CN104263082B - Graphene organic silver conductive printing ink and preparation method thereof - Google Patents
Graphene organic silver conductive printing ink and preparation method thereof Download PDFInfo
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- CN104263082B CN104263082B CN201410432869.3A CN201410432869A CN104263082B CN 104263082 B CN104263082 B CN 104263082B CN 201410432869 A CN201410432869 A CN 201410432869A CN 104263082 B CN104263082 B CN 104263082B
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
Abstract
The invention discloses a graphene organic silver conductive printing ink and a preparation method thereof. The conductive printing ink comprises a conductive function unit precursor, an organic silver complexing agent, an adhesive, a solvent and auxiliaries. The preparation method comprises the following steps: (A) stirring and ultrasonically dispersing the organic silver, the solvent and the organic silver complexing agent under a lucifugal condition to obtain an organic silver complexing solution; and (B) putting the graphene, the resin adhesive, the auxiliaries and the organic silver complexing solution in the lucifugal condition and stirring and ultrasonically dispersing in an environment lower than 10 DEG C, wherein the obtained uniform mixture is the graphene organic silver conductive printing ink. The graphene organic silver conductive printing ink prepared by the method disclosed by the invention is low in solid content, good in stability, good in printing performance and wide in application.
Description
Technical field
The present invention relates to electrically conductive ink field, particularly a kind of Graphene organic silver electrically conductive ink and preparation method thereof.
Background technology
With the high speed development of science and technology, the large-scale use of integrated circuit, microelectronic component is increasingly minimized, printing electricity
The electronic circuit of road, intelligent label, flexible display device, sensor etc. also to it is small, become more meticulous, various sexual development, its correspondence
Mode of printing and base material species it is more and more.Printing process include method for printing screen, gravure process, engraving method,
Rotating coating, electro-plating method, chemical gaseous phase depositing process, inkjet printing methods, direct write method etc.；As printing
Base material, can be divided into rigid base material, such as glass, metal, semiconductor, silicon chip, ceramics, epoxy resin；And flexible parent metal, such as
PET film, polyimide film etc..
Electrically conductive ink is generally made up of conducting function unit, solvent, binding agent, dispersant, property-modifying additive etc., Ke Yifen
It is metal or metal oxide system, carbon system, compound system three major types；The conducting function of metal or metal oxide system electrically conductive ink
Unit mainly has bronze, silver powder, copper powder etc., and its performance is good, but bronze is expensive, and copper powder is easily because oxidation reduces electric conductivity；
Therefore be currently mainly used silver powder system electrically conductive ink, but silver powder easily migrate, sintering process it is easy to crack, bending resistance is poor, so
It is mainly used in low resistance rigid base material conducting channel.The conducting function unit of carbon series conductive ink mainly has graphite, carbon black, second
Acetylene black etc., its stable performance is not oxidizable, corrosion-resistant after solidification, but resistivity is relatively low, is mainly used in thin film switch.On
The ink material for stating material all has the advantage and disadvantage of itself, to improve printing part performance, expands the use model of electrically conductive ink
Enclose, the improvement and exploration of conducting function unit are using the trend that new conductive unit is that domestic and international electrically conductive ink is researched and developed.
Graphene is the nano-carbon material of new generation of the report of Geim groups in 2004, with high electron mobility, excellent
The features such as different thermal conductivity, room temperature abnormality quantum hall effect, Dual-polarized electricity field-effect and high Young's modulus, composite,
The fields such as energy storage device, transparency electrode have great application prospect.Graphene conductive is high, and density is much smaller than copper, silver, bending resistance
Qu Xingneng is good, stabilization itself；With the maturation of Graphene preparation technology, price is more and more cheaper, therefore Graphene replaces copper, silver
Not only conform to that microelectronic industry is integrated, light-weighted developing direction as the wire of printed circuit, noble metal can also be reduced
Consume.
