CN104992752A - Production method of silver nanowire transparent conductive film - Google Patents
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- CN104992752A CN104992752A CN201510419011.8A CN201510419011A CN104992752A CN 104992752 A CN104992752 A CN 104992752A CN 201510419011 A CN201510419011 A CN 201510419011A CN 104992752 A CN104992752 A CN 104992752A
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Abstract
The invention provides a production method of a silver nanowire transparent conductive film. The production method comprises the steps of: preparing a silver nanowire coating liquid, and coating the silver nanowire coating liquid on a base material sheet to obtain a silver nanowire conductive coating; coating an oxide sol on the upper surface of the silver nanowire conductive coating to obtain an oxide protective layer; and forming the silver nanowire transparent conductive film on the base material sheet after baking and curing. The transmittance of the silver nanowire transparent conductive film prepared by adopting the method can reach 85 to 91%, the haze of the same is less than or equal to 2%, the surface resistivity of the same ranges from 10 to 200ohm/sq, and the surface hardness of the same ranges from 6 to 8H.
Description
Technical field
The present invention relates to the technical field of transparent conductive film, especially relate to the production method of nano-silver thread transparent conductive film.
Background technology
Transparent conductive film (TCFs) refers to that (λ=380-780nm) has higher light transmittance in visible-range, and (resistivity is generally lower than 10 for excellent conductivity
-3Ω cm) thin-film material.Nesa coating application widely, is mainly used in photoelectric device as fields such as the transparency electrodes of the transparency electrode of liquid crystal display, touch-screen, thin-film solar cells.Light transmittance and conductivity are two indexs mutually pind down, and in general, conductivity improves, and light transmittance will decline, otherwise too.Transparent conductive film common at present comprises ITO (Indium TinOxides tin dope three indium oxide), GZO (Gallium Zinc Oxides Ga-doped zinc oxide), AZO (Aluminum Zinc Oxides aluminium-doped zinc oxide) etc., these oxides only absorb ultraviolet light, do not absorb visible ray.
In nearest 20 years, nesa coating application is main based on ITO material, and based on magnetic control sputtering plating technique on processing procedure.High visible light transmittance rate and quite low resistivity combine, and make one of ito thin film transparent conductive material becoming excellent combination property.But ITO material itself exposes many defects, as raw material lack, high, the complicated process of preparation of cost etc., some enterprises and research institution are devoted to find its substitution material always.
Nano silver wire (AgNW) film owing to having good characteristic in electricity, optics and mechanicalness, to cause the extensive concern of researcher in recent years, nano silver wire is due to its high-specific surface area, good conductivity, thermal conductivity, flexible resistance and nanocomposite optical character, and surface plasma effect, be thus widely used in fields such as solar cell, medical imaging, Surface-enhanced spectroscopic, high-brightness LED, conducting resinl, touch-screen, liquid crystal display, transducer, environmental protection, catalyst.
In prior art, nano-silver thread is coated on the production method base materials such as clear glass being formed transparent conductive film to be generally: first modulate nano-silver thread coating fluid, then by the nano-silver thread coating solution that modulates at transparent substrate surface, form nano-silver thread conductive coating, finally baking-curing forms again.Such as patent application 201410229548.3, discloses this method.Wherein, the modulation of nano-silver thread coating fluid is generally by nano-silver thread uniform stirring in glue, and then adds or do not add adjuvant (a kind of mixture containing dispersant, curing agent and solvent) wherein.The main component of glue is one or more macromolecule organics; these macromolecule organics can reduce transmitance and the conductivity of nano-silver thread conductive layer usually; transmitance about 85% time, the sheet resistance value of nano-silver thread conductive film generally can only reach about 50 Ω/sq.
And, the case hardness general lower (generally can only reach 3-4H) of the nano-silver thread transparent conductive film that prior art is prepared on the base materials such as clear glass, resistance to wear is not good enough, etch through gold-tinted (or laser) transparency electrode formed to be easy to because of slight physical damnification or chemical damage and breakpoint, thus cause product function bad.Therefore, nano-silver thread transparent conductive film limitation in application that prior art is produced is very large, is difficult to popularize.
Summary of the invention
For the deficiency that prior art exists, the invention provides a kind of production method of nano-silver thread transparent conductive film, the method is intended to the conductivity, case hardness and the resistance to wear that ensure greatly to improve nano-silver thread transparent conductive film while light transmission.
