CN109575693A - A kind of environment-protection nano graphite alkene conductive ink and its preparation method and application - Google Patents
A kind of environment-protection nano graphite alkene conductive ink and its preparation method and application Download PDFInfo
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- CN109575693A CN109575693A CN201811433121.XA CN201811433121A CN109575693A CN 109575693 A CN109575693 A CN 109575693A CN 201811433121 A CN201811433121 A CN 201811433121A CN 109575693 A CN109575693 A CN 109575693A
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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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- C—CHEMISTRY; METALLURGY
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- 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
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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Abstract
The invention proposes a kind of environment-protection nano graphite alkene conductive inks, be prepared by weight by following raw material: 26 parts of modified graphene oxide, 20 parts of silver citrate, 17 parts of copper citrate, 6 parts of aniline, 4 parts of gelatin, 2.5 parts of dispersing agent, 4 parts of antioxidant, 3 parts of auxiliary agent, 60 parts of ethyl alcohol and 30 parts of water, the modified graphene oxide is prepared by following methods: graphene oxide is made using liquid phase stripping method in S1.；S2. the graphene oxide of preparation is added in deionized water, ultrasonic agitation uniformly, is added silane coupling agent, is stirred to react, is cooled to room temperature in 60 DEG C, is centrifuged, and discards supernatant liquor, and solid is dried to get silane coupler modified graphene oxide.Preparation method of the present invention is simple, and raw material sources are wide, and conductive ink resistivity is low, strong with substrate adhesive force, not oxidizable, and stability is good, can satisfy printability requirement and safety and environmental protection.
Description
Technical field
The present invention relates to terahertz wave quasi-optics fields, and in particular to an environment-protection nano graphite alkene conductive ink.
Background technique
The direct writing of complex pattern may be implemented in inkjet printing technology, is to realize that pattern of functional material most has prospect
One of method.The important activity ingredient of many devices can be all ink-jet printed, including conductive electrode, transistor, solar-electricity
Pond, light emitting diode, battery and sensor etc..However, the patterned electrodes exploitation with high transparency, low-resistivity is still
One important challenge, especially in terms of developing highly integrated system regions.Although having difference in terms of making electrode
Metal material is prepared to solution, but can not often be stablized in environmental-friendly solvent (as in deionized water) by them
Dispersion, needs a large amount of organic additives.And these additives usually require to degrade the time for several years, it is also necessary to high annealing
The raw material and low electrode conductivity of temperature and high price, limit further applying for they.
Conductive ink is the basis for developing electronic component, is the critical material of encapsulation, electrode and interconnection, is applied to electronics
The every field of industry.The final structure and applications to nanostructures of conductive ink are undivided.No matter conductive ink is to use
Metallic conduction or non-metallic materials are conductive, and it is nanometer respectively that conductive material contained by conductive ink, which is all nanometer materials,
The size of size and floated combination nozzle printing conducting wire.Conductive ink can conveniently and quickly designed lines, exist now
The made conductive ink of conductive material mixing is added in liquid, through printing technique, in the circuit board, ink jet type printing is conductive for print
Route is normal convenient.
As the demand of flexible circuit increasingly increases, using electric conductivity ink or conductive ink in flexible insulating substrate
On by modes such as writing, printing or printings prepare the broad interest that conducting wire causes research worker.These years
Scientific investigations showed that most possible have metal grill and nano wire, conducting polymer, carbon as next-generation flexible electrode material
Nanotube and graphene.Wherein using most stable of benzene hexatomic ring as its basic structural unit, C-C bond distance is graphene
0.14nm, thickness only have 0.34nm, and thickness only has 20 a ten thousandths of hair.Thoroughly due to the two-dimensional characteristics of graphene, height
Lightness, excellent electron transport properties, the high and low cost of chemical and thermal stability and outstanding mechanical performance, cause science
The very big concern on boundary prepares graphene flexible circuit and also results in the extensive interest of people, and researcher wishes to pass through graphene
Ink prepares flexible circuit to obtain electronic product foldable, flexible.Recently, there is researcher by graphene and metal material
Material is combined to improve the conductivity of material.There is document report to beat graphene oxide and the compound progress ink-jet of silver nano-grain
Print, but silver is easily oxidized, so the compound ink of graphene oxide and silver has limitation.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of environment-protection nano graphite alkene conductive ink and its preparation side
Method and application, it is intended that a kind of environment-protection nano graphite alkene conductive ink is provided, by the conduction for adding not metallic particles
Silver-colored source and copper source: silver citrate and copper citrate, ink fluency is more preferable, is more soluble in ethanol solution, by with aniline reaction
Silver-amine complex, copper-amine complex are generated, stability is more preferable, can satisfy printability requirement.