However, there is lamellar interface resistance when preparing conductive material using Graphene, prepared electrically conductive ink is easily reunited,
Bad dispersibility, actual electric conductivity has a long way to go with Graphene theory electric conductivity.At present using the addition Nano Silver in Graphene
Mode ensures that it leads performance, and the addition of the method Nano Silver is generally higher than 50 wt%；The preparation of Nano Silver also very complicated, this
Undoubtedly increased production cost；In addition, Graphene is solid-state with argent in the electrically conductive ink of this state, ink configuration is given
The dispersion of middle particle and some mode of printings（Such as ink-jet, direct write）Using difficulty is brought, therefore it provides one kind is adjustable to be made liquid
Silver-colored forerunner's body method prepare Graphene and the electrically conductive ink of silver-colored compound type is of great immediate significance.
Organic silver is the organic compound of silver, can be modulated into liquid by being complexed, but organic silver is unstable, additional
Component easily causes its fast decoupled to reduce, therefore there is not compound other conductive units structure novel conductive ink in organic silver
Report.Our research confirms that Graphene does not have reproducibility or reproducibility is weaker, by rational configuration technique, Graphene with have
Machine silver can stably coexist.
The content of the invention
The present invention provides a kind of Graphene organic silver electrically conductive ink of stabilization and preparation method thereof, all with conductive unit
The electrically conductive ink of Graphene or Nano Silver is compared, and the electrically conductive ink solid content is low, and the good stability of ink, printing performance is good, should
With extensive, what the present invention was realized in：A kind of Graphene organic silver electrically conductive ink, it is characterised in that raw material is with component such as
Under, by percentage to the quality, including：
Conducting function unit presoma 23-40%,
Organic silver complexing agent 25-57%,
Binding agent 3-10%
Solvent 0.5-20%,
Auxiliary agent 2.5-6%；
The conducting function unit presoma is made up of Graphene and organic silver, the matter of elemental silver in Graphene and organic silver
Amount is than being 4-92:96-8.
Preferably, in the present invention, in the conducting function unit presoma, the quality of elemental silver in Graphene and organic silver
Than being 4-20：96-80 or 80-92:20-8.
Preferably, in the present invention, in the conducting function unit presoma, the quality of elemental silver in Graphene and organic silver
Than being 4:96-82:18.
Preferably, in the present invention, the Graphene is the lamellar structure of single or multiple lift.
Preferably, in the present invention, the organic silver is pungent capric acid silver, beta-keto acid silver, 2- [2- (2- methoxyethoxies) ethoxies
Base] silver acetate, butyric acid silver, silver citrate, succinic acid silver, the one kind in malic acid silver, silver tartrate, silver acetate, silver oxalate.
Preferably, in the present invention, the binding agent is ethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, phenolic aldehyde tree
Fat, polyester resin, polyimide resin, epoxy resin, organic siliconresin, fluorocarbon resin, polyester resin, vinylite, third
Olefin(e) acid resin, acrylate quasi-oligomer and activated monomer, alkyd resin, synthetic cellulose, polyamide, vinyl chloride-vinyl acetate resin,
Polyurethane resin, polyvinylidene fluoride resin, thermoplastic resin, synthetic rubber, silicon-modified epoxy, polyurethane modified epoxy,
Epoxy modified acrylic resin, organosilicon-modified acrylic epoxy resin, acrylic resin modified, modified phenolic, acid modified alcoholic
One kind in resin.
Preferably, in the present invention, described organic silver complexing agent is aminated compounds or amido class compound；Wherein, institute
It refers to ammoniacal liquor, n-propylamine, n-butylamine, isobutyl amine, n-hexylamine, n-octyl amine, 1,2- propane diamine, 1,3- the third two to state aminated compounds
Amine, diisopropylamine, di-n-butylamine, diethanol amine, triethylamine, tripropyl amine (TPA) or sec-butylamine；The amido class compound refers to 2-（First
Amino）Ethanol, 3- aminopropyls Ethoxysilane or diethylaminoethanol.
Preferably, in the present invention, the solvent is water, aromatic hydrocarbon solvent, fat hydrocarbon solvent, ether solvent, alcohols
One or more in solvent, alcohol ethers solvent, amide solvent, ketones solvent, esters solvent.