The method can be applicable to nano-silver thread film forming at transparent glass sheet, transparent PET (plastics) sheet, transparent organic glass sheet simultaneously, and on the multiple base material such as TFT (thin-film transistor) sheet, and the nano-silver thread transparent conductive film transmitance of preparation can reach 85 ~ 91%, mist degree≤2%, surface resistivity 10 ~ 200ohm/sq, case hardness 6-8H.Thus make the nano-silver thread transparent conductive film prepared by the method be provided with application widely, can be used in the transparency electrode preparing the multiple components and parts such as LED display, touch-screen, thin-film solar cells, and conducting resinl, heat-conducting glue etc.Along with film-forming process mates with perfect with the continuous of equipment, the performance of the nano-silver thread transparent conductive film prepared by the art of this patent and yield will be stablized further and promote, cost constantly declines, thus progressively will substitute ITO, becomes the first-selection of transparent conductive film material.
For achieving the above object, the technical solution adopted in the present invention is:
A production method for nano-silver thread transparent conductive film, comprises the following steps:
(1) by nano-silver thread uniform stirring in TiO 2 sol, obtain nano-silver thread coating fluid; Wherein contain 2g ~ 8g nano-silver thread in 1kg nano-silver thread coating fluid; The diameter of described nano-silver thread is less than or equal to 200 nanometers, and length is 20 microns ~ 200 microns, and draw ratio is 500 ~ 1000; Described TiO 2 sol solids content is 0.5wt% ~ 5wt%, and average grain diameter is 20 nanometer ~ 100 nanometers;
(2) by described nano-silver thread coating solution in substrate sheets, coating thickness is 5 microns ~ 100 microns, after natural drying nano-silver thread conductive coating;
(3) at the upper surface coating oxide sol of described nano-silver thread conductive coating, coating thickness is 5 microns ~ 100 microns, obtains protective oxide film after natural drying; Described oxide sol is silicon dioxide gel or other metal oxide sol;
(4) in described substrate sheets, nano-silver thread transparent conductive film is formed after baking-curing.
The preparation method of step (1) described TiO 2 sol preferably includes following steps: by titanium alkoxide, acid catalyst and alcohol titanium alkoxide in mass ratio: acid catalyst: stir 1 ~ 3h, obtained solution a after alcohol=1:0.1 ~ 0.5:8 ~ 25 mix; By deionized water, alcohol and inhibitor according to quality than deionized water: alcohol: inhibitor=1:15 ~ 30:0.03 ~ 0.06 mix and blend 1 ~ 3h obtains solution b; Solution b is added drop-wise in the solution a constantly stirred, drips rear continuation stirring 2 ~ 5h, finally obtained solution is obtained TiO 2 sol after at room temperature ageing 24-48 hour.
Wherein one or more such as hydrochloric acid, nitric acid, sulfuric acid, glacial acetic acid, gallic acid, acrylic acid preferably chosen by described acid catalyst.
Wherein one or more such as monoethanolamine, diethanol amine, triethanolamine, triethylamine preferably chosen by described inhibitor.
Wherein one or more such as ethanol, propyl alcohol, butanols, amylalcohol preferably chosen by described alcohol.
Described titanium alkoxide is preferably butyl titanate.
Step (1) described nano-silver thread is preferably prepared into nano-silver thread suspension in accordance with the following methods and is added in described TiO 2 sol again: by silver-colored source, catalyst, dispersant and solvent hold concurrently reducing agent by silver-colored source: catalyst: dispersant: the hold concurrently mass ratio of reducing agent of solvent is inject reactor after 1:0.0001 ~ 0.0005:0.5 ~ 10:250 ~ 300 mix, reactor homogeneous heating to 160 DEG C ~ 240 DEG C is kept 3 ~ 5h, obtain nano-silver thread, then adopt the method for centrifugation by nano-silver thread purifying, finally the nano-silver thread after purifying is kept in alcoholic solvent, obtain nano-silver thread suspension.
Further preferred version: described silver-colored source is selected from silver nitrate or silver acetate; Described catalyst is selected from by one or more in sodium chloride, copper chloride, iron chloride or zinc chloride; Described dispersant is selected from the one in polyvinylpyrrolidone, softex kw or aniline; Described solvent is held concurrently one or more that reducing agent is selected from ethylene glycol, propylene glycol, butanediol, pentanediol, glycerol.
The nano-silver thread purge process of described employing centrifugal separation method comprises 1-4 desalt, then carries out 1-2 alcohol purifying;
Step (2) described substrate sheets is preferably selected from transparent glass sheet, transparent PET sheet, transparent organic glass sheet or liquid-crystalline glasses sheet.
The thickness of step (2) described substrate sheets preferably >=0.1mm.
Step (3) other metal oxide sol described is preferably selected from TiO 2 sol, alundum (Al2O3) colloidal sol, zirconia sol or zinc oxide colloidal sol.