The present invention provides a kind of environment-protection nano graphite alkene conductive ink, is prepared from the following materials: modified graphite oxide
Alkene, silver citrate, copper citrate, aniline, gelatin, dispersing agent, antioxidant, auxiliary agent, second alcohol and water；
The modified graphene oxide is prepared by following methods:
S1. graphene oxide is made using liquid phase stripping method；
S2. the graphene oxide prepared by step S1 is added in deionized water, and uniformly, silane coupling agent is added in ultrasonic agitation, in
60 DEG C are stirred to react 1-3h, are cooled to room temperature, centrifugation, discard supernatant liquor, and solid is dried to get silane coupler modified oxygen
Graphite alkene.
As further improvement of the invention, it is prepared by weight by following raw material: modified graphene oxide 20-35
Part, 15-25 parts of silver citrate, 15-20 parts of copper citrate, 3-10 parts of aniline, 2-5 parts of gelatin, 1-3 parts of dispersing agent, antioxidant 2-5
Part, 1-5 parts of auxiliary agent, 50-70 parts of ethyl alcohol and 30-50 parts of water.
As further improvement of the invention, it is prepared by weight by following raw material: modified graphene oxide 22-30
Part, 17-23 parts of silver citrate, 16-19 parts of copper citrate, 4-8 parts of aniline, 3-5 parts of gelatin, 2-3 parts of dispersing agent, antioxidant 3-5
Part, 2-4 parts of auxiliary agent, 55-65 parts of ethyl alcohol and 25-45 parts of water.
As further improvement of the invention, it is prepared by weight by following raw material: 26 parts of modified graphene oxide,
20 parts of silver citrate, 17 parts of copper citrate, 6 parts of aniline, 4 parts of gelatin, 2.5 parts of dispersing agent, 4 parts of antioxidant, 3 parts of auxiliary agent, ethyl alcohol
60 parts and 30 parts of water.
Improved as of the invention further, the dispersing agent be selected from ethylene group bis-stearamides, glyceryl monostearate,
One of microcrystalline wax, calcium stearate, cadmium stearate, magnesium stearate, barium stearate, zinc stearate and copper stearate are several
Kind.
As further improvement of the invention, the antioxidant is selected from 2,6- three-level butyl -4- methylphenol, bis- (3,5-
Three-level butyl -4- hydroxy phenyl) thioether, four (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) pentaerythritol esters, hexichol
One or more of amine, p-phenylenediamine and dihydroquinoline.
As further improvement of the invention, the auxiliary agent includes polyethylene glycol 400, sorbierite, dimethicone and spits
Temperature.
As further improvement of the invention, the auxiliary agent is made of by weight following raw material: polyethylene glycol 400 10-
15 parts, 2-5 parts of sorbierite, 1-2 parts of dimethicone, 2-5 parts of tween.
The present invention further protects a kind of preparation method of above-mentioned environment-protection nano graphite alkene conductive ink, in accordance with the following methods
Preparation: modified graphene oxide is added in ethanol solution, and uniformly, silver citrate is added under ultrasonication in 500W ultrasonic agitation
And copper citrate, stirring and dissolving, gelatin, aniline, dispersing agent, antioxidant and auxiliary agent are sequentially added, in agitated under sonication 2-3 h
Afterwards, ink is filtered to obtain environment-protection nano graphite alkene conductive ink with the syringe filter disk in 0.45 μm of aperture.
The present invention further protects a kind of application of environment-protection nano graphite alkene conductive ink, and above-mentioned ink is applied to flexibility
In the printing of circuit.