Preferably, the present invention in, the auxiliary agent be dispersant, stabilizer, protective agent, film forming agent, coupling agent, plasticizer,
One or more in defoamer, thickener, wetting agent, levelling agent, thixotropic agent, crosslinking agent, ultraviolet absorber.
A kind of preparation method of Graphene organic silver electrically conductive ink of the present invention, it is comprised the following steps that：
A organic silver, solvent and organic silver complexing agent) are stirred into 0.5-12 h, ultrasound point under the conditions of lucifuge in proportion
1-12 h are dissipated, organic silver complex solution is obtained；
B) the organic silver complex solution in proportion obtaining Graphene, binding agent, auxiliary agent and step A is in lucifuge, temperature
Stirring reaction 0.5-12 h or ultrasonic disperse 0.5-12 h or ball milling 0.5-1 h are well mixed in environment less than 10 °C, gained
Product is Graphene organic silver electrically conductive ink.
Preferably, in the present invention, what the organic silver was obtained by：Silver salt or silver oxide solution are slowly dropped into accordingly
In organic solution, 0.5-2 h are stirred under the conditions of lucifuge, washing of precipitate, the filtering that will be obtained, room temperature lucifuge are dried in the shade, and gained is produced
Thing is organic silver.
The beneficial effects of the present invention are：
1st, the physics such as electrically conductive ink conductive unit charge ratio provided by the present invention, solid content, surface tension and viscosity
The product conduction needs that property can print according to actual needs are adjusted, and the electrically conductive ink sintering temperature is minimum can be to 150
°C, therefore the range of choice of its printed substrate is wider, such as glass, ceramics, metal, semiconductor, silicon chip, ceramics, epoxy resin
Rigid base material；Because containing Graphene in electrically conductive ink, fine silver ink bending resistance is significantly improved, meet flexible device
Print request, it is also suitable the flexible parent metals such as polyimide film.
2nd, the viscosity of Graphene organic silver electrically conductive ink prepared by the inventive method can be adjusted in scope wider
It is whole, specifically changed according to preparation method and using process, preferably 1-1500 cP, such as relatively low conductive ink of viscosity are adapted to
Various mode of printings such as ink jet printing, direct pen are write, rotating coating；Viscosity conductive ink higher then can apply to recessed
Various mode of printings such as version printing, silk-screen printing.
3rd, electric conductivity is controllable, and the present invention can be different according to requirement of the printing device to electric conductivity, led by changing
In electric ink in conductive unit presoma Graphene and organic silver charge ratio and solid content, while use requirement is met,
To change using Graphene and organic silver content, ink cost is reduced.
4th, printed matter good stability, compared with Graphene silver electrically conductive ink, has in electrically conductive ink provided by the present invention
Machine silver directly exists in ink in the form of a solution with organic additive complexing, it is not necessary to considers that Argent grain is reunited and is difficult to effectively dispersion
Influence to end article electric conductivity.
5th, it is of the invention compared with silver-colored electrically conductive ink, Graphene silver electrically conductive ink, conductive unit needed for identical electric conductivity
Addition is reduced, and the heat treatment temperature of ink is extremely low, is optimized performance and cost.
6th, electrically conductive ink printed matter of the present invention is not oxidizable, corrosion-resistant, and silver content is relatively low in electrically conductive ink of the present invention, leads
Electrically significantly improved relative to Graphene ink, electric conductivity is suitable with simple silver-colored ink, greatly reduces ink cost, it is easy to push away
Wide application；Additionally, carbon slurry, the silver paste printing ink, the solid of provided by the present invention electrically conductive ink highly filled relative to tradition
Granule content is low, and stably dispersing will get well, and easily store and use.
Specific embodiment
The present invention will be further described by the following examples, and embodiment is not limitation of the present invention.