The preparation method of step (3) described oxide sol preferably includes: stir 60 ~ 90min, obtained solution a after siliceous organic substance or metal alkoxide class material being mixed by the mass ratio of 1:8 ~ 15 with alcohol; Deionized water, alcohol and acid catalyst are obtained solution b by stirring 60 ~ 90min after the mass ratio mixing of 1:2 ~ 4:0.04 ~ 0.06; Solution b is added drop-wise in solution a, drips rear continuation stirring 90 ~ 120min, more described mixed solution is obtained oxide sol at room temperature ageing 24-48 hour; Described oxide sol solids content is 0.2 ~
10wt%, average grain diameter is 10 nanometer ~ 100 nanometers.Wherein the preferred selection range of alcohol and acid catalyst is with mentioned above.
Described siliceous organic substance is preferably tetraethoxysilane.
Step (4) described baking temperature is preferably 80 DEG C-180 DEG C.
After step (4) baking-curing, the gross thickness of described nano-silver thread transparent conductive film is preferably 50 nanometer ~ 300 nanometers.
The present invention has two major features:
Feature one: the present invention adopts increases one deck protective oxide film by nano-silver thread conductive layer tight bond on the surface of substrate sheets, in the solidification process of protective layer, solvent in nano-silver thread coating fluid and protective layer colloidal sol, and other materials lower boiling all can volatilize, Si oxide in the protective layer stayed or metal oxide and nano-silver thread film surface and substrate surface form silicon oxygen bond or metal oxygen bridged bond, and the network configuration formed after protective layer solidification neither affects the conductivity of nano-silver thread rete, nano-silver thread can be protected again not oxidized or come off, thus it is good to obtain electric conductivity, transmitance and the higher nano-silver thread transparent conductive film of case hardness, no matter this conductive film is in mechanical performance (case hardness and resistance to wear etc.), or the conductive film all prepared than prior art in chemical property (acid-proof alkali prevention etc.) is superior many.
Feature two: the present invention takes the method modulation nano-silver thread coating fluid of nano-silver thread uniform stirring in TiO 2 sol, described TiO 2 sol not only can strengthen the discreteness of nano-silver thread thus the agglomeration traits of solution nano-silver thread, and nano-silver thread even handing-over each other can be promoted when film forming thus improve its conductivity, also minimum on the transmitance impact of nano-silver thread coating, transmitance about 85% time, the sheet resistance value of nano-silver thread conductive film can reach about 20 Ω/sq.
The nano-silver thread transparent conductive film light transmission rate that the present invention prepares on transparent glass sheet reaches as high as 91%, surface resistivity reaches as high as that 10 Ω/sq, mist degree preferably can reach 1%, case hardness reaches as high as 9H.
Compared with prior art, main advantage of the present invention has following three aspects:
(1) invention increases the case hardness of nano-silver thread conductive film, improve silver-colored line rete at the adhesive force of substrate surface, resistance to wear and acid-fast alkali-proof, overcome that the nano-silver thread transparent conductive film that prior art produces easily scratches when preparing transparency electrode and circuit, the shortcoming such as lateral erosion and oxidation, nano-silver thread transparent conductive film case hardness prepared by prior art can only reach 3-4H, and nano-silver thread conductive film case hardness prepared by the technology of the present invention can reach 6-8H.
(2) the present invention improves the conductivity of nano-silver thread transparent conductive film exponentially under equal transmitance condition, prior art is when meeting nano-silver thread transparent conductive film transmitance about 85%, sheet resistance value can only reach about 50 Ω/sq, and the present invention under equal conditions can make the sheet resistance value of conductive film reach about 20 Ω/sq.
(3) simple process prepared of nano-silver thread of the present invention, quality is easily controlled, and production cost is lower, is convenient to industrial volume production and application.
Accompanying drawing explanation
The SEM figure of the nano-silver thread of Fig. 1 prepared by the present invention;
The hardness test figure of the nano-silver thread conductive film of Fig. 2 prepared by the present invention; Fig. 2 (a) is the delineation of 7H pencil, and Fig. 2 (b) is the delineation of 8H pencil, and Fig. 2 (c) is the delineation of 9H pencil;
The transmission measurement result figure of the nano-silver thread conducting film prepared by Fig. 3 the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
The transparent production method leading glass of nano-silver thread, comprises the following steps:
(1) base material is chosen: select specification to be the transparent glass sheet of 450mm × 550mm × 0.7mm;
(2) nano-silver thread suspension is modulated, adopt alcohol reducing process, reactor is injected after silver nitrate, copper chloride, polyvinylpyrrolidone and glycerol being pressed the mass ratio mixing of 1:0.0002:3:250, by sustained response 4h after about reactor homogeneous heating to 200 DEG C, naturally namely obtaining diameter after cooling is 30 ~ 40 nanometers, and length is the nano-silver thread of 10 ~ 30 μm.Then by the method for centrifugation, remove by intermediate water purifying, an ethanol purification solvent, dispersant and other impurity that are blended in nano-silver thread successively.Finally the nano-silver thread after purifying is kept in absolute ethyl alcohol.