The invention has the following beneficial effects:
1. environment-protection nano graphite conductive ink of the present invention is after being added gelatin and aniline, stability, which has, to be obviously improved, gelatin
Being added has the effect being remarkably reinforced to the adhesive force between enhancing ink and substrate, while after aniline is added, can effectively drop
The resistivity of low ink；
2. conductive silver source and copper source that the present invention adds are silver citrate and copper citrate, without metallic particles, ink fluency
More preferably, it is more soluble in ethanol solution, by generating silver-amine complex, copper-amine complex with aniline reaction, stability is more preferable, can
To meet printability requirement；
3. graphene oxide of the present invention is made by liquid phase stripping method, and is modified with silane coupling agent, obtained modified oxidized
Graphene is nanoscale, smaller, meets the conductive demand of conductive ink and the demand of printing fluency, meanwhile, with substrate
Between connected by chemical bond key, it is stronger to be not easy to tear；
4. this law uses second alcohol and water for solvent, harmful organic solvent, VOC free, without harmful additive, safety and environmental protection are not added；
5. preparation method of the present invention is simple, raw material sources are wide, and conductive ink resistivity is low, strong with substrate adhesive force, are not easy oxygen
Change, stability is good, can satisfy printability requirement and safety and environmental protection.
Detailed description of the invention
Fig. 1 is the preparation flow figure of environment-protection nano graphite conductive ink of the present invention.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, the embodiment described is the embodiment of part of representative of the invention, rather than whole embodiments, this field are general
Other all embodiments obtained belong to protection of the invention to logical technical staff without making creative work
Range.
Embodiment 1
Raw material forms (parts by weight): 20 parts of modified graphene oxide, 15 parts of silver citrate, 15 parts of copper citrate, 3 parts of aniline, bright
2 parts of glue, 1 part of magnesium stearate, four (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) 2 parts of pentaerythritol esters, 1 part of auxiliary agent, second
50 parts and 30 parts of water of alcohol；
The auxiliary agent is made of by weight following raw material: 10 parts of polyethylene glycol 400,2 parts of sorbierite, 1 part of dimethicone,
2 parts of tween.
The modified graphene oxide is prepared by following methods:
S1. graphene oxide is made using liquid phase stripping method；
S2. the graphene oxide prepared by step S1 is added in deionized water, and uniformly, silane coupling agent is added in ultrasonic agitation, in
60 DEG C are stirred to react 1h, are cooled to room temperature, centrifugation, discard supernatant liquor, and solid is dried to get silane coupler modified oxidation
Graphene；
A kind of preparation method of environment-protection nano graphite alkene conductive ink, prepares in accordance with the following methods: by modified graphene oxide plus
Entering in ethanol solution, 500W ultrasonic agitation is uniform, addition silver citrate and copper citrate under ultrasonication, stirring and dissolving, according to
Secondary addition gelatin, aniline, magnesium stearate, four (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) pentaerythritol esters and auxiliary agent,
After agitated under sonication 2h, ink is filtered to obtain environment-protection nano graphite alkene with the syringe filter disk in 0.45 μm of aperture and is led
Electric ink.
The ink of preparation is injected separately into print cartridge, printed substrates are printed using printer, printed substrates material is
Polypropylene, print temperature are 55 DEG C；It is put into the printed substrates after inkjet printing in 170mm size vacuum drier, and is put into
Small beaker equipped with 1mL hydroiodic acid opens mechanical pump, is evacuated to 1000Pa and turns off mechanical pump, is then heated to 120 DEG C, warp
3h is crossed, is taken out.As a result, it has been found that environment-protection nano graphite alkene conductive ink manufactured in the present embodiment can be carried out inkjet printing, obtain
Pattern with high transparency, the transparent pattern obtained after reduction show high electrical conductivity (film resistor is 150 Ω/m) and height
Transparent (transmitance 95%).
Embodiment 2
Raw material forms (parts by weight): 35 parts of modified graphene oxide, 25 parts of silver citrate, 20 parts of copper citrate, 10 parts of aniline, bright
5 parts of glue, 3 parts of zinc stearate, 5 parts of diphenylamines, 5 parts of auxiliary agent, 70 parts of ethyl alcohol and 50 parts of water；
The auxiliary agent is made of by weight following raw material: 15 parts of polyethylene glycol 400,5 parts of sorbierite, 2 parts of dimethicone,
5 parts of tween.