Embodiment 1 prepares Graphene malic acid silver electrically conductive ink
（1）The preparation of malic acid silver, at room temperature, 1.3g DL-sodium malates is dissolved in 50mL deionized waters, then will
2.5g silver nitrates are dissolved in 40mL deionized waters, and silver nitrate aqueous solution is slowly added dropwise in the natrium malicum aqueous solution with dropper
（Silver nitrate is 2 with the mol ratio of natrium malicum:1, to ensure that silver nitrate is slightly excessive）, occur white precipitate, lucifuge stirring 2 at once
H, afterwards by washing of precipitate, filtering, room temperature lucifuge is dried in the shade, and obtains malic acid silver solid.
（2）By mass percentage, the following raw material is weighed：Malic acid silver, 3% oxide-reduction method that 20% step 1 is obtained
The Graphene of preparation（Thickness is about 7nm, the number of plies<10）, 3% binding agent（Polyurethane resin）, 52% organic silver complexing agent（Diisopropyl
Amine）, 16% solvent（Terpinol）, 5.5% dispersion protective agent（Span-80）, 0.5% defoamer.
（3）The malic acid silver mixing in proportion obtaining terpinol, diisopropylamine and step 1,10 °C are less than in lucifuge
Under the conditions of 2 h are stirred with the rotating speed of 500 rpm, again with the h of 80 KHz ultrasonic disperses 2, obtain homogeneous malic acid silver complexing molten
Liquid.
（4）The malic acid silver complexing that Graphene, polyurethane resin, terpinol, Span-80, defoamer and step 3 are obtained
Solution is under conditions of lucifuge, temperature are less than 10 °C with 2 h of rotating speed stirring of 800rpm, again with the rotating speed ball milling 2 of 300rpm
Min, the uniform sizing material mixture for being obtained as Graphene malic acid silver electrically conductive ink（Graphene is about with elemental silver mass ratio
80:20）.
The Graphene malic acid silver electrically conductive ink for being obtained embodiment 1 using the method that is coated with is printed on Kapton,
200 °C of 1 h for the treatment of, four probe instruments measure square resistance for 0.9 Ω/.
Embodiment 2 prepares Graphene silver citrate electrically conductive ink
（1）Silver citrate is prepared, at room temperature, 1.35g sodium citrates is dissolved in 50mL deionized waters, then by 2.5g nitre
Sour silver is dissolved in 40mL deionized waters, and silver nitrate aqueous solution is slowly added dropwise in sodium citrate aqueous solution with dropper, at once
There is white precipitate, lucifuge stirs 2 h, afterwards by washing of precipitate, filtering, room temperature lucifuge is dried in the shade, and silver citrate solid is obtained.
（2）By mass percentage, the following raw material is weighed：It is prepared by the silver citrate of 34% step 1 acquisition, 1% Physical
Single-layer graphene, 5% binding agent（Hydroxyethyl cellulose）, 57% organic silver complexing agent（1,2- propane diamine）, 0.5% solvent（Isopropyl
Alcohol）, 1.5% dispersion protective agent（Span -85）, 0.5% defoamer, 0.5% stabilizer.
（3）Isopropanol, 1,2- propane diamine and silver citrate are mixed in proportion, is stirred under the conditions of lucifuge is less than 10 °C
Mix (500 r/min) 12 h, ultrasound（80 KHz）Disperse 2 h, obtain homogeneous silver citrate complex solution.
（4）The silver citrate that Graphene, binding agent, solvent, dispersion protective agent, defoamer, stabilizer and step 3 are obtained
Complex solution stirs (800 r/min) 2 h, ultrasound under conditions of lucifuge, temperature are less than 10 °C（80 KHz）Disperse 0.5 h,
Again with the min of rotating speed ball milling 5 of 300rpm, Graphene silver citrate is well mixed, that is, obtains Graphene silver citrate conductive oil
Ink（Graphene is about 4 with elemental silver mass ratio:96）.
The Graphene silver citrate electrically conductive ink that embodiment 2 is obtained through silk-screen printing on Kapton, 200 °
C processes 1 h, and four probe instruments measure square resistance for 0.03 Ω/.
