added in silver nitrate and Polyvinylpyrrolidone mixed solution, solution is warming up to 205 DEG C simultaneously, be then naturally cooling to room temperature;By the nano-silver thread of preparation, respectively deionized water and ethanol, with the rotating speed centrifuge washing 30 minutes of 7000 rpm, and respectively wash 2 times, obtain purified nanotubes silver wire;(2)By step(1)The nano-silver thread of preparation is added in isopropanol, ultrasonic vibration 90-180 minute, then is centrifuged 30 minutes with the rotating speed of 10000 rpm, obtains the nano-silver thread refining;(3)PVP K90 is dissolved in isopropanol, diethylene glycol and diethylene glycol monobutyl ether mixed solution, then by step(2)In nano-silver thread be added in mixed solution, ultrasonic disperse is after 10 minutes, then in 1200-1800 rpm min-1Under the conditions of mechanical agitation 30-60 minute, obtain ink-jet nano silver wire conductive ink.
2. a kind of nano-silver thread spray printing conductive ink according to claim 1 is it is characterised in that described step(1)The nano-silver thread diameter 20-60 nm, length 2-15 m of middle acquisition.
3. a kind of nano-silver thread spray printing conductive ink according to claim 1 is it is characterised in that described step(1)In the molecular weight of PVP K30 be 58000.
4. a kind of nano-silver thread spray printing conductive ink according to claim 1 is it is characterised in that described step(2)The nano-silver thread diameter 30-60 nm, length 2-4 m of middle acquisition.
5. a kind of nano-silver thread spray printing conductive ink according to claim 1 is it is characterised in that described step((3)In the molecular weight of PVP K90 be 130000.
6. a kind of nano-silver thread spray printing conductive ink according to claim 1 is it is characterised in that described step(2)In ultrasonic vibration condition be supersonic frequency 40 KHz, carry out under the conditions of ultrasonic power 70-100W.
7. a kind of nano-silver thread spray printing conductive ink according to claim 1 is it is characterised in that described step(3)The each quality of material degree of middle conductive ink:Nano-silver thread is 0.8-2%, and PVP K90 is 0.01-0.08%, and isopropanol is 78-87%, and diethylene glycol is 8-15%, diethylene glycol monobutyl ether 3-6%, and the mass percentage content sum of above-mentioned each component is 100%.
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN107384025A (en) * 2017-08-10 2017-11-24 珠海纳金科技有限公司 One kind spraying electrically conducting transparent ink and its preparation method and application
CN109380298A (en) * 2017-08-08 2019-02-26 电子科技大学中山学院 Colorless and transparent anti-color-change nano-silver composite antibacterial agent solution
CN110289125A (en) * 2019-06-18 2019-09-27 电子科技大学中山学院 Preparation method of silver nanowire conductive film and additive thereof
CN111151767A (en) * 2020-01-16 2020-05-15 江苏镭明新材料科技有限公司 Preparation method of composite nano-silver ink-jet conductive ink
CN111180107A (en) * 2020-01-06 2020-05-19 青岛理工大学 Preparation method for electric field driven injection of micro-nano 3D printing nano silver paste
CN113885739A (en) * 2021-09-22 2022-01-04 深圳市华科创智技术有限公司 Preparation process of single-layer nano silver conductive film touch sensor based on printing technology and single-layer nano silver conductive film touch sensor

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109380298A (en) * 2017-08-08 2019-02-26 电子科技大学中山学院 Colorless and transparent anti-color-change nano-silver composite antibacterial agent solution
CN107384025A (en) * 2017-08-10 2017-11-24 珠海纳金科技有限公司 One kind spraying electrically conducting transparent ink and its preparation method and application
CN107384025B (en) * 2017-08-10 2020-10-27 珠海纳金科技有限公司 Spraying transparent conductive ink and preparation method and application thereof
CN110289125A (en) * 2019-06-18 2019-09-27 电子科技大学中山学院 Preparation method of silver nanowire conductive film and additive thereof
CN110289125B (en) * 2019-06-18 2022-08-12 电子科技大学中山学院 Preparation method of silver nanowire conductive film and additive thereof
CN111180107A (en) * 2020-01-06 2020-05-19 青岛理工大学 Preparation method for electric field driven injection of micro-nano 3D printing nano silver paste
CN111180107B (en) * 2020-01-06 2021-09-21 青岛理工大学 Preparation method for electric field driven injection of micro-nano 3D printing nano silver paste
CN111151767A (en) * 2020-01-16 2020-05-15 江苏镭明新材料科技有限公司 Preparation method of composite nano-silver ink-jet conductive ink
CN113885739A (en) * 2021-09-22 2022-01-04 深圳市华科创智技术有限公司 Preparation process of single-layer nano silver conductive film touch sensor based on printing technology and single-layer nano silver conductive film touch sensor

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