The modified graphene oxide is prepared by following methods:
S1. graphene oxide is made using liquid phase stripping method；
S2. the graphene oxide prepared by step S1 is added in deionized water, and uniformly, silane coupling agent is added in ultrasonic agitation, in
60 DEG C are stirred to react 3h, are cooled to room temperature, centrifugation, discard supernatant liquor, and solid is dried to get silane coupler modified oxidation
Graphene；
A kind of preparation method of environment-protection nano graphite alkene conductive ink, prepares in accordance with the following methods: by modified graphene oxide plus
Entering in ethanol solution, 500W ultrasonic agitation is uniform, addition silver citrate and copper citrate under ultrasonication, stirring and dissolving, according to
Secondary addition gelatin, aniline, zinc stearate, diphenylamines and auxiliary agent, after 3 h of agitated under sonication, with 0.45 μm of the syringe-type in aperture
Filter is filtered ink to obtain environment-protection nano graphite alkene conductive ink.
The ink of preparation is injected separately into print cartridge, printed substrates are printed using printer, printed substrates material is
Polypropylene, print temperature are 55 DEG C；It is put into the printed substrates after inkjet printing in 170mm size vacuum drier, and is put into
Small beaker equipped with 1mL hydroiodic acid opens mechanical pump, is evacuated to 1000Pa and turns off mechanical pump, is then heated to 120 DEG C, warp
3h is crossed, is taken out.As a result, it has been found that environment-protection nano graphite alkene conductive ink manufactured in the present embodiment can be carried out inkjet printing, obtain
Pattern with high transparency, the transparent pattern obtained after reduction show high electrical conductivity (film resistor is 147 Ω/m) and height
Transparent (transmitance 96%).
Embodiment 3
Raw material forms (parts by weight): 22 parts of modified graphene oxide, 17 parts of silver citrate, 16 parts of copper citrate, 4 parts of aniline, bright
3 parts of glue, 2 parts of ethylene group bis-stearamides, 3 parts of 2,6- three-level butyl -4- methylphenol, 2 parts of auxiliary agent, 55 parts of ethyl alcohol and water 25
Part；
The auxiliary agent is made of by weight following raw material: 12 parts of polyethylene glycol 400,3 parts of sorbierite, dimethicone 1.2
Part, 3 parts of tween.
The modified graphene oxide is prepared by following methods:
S1. graphene oxide is made using liquid phase stripping method；
S2. the graphene oxide prepared by step S1 is added in deionized water, and uniformly, silane coupling agent is added in ultrasonic agitation, in
60 DEG C are stirred to react 2h, are cooled to room temperature, centrifugation, discard supernatant liquor, and solid is dried to get silane coupler modified oxidation
Graphene；
A kind of preparation method of environment-protection nano graphite alkene conductive ink, prepares in accordance with the following methods: by modified graphene oxide plus
Entering in ethanol solution, 500W ultrasonic agitation is uniform, addition silver citrate and copper citrate under ultrasonication, stirring and dissolving, according to
Secondary addition gelatin, aniline, ethylene group bis-stearamides, 2,6- three-level butyl -4- methylphenol and auxiliary agent, in agitated under sonication
After 2.5 h, ink is filtered to obtain environment-protection nano graphite alkene conductive ink with 0.45 μm of the syringe filter disk in aperture.
The ink of preparation is injected separately into print cartridge, printed substrates are printed using printer, printed substrates material is
Polypropylene, print temperature are 55 DEG C；It is put into the printed substrates after inkjet printing in 170mm size vacuum drier, and is put into
Small beaker equipped with 1mL hydroiodic acid opens mechanical pump, is evacuated to 1000Pa and turns off mechanical pump, is then heated to 120 DEG C, warp
3h is crossed, is taken out.As a result, it has been found that environment-protection nano graphite alkene conductive ink manufactured in the present embodiment can be carried out inkjet printing, obtain
Pattern with high transparency, the transparent pattern obtained after reduction show high electrical conductivity (film resistor is 145 Ω/m) and height
Transparent (transmitance 96%).
Embodiment 4
Raw material forms (parts by weight): 30 parts of modified graphene oxide, 23 parts of silver citrate, 19 parts of copper citrate, 8 parts of aniline, bright
5 parts of glue, 3 parts of microcrystalline wax, four (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) 5 parts of pentaerythritol esters, 4 parts of auxiliary agent, second
65 parts and 45 parts of water of alcohol；
The auxiliary agent is made of by weight following raw material: 13 parts of polyethylene glycol 400,4 parts of sorbierite, dimethicone 1.7
Part, 4 parts of tween.