Embodiment 3 prepares Graphene silver citrate electrically conductive ink
（1）Silver citrate is prepared, at room temperature, 1.35g sodium citrates is dissolved in 50mL deionized waters, then by 2.5g nitre
Sour silver is dissolved in 40mL deionized waters, and silver nitrate aqueous solution is slowly added dropwise in sodium citrate aqueous solution with dropper, at once
There is white precipitate, lucifuge stirs 2 h, afterwards by washing of precipitate, filtering, room temperature lucifuge is dried in the shade, and silver citrate solid is obtained.
（2）By mass percentage, the following raw material is weighed：Silver citrate, 3% chemical method system that 36% step 1 is obtained
Standby Graphene, 3% binding agent（It is acrylic resin modified）, 54% organic silver complexing agent（1,2- propane diamine）, 1.5% solvent（Isopropyl
Alcohol）, 1.5% dispersion protective agent（Span -85）, 0.5% defoamer, 0.5% stabilizer.
（3）Isopropanol, 1,2- propane diamine and silver citrate are mixed in proportion, is stirred under the conditions of lucifuge is less than 10 °C
Mix (500 r/min) 12 h, ultrasound（80 KHz）Disperse 2 h, obtain homogeneous silver citrate complex solution.
（4）The silver citrate that Graphene, binding agent, solvent, dispersion protective agent, defoamer, stabilizer and step 3 are obtained
Complex solution stirs (800 r/min) 2 h, ultrasound under conditions of lucifuge, temperature are less than 10 °C（80 KHz）Disperse 0.5 h,
Again with the min of rotating speed ball milling 3 of 300rpm, Graphene silver citrate is well mixed, that is, obtains Graphene silver citrate conductive oil
Ink（Graphene is about 8 with elemental silver mass ratio:92）.
The Graphene silver citrate electrically conductive ink that embodiment 3 is obtained through silk-screen printing on Kapton, 150 °
C processes 1 h, and four probe instruments measure square resistance for 17 Ω/.
Embodiment 4 prepares Graphene silver acetate electrically conductive ink
（1）Silver acetate is prepared, at room temperature, 0.6g sodium acetates is dissolved in 50mL deionized waters, the dissolving of 2.5g silver nitrates
In 40mL deionized waters, silver nitrate aqueous solution is slowly added dropwise in sodium acetate aqueous solution with dropper,（Silver nitrate and sodium acetate
Mol ratio be 3:1, to ensure that silver nitrate is slightly excessive）, occurring white precipitate at once, lucifuge stirs 2 h, afterwards washes precipitation
Wash, filter, room temperature lucifuge is dried in the shade, silver acetate solid is obtained.
（2）By mass percentage, the following raw material is weighed：Silver acetate, the preparation of 35.5% Physical that 4.5% step 1 is obtained
Single-layer graphene, 10% resinoid bond（Acrylic resin）, 25% organic silver complexing agent（2-（Methylamino）Ethanol）, 20 % it is molten
Agent（Cyclohexanone）, 4.7% Span-80（Dispersion protective agent）, 0.3% defoamer.
（3）In proportion by cyclohexanone, 2-（Methylamino）Ethanol and silver acetate mix, and are less than under the conditions of 10 °C in lucifuge
Stirring (500 r/min) 12 h, ultrasound（80 KHz）Disperse 2 h, obtain homogeneous silver acetate complex solution.
（4）The silver acetate complex solution that Graphene, binding agent, solvent, dispersion protective agent, defoamer and step 3 are obtained
(800 r/min) 2 h, ultrasound are stirred under conditions of lucifuge, temperature are less than 10 °C（80 KHz）Dispersion 0.5h, then with
The min of rotating speed ball milling 3 of 300rpm, Graphene silver acetate is well mixed, that is, obtain Graphene silver acetate electrically conductive ink（Graphite
Alkene is about 92 with elemental silver mass ratio:8）.
Through silk-screen printing on glass, 250 °C process 1 h to the Graphene silver acetate electrically conductive ink that embodiment 4 is obtained,
Four probe instruments measure square resistance for 8 Ω/.