The modified graphene oxide is prepared by following methods:
S1. graphene oxide is made using liquid phase stripping method；
S2. the graphene oxide prepared by step S1 is added in deionized water, and uniformly, silane coupling agent is added in ultrasonic agitation, in
60 DEG C are stirred to react 2h, are cooled to room temperature, centrifugation, discard supernatant liquor, and solid is dried to get silane coupler modified oxidation
Graphene；
A kind of preparation method of environment-protection nano graphite alkene conductive ink, prepares in accordance with the following methods: by modified graphene oxide plus
Entering in ethanol solution, 500W ultrasonic agitation is uniform, addition silver citrate and copper citrate under ultrasonication, stirring and dissolving, according to
Secondary addition gelatin, aniline, microcrystalline wax, four (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) pentaerythritol esters and auxiliary agent,
After 2.5 h of agitated under sonication, ink is filtered to obtain environment-protection nano graphite with 0.45 μm of the syringe filter disk in aperture
Alkene conductive ink.
The ink of preparation is injected separately into print cartridge, printed substrates are printed using printer, printed substrates material is
Polypropylene, print temperature are 55 DEG C；It is put into the printed substrates after inkjet printing in 170mm size vacuum drier, and is put into
Small beaker equipped with 1mL hydroiodic acid opens mechanical pump, is evacuated to 1000Pa and turns off mechanical pump, is then heated to 120 DEG C, warp
3h is crossed, is taken out.As a result, it has been found that environment-protection nano graphite alkene conductive ink manufactured in the present embodiment can be carried out inkjet printing, obtain
Pattern with high transparency, the transparent pattern obtained after reduction show high electrical conductivity (film resistor is 142 Ω/m) and height
Transparent (transmitance 97%).
Embodiment 5
Raw material forms (parts by weight): 26 parts of modified graphene oxide, 20 parts of silver citrate, 17 parts of copper citrate, 6 parts of aniline, bright
4 parts of glue, 2.5 parts of calcium stearate, bis- (3,5- three-level butyl -4- hydroxy phenyl) 4 parts of thioether, 3 parts of auxiliary agent, 60 parts of ethyl alcohol and water 30
Part；
The auxiliary agent is made of by weight following raw material: 13 parts of polyethylene glycol 400,3 parts of sorbierite, dimethicone 1.5
Part, 3 parts of tween.
The modified graphene oxide is prepared by following methods:
S1. graphene oxide is made using liquid phase stripping method；
S2. the graphene oxide prepared by step S1 is added in deionized water, and uniformly, silane coupling agent is added in ultrasonic agitation, in
60 DEG C are stirred to react 2h, are cooled to room temperature, centrifugation, discard supernatant liquor, and solid is dried to get silane coupler modified oxidation
Graphene；
A kind of preparation method of environment-protection nano graphite alkene conductive ink, prepares in accordance with the following methods: by modified graphene oxide plus
Entering in ethanol solution, 500W ultrasonic agitation is uniform, addition silver citrate and copper citrate under ultrasonication, stirring and dissolving, according to
Secondary addition gelatin, aniline, calcium stearate, bis- (3,5- three-level butyl -4- hydroxy phenyl) thioethers and auxiliary agent, in agitated under sonication
After 2.5 h, ink is filtered to obtain environment-protection nano graphite alkene conductive ink with 0.45 μm of the syringe filter disk in aperture.
The ink of preparation is injected separately into print cartridge, printed substrates are printed using printer, printed substrates material is
Polypropylene, print temperature are 55 DEG C；It is put into the printed substrates after inkjet printing in 170mm size vacuum drier, and is put into
Small beaker equipped with 1mL hydroiodic acid opens mechanical pump, is evacuated to 1000Pa and turns off mechanical pump, is then heated to 120 DEG C, warp
3h is crossed, is taken out.As a result, it has been found that environment-protection nano graphite alkene conductive ink manufactured in the present embodiment can be carried out inkjet printing, obtain
Pattern with high transparency, the transparent pattern obtained after reduction show high electrical conductivity (film resistor is 140 Ω/m) and height
Transparent (transmitance 98%).
Comparative example 1
It is led according to the transparent patterning of a kind of graphene-based water-based ink of 201410472694 .9(of patent ZL and its inkjet printing
The application of electrode) method preparation, the method is as follows:
Graphene-based water-based ink is made of the compound and water of graphene oxide and silver nano-grain, graphene oxide and Yin Na
The mass fraction of the compound of rice grain is 2.4%, and graphene oxide and silver nano-grain mass ratio are 0.5；Graphene oxide
Diameter less than 2 μm；The partial size of silver nano-grain is less than 100nm.