Embodiment 5 prepares the grapheme modified silver citrate electrically conductive ink of argent
(1) silver citrate is prepared, at room temperature, 1.35g sodium citrates is dissolved in 50mL deionized waters, then by 2.5g
Silver nitrate is dissolved in 40mL deionized waters, and silver nitrate aqueous solution is slowly added dropwise in sodium citrate aqueous solution with dropper,（Nitre
Sour silver is 3 with the mol ratio of sodium citrate:1, to ensure that silver nitrate is slightly excessive）, occurring white precipitate at once, lucifuge stirs 2 h,
Afterwards by washing of precipitate, filtering, room temperature lucifuge is dried in the shade, and silver citrate solid is obtained.
(2) prepare argent grapheme modified, at room temperature, the silver nitrate of the graphene oxide of 56mg and 144mg is disperseed
In 400mL deionized waters, ultrasound（80 KHz）Disperse 1 h.Mixed solution is placed in there-necked flask, 20 are stirred at room temperature
H, adds 80% hydrazine hydrate of 5mL, 95 °C of h of lower reductase 12 4.With deionized water and absolute ethanol washing product to neutrality, will
Product is vacuum dried under 30 °C, argent is obtained grapheme modified.
（3）By mass percentage, the following raw material is weighed：The silver citrate of 34.5% step 1 acquisition, 5.5% step 2 are obtained
Argent is grapheme modified, 5% resinoid bond（Alkyd resin）, 45% organic silver complexing agent（1,2- propane diamine）, 5% solvent
（Isopropanol）, 4.2% Span-80（Dispersion protective agent）, 0.3% defoamer, 0.5% stabilizer.
（4）Isopropanol and 1,2- propane diamine are mixed in proportion, (500 r/ are stirred under the conditions of lucifuge is less than 10 °C
Min) 12 h, ultrasound（80 KHz）Disperse 2 h, obtain homogeneous silver citrate complex solution.
（5）The lemon that Graphene, binding agent, solvent, dispersion protection agent aid, defoamer, stabilizer and step 4 are obtained
Sour silver complex solution stirs (800 r/min) 2 h, ultrasound under conditions of lucifuge, temperature are less than 10 °C（80 KHz）Dispersion 1
H, then with the min of rotating speed ball milling 5 of 400rpm, Graphene silver citrate is well mixed, that is, obtain the grapheme modified lemon of argent
Lemon acid silver electrically conductive ink（The Graphene of modification is about 20 with elemental silver mass ratio:80）.
The grapheme modified silver citrate electrically conductive ink of argent for being obtained embodiment 5 using the method that is coated with is printed in glass
On, 250 °C of 1 h for the treatment of, four probe instruments measure square resistance for 0.4 Ω/.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of Graphene organic silver electrically conductive ink, it is characterised in that raw material is as follows with component, by percentage to the quality, including：
Conducting function unit presoma 23-40%,
Organic silver complexing agent 25-57%,
Binding agent 3-10%
Solvent 0.5-20%,
Auxiliary agent 2.5-6%；
The conducting function unit presoma is made up of Graphene and organic silver, the mass ratio of elemental silver in Graphene and organic silver
It is 4-20：96-80 or 80-92:20-8；
The Graphene is the lamellar structure of single or multiple lift；
Described organic silver complexing agent is aminated compounds or amido class compound；Wherein, the aminated compounds refer to ammoniacal liquor,
N-propylamine, n-butylamine, isobutyl amine, n-hexylamine, n-octyl amine, 1,2- propane diamine, 1,3- propane diamine, diisopropylamine, di-n-butylamine,
Diethanol amine, triethylamine, tripropyl amine (TPA) or sec-butylamine；The amido class compound refers to 2-（Methylamino）Ethanol, 3- aminopropyl second
TMOS or diethylaminoethanol.
2. Graphene organic silver electrically conductive ink according to claim 1, it is characterised in that the organic silver be pungent capric acid silver,
β-ketone acid silver, 2- [2- (2- methoxyethoxies) ethyoxyl] silver acetate, butyric acid silver, silver citrate, succinic acid silver, malic acid
One kind in silver, silver tartrate, silver acetate, silver oxalate.
3. Graphene organic silver electrically conductive ink according to claim 1, it is characterised in that the binding agent be polyvinyl alcohol,
Phenolic resin, epoxy resin, organic siliconresin, fluorocarbon resin, vinylite, acrylic resin, acrylate quasi-oligomer
With activated monomer, alkyd resin, synthetic cellulose, vinyl chloride-vinyl acetate resin, polyurethane resin, thermoplastic resin, synthetic rubber, organosilicon
It is modified epoxy, polyurethane modified epoxy organosilicon-modified acrylic epoxy resin, acrylic resin modified, modified phenolic, modified
One kind in alkyd resin.
4. Graphene organic silver electrically conductive ink according to claim 1, it is characterised in that the solvent is water, arene
In solvent, fat hydrocarbon solvent, ether solvent, alcohols solvent, alcohol ethers solvent, amide solvent, ketones solvent, esters solvent
One or more.
5. Graphene organic silver electrically conductive ink according to claim 1, it is characterised in that the auxiliary agent is dispersant, stabilization
It is agent, protective agent, film forming agent, coupling agent, plasticizer, defoamer, thickener, wetting agent, levelling agent, thixotropic agent, crosslinking agent, ultraviolet
One or more in absorbent.
6. as described in claim 1 Graphene organic silver electrically conductive ink preparation method, it is comprised the following steps that：
A organic silver, solvent and organic silver complexing agent) are stirred into 0.5-12 h, ultrasonic disperse under the conditions of lucifuge in proportion
1-12 h, obtain organic silver complex solution；
B the organic silver complex solution for) in proportion obtaining Graphene, binding agent, auxiliary agent and step A is low in lucifuge, temperature
Stirring reaction 0.5-12 h or ultrasonic disperse 0.5-12 h or ball milling 0.5-1 h are well mixed in 10 DEG C of environment, gained
Product is Graphene organic silver electrically conductive ink；
Wherein, the organic silver is obtained by：Silver salt or silver oxide solution are slowly dropped into corresponding organic solution, are kept away
0.5-2h is stirred under optical condition, washing of precipitate, the filtering that will be obtained, room temperature lucifuge are dried in the shade, and products therefrom is organic silver.
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| CH719595A1 (en) * | 2022-04-12 | 2023-10-31 | Graphenaton Tech Sa | Conductive ink containing graphene. |
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| KR100660928B1 (en) * | 2004-09-25 | 2006-12-26 | 주식회사 잉크테크 | Organic silver ink for direct wiring |
| KR20120088313A (en) * | 2011-01-31 | 2012-08-08 | 엘에스전선 주식회사 | Conductive Ink Composition Having Bimodal Particle Distribution |
| US20140151607A1 (en) * | 2012-11-30 | 2014-06-05 | Nthdegree Technologies Worldwide Inc. | Ultraviolet-Curable Conductive Ink and Dielectric Ink Compositions Having a Common Binding Medium, with Manufactures and Fabrication Methods |
| KR20140079668A (en) * | 2012-12-18 | 2014-06-27 | 한국기계연구원 | Vibration Assisted Contact-type printing machine |
| CN103013229B (en) * | 2012-12-30 | 2014-08-20 | 中国科学院宁波材料技术与工程研究所 | Graphene based conductive ink and preparation method thereof as well as flexible conductive thin film |
| KR101433682B1 (en) * | 2013-02-26 | 2014-08-26 | (주)피이솔브 | Silver Inks |
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| WO2019060167A1 (en) * | 2017-09-25 | 2019-03-28 | Eastman Kodak Company | Silver-containing non-aqueous composition containing cellulosic polymers |
| US10246561B1 (en) | 2017-09-25 | 2019-04-02 | Eastman Kodak Company | Method of making silver-containing dispersions with nitrogenous bases |
| CH719595A1 (en) * | 2022-04-12 | 2023-10-31 | Graphenaton Tech Sa | Conductive ink containing graphene. |
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