The synthesis of graphene oxide: the graphene oxide for using the Hummer method of improvement to be prepared is golden yellow production
Object；Product ultrasonic disruption machine 200W is handled 2 hours, later by 1 μM of filter membrane, removes large scale graphene oxide；It obtains
Solid carry out at room temperature overnight vacuum it is dry to get.
The synthesis of silver nano-grain: the silver nitrate of the 10wt% sodium citrate solution of 100 μ L and the 10wt% of 50 μ L is molten
Liquid is added in 1mL water, is stirred at room temperature to color from white to colourless, is obtained mixed solution A；By the 0.1mmol/ of 49 μ L
The liquor kalii iodide of 5 μm of ol/L of the ascorbic acid solution of L and 49 μ L mix, and being added to volume is 1000 times of ascorbic acid solution
80 DEG C of water in, stir evenly, obtain mixed solution B；After heating makes mixed solution B boil, mixed solution A is injected into mixed
It closes in solution B, uniform stirring makes the reaction solution of yellow in 100 DEG C of holding 1h, obtains crude product, washs through water and dehydrated alcohol
Afterwards, it is collected using centrifugation and rotary evaporation in vacuo, obtains monodispersity polyhedral silver nano-grain.
The preparation of ink: by the graphene oxide of above-mentioned preparation and silver nano-grain using 1h ultrasonic disperse in water,
The compound of graphene oxide and silver nano-grain is obtained, is then filtered out impurity with the filter that filter sizes are 0.8 μm.
The printing of electrode: injecting ink into print cartridge, is printed using printer to printed substrates, and printed substrates material is
Sheet glass, print temperature are 40 DEG C；It is put into the printed substrates after inkjet printing in 150mm size vacuum drier, and is put into
Small beaker equipped with 1mL hydrazine hydrate opens mechanical pump, and being evacuated to vacuum gage pressure readings is that -0.1 megapascal turns off mechanical pump, so
After be heated to 90 DEG C, by 3h, take out, obtain the conductive pattern polarizing electrode with high transparency.
As a result, it has been found that the ink made of monodispersity polyhedral silver nano-grain-graphene oxide can be used for ink-jet
Printing, can be obtained pattern (see Fig. 1) after reduction, the transparent pattern of acquisition show high conductivity (film resistor is 639 Ω/m) and
High transparency (transmitance 87%).
After the printing of conductive inks prepared by the conductive ink and comparative example 1 of comparison 1-5 of embodiment of the present invention preparation
Film resistor and transmitance to transparent pattern are found, obtain transparent pattern after the printing of conductive inks of preparation of the embodiment of the present invention
Film resistor between 140-150 Ω/m (1 film resistor of comparative example be 639 Ω/m), transmitance is (right between 95%-98%
87%) 1 transmitance of ratio is that therefore, the resistivity after printing of conductive inks of the invention is lower, and transmitance is higher, hence it is evident that excellent
In the prior art.
Compared with prior art, after gelatin and aniline is added, stability has environment-protection nano graphite conductive ink of the present invention
It is obviously improved, the addition of gelatin has an effect being remarkably reinforced to the adhesive force between enhancing ink and substrate, is added simultaneously
After aniline, the resistivity of ink can be effectively reduced；The conductive silver source and copper source that the present invention adds are silver citrate and citric acid
Copper, without metallic particles, ink fluency is more preferable, is more soluble in ethanol solution, is complexed by generating silver-amine with aniline reaction
Object, copper-amine complex, stability is more preferable, can satisfy printability requirement；Graphene oxide of the present invention removes legal system by liquid phase
, and be modified with silane coupling agent, modified graphene oxide obtained is nanoscale, it is smaller, meet conductive ink
Conductive demand and printing fluency demand, meanwhile, connected between substrate by chemical bond key, it is stronger to be not easy to tear；This
Method uses second alcohol and water for solvent, does not add harmful organic solvent, VOC free, without harmful additive, safety and environmental protection；System of the present invention
Preparation Method is simple, and raw material sources are wide, and conductive ink resistivity is low, strong with substrate adhesive force, not oxidizable, and stability is good, can be with
Meet printability requirement and safety and environmental protection.
Those skilled in the art is not under conditions of departing from the spirit and scope of the present invention that claims determine, also
Various modifications can be carried out to the above content.Therefore the scope of the present invention is not limited in above explanation, but by
The range of claims determines.
Claims (10)
1. a kind of environment-protection nano graphite alkene conductive ink, which is characterized in that be prepared from the following materials: modified graphite oxide
Alkene, silver citrate, copper citrate, aniline, gelatin, dispersing agent, antioxidant, auxiliary agent, second alcohol and water；
The modified graphene oxide is prepared by following methods:
S1. graphene oxide is made using liquid phase stripping method；
S2. the graphene oxide prepared by step S1 is added in deionized water, and uniformly, silane coupling agent is added in ultrasonic agitation, in
60 DEG C are stirred to react 1-3h, are cooled to room temperature, centrifugation, discard supernatant liquor, and solid is dried to get silane coupler modified oxygen
Graphite alkene.
2. a kind of environment-protection nano graphite alkene conductive ink according to claim 1, which is characterized in that by weight by following raw material
Part be prepared: 20-35 parts of modified graphene oxide, 15-25 parts of silver citrate, 15-20 parts of copper citrate, 3-10 parts of aniline,
2-5 parts of gelatin, 1-3 parts of dispersing agent, 2-5 parts of antioxidant, 1-5 parts of auxiliary agent, 50-70 parts of ethyl alcohol and 30-50 parts of water.
3. a kind of environment-protection nano graphite alkene conductive ink according to claim 2, which is characterized in that by weight by following raw material
It part is prepared: 22-30 parts of modified graphene oxide, 17-23 parts of silver citrate, 16-19 parts of copper citrate, 4-8 parts of aniline, bright
3-5 parts of glue, 2-3 parts of dispersing agent, 3-5 parts of antioxidant, 2-4 parts of auxiliary agent, 55-65 parts of ethyl alcohol and 25-45 parts of water.
4. a kind of environment-protection nano graphite alkene conductive ink according to claim 3, which is characterized in that by weight by following raw material
Part is prepared: 26 parts of modified graphene oxide, 20 parts of silver citrate, 17 parts of copper citrate, 6 parts of aniline, 4 parts of gelatin, dispersion
2.5 parts of agent, 4 parts of antioxidant, 3 parts of auxiliary agent, 60 parts of ethyl alcohol and 30 parts of water.
5. a kind of environment-protection nano graphite alkene conductive ink according to claim 1, which is characterized in that the dispersing agent is selected from second
It is support group bis-stearamides, glyceryl monostearate, microcrystalline wax, calcium stearate, cadmium stearate, magnesium stearate, barium stearate, hard
One or more of resin acid zinc and copper stearate.
6. a kind of environment-protection nano graphite alkene conductive ink according to claim 1, which is characterized in that the antioxidant is selected from 2,
6- three-level butyl -4- methylphenol, bis- (3,5- three-level butyl -4- hydroxy phenyl) thioethers, four (β-(3,5- three-level butyl -4- hydroxyls
One or more of base phenyl) propionic acid) pentaerythritol ester, diphenylamines, p-phenylenediamine and dihydroquinoline.
7. a kind of environment-protection nano graphite alkene conductive ink according to claim 1, which is characterized in that the auxiliary agent includes poly- second
Glycol 400, sorbierite, dimethicone and tween.
8. a kind of environment-protection nano graphite alkene conductive ink according to claim 1, which is characterized in that the auxiliary agent is by following original
Material forms by weight: 10-15 parts of polyethylene glycol 400,2-5 parts of sorbierite, 1-2 parts of dimethicone, 2-5 parts of tween.
9. a kind of preparation method of environment-protection nano graphite alkene conductive ink described in -8 any claims according to claim 1,
It being characterized in that, prepares in accordance with the following methods: modified graphene oxide is added in ethanol solution, 500W ultrasonic agitation is uniform,
Silver citrate and copper citrate, stirring and dissolving are added under ultrasonication, sequentially adds gelatin, aniline, dispersing agent, antioxidant and helps
Agent is filtered ink to obtain environment-friendly nano stone after agitated under sonication 2-3 h with 0.45 μm of the syringe filter disk in aperture
Black alkene conductive ink.
10. a kind of application of environment-protection nano graphite alkene conductive ink, which is characterized in that by claim 1-8 any claim
The ink is applied in the printing of flexible circuit.
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Application publication date: 20190405 |