(3) modulate TiO 2 sol, by butyl titanate, ethanol and hydrochloric acid with after the mixing of the mass ratio of 1:10:0.006, under the rotating speed of 800r/min, Keep agitation 120min obtains solution a; Deionized water, ethanol and monoethanolamine are obtained solution b to stir 120min after the mixing of the mass ratio of 1:30:0.05 under the rotating speed of 800r/min; Then solution b is added drop-wise in solution a with the speed of 4mL/min, drips in backward mixed liquor and add a small amount of additive, leave standstill 24h after continuing to stir 150min and namely obtain titanium dioxide dispersion sol.
(4) modulate nano-silver thread coating fluid, nano-silver thread suspension is mixed with the volume ratio of TiO 2 sol according to 1:5, makes the nano-silver thread coating fluid needed for the present embodiment.Wherein contain 4g nano-silver thread in 1Kg nano-silver thread coating fluid; Diameter 30 ~ 40 nanometer of described nano-silver thread, and length is 10 ~ 30 microns, draw ratio is 500 ~ 1000; Solids content in TiO 2 sol is about 0.8wt%, average grain diameter about 50 nanometer of colloidal sol;
(5) modulate silicon dioxide gel, after being mixed by the mass ratio of 1:10 with ethanol by tetraethoxysilane, under the rotating speed of 800r/min, stir 90min, obtained solution a; Deionized water, ethanol and hydrochloric acid are obtained solution b by stirring 60min after the mass ratio mixing of 1:3:0.05 under the rotating speed of 800r/min; Solution b is added drop-wise in solution a with the speed of 4mL/min, drips rear continuation and stir 120min, the more at room temperature ageing of described mixed solution can be obtained silicon dioxide gel in 24 hours.Described silicon dioxide gel solids content is about 0.7wt%, and average grain diameter is about 40 nanometers;
(6) nano-silver thread conductive layer is coated with, transparent glass sheet is transmitted by the conveyer belt of coating apparatus, by the upper surface even spread nano-silver thread coating fluid of the coating mechanism above conveyer belt at transparent glass sheet, after coating, at room temperature natural air drying 50s can obtain nano-silver thread conductive layer, and the thickness being coated on the nano-silver thread coating fluid on transparent glass sheet surface is about 10-25 μm;
(7) coat protective layer; the sheet glass being coated with nano-silver thread conductive layer is sent to next coating apparatus; on nano-silver thread conductive layer, be coated with layer of silicon dioxide colloidal sol again as protective layer by the coating mechanism above conveyer belt, wherein the thickness of silicon dioxide layer of protection is about 10-20 μm.
(8) solidify, transmit transparent glass sheet by drying baker by conveyer belt, complete in drying baker and dry and drying, baking temperature is 150 DEG C, and baking time is 180min.After dry, the gross thickness of conductive film layer is about 70-150 nanometer.
(9) finished product, makes nano-silver thread transparent conducting glass, and basic mechanical design feature index is as follows: transmitance 87 ~ 90%, mist degree 1 ~ 2%, sheet resistance 20 ~ 50ohm/sq, and case hardness is 7 ~ 8H.
Fig. 1 is the SEM figure of the nano-silver thread of preparation, and as can be seen from Figure 1, the nano-silver thread good dispersion of preparation, caliber even thickness, silver-colored linear diameter is 30-40 nanometer, and length is at 15-30 micron, and draw ratio is 1000:1.Fig. 2 is the hardness test figure of the nano-silver thread conductive film of preparation, and as can be seen from Figure 2, draw caudacoria without obvious cut through 8H pencil, the hardness of visible film reaches 7-8H.Fig. 3 is the transmission measurement result of the nano-silver thread conducting film of preparation, and can find out, in whole visible region (wavelength 380-650 nanometer), the average light transmitance of film reaches 90%.In addition, show that its sheet resistance is 20-50 Ω/sq after tested, there is good electric conductivity.
Embodiment 2
The transparent production method leading glass of nano-silver thread, comprises the following steps: (1) chooses base material: select specification to be the transparent glass sheet of 450mm × 550mm × 0.7mm;
(2) nano-silver thread suspension is modulated, adopt alcohol reducing process, reactor is injected after silver nitrate, copper chloride, polyvinylpyrrolidone and glycerol being pressed the mass ratio mixing of 1:0.0003:4:300, by sustained response 4h after about reactor homogeneous heating to 220 DEG C, naturally namely obtaining diameter after cooling is 25 ~ 35 nanometers, and length is the nano-silver thread of 10 ~ 20 μm.Then by the method for centrifugation, remove by intermediate water purifying, an ethanol purification solvent, dispersant and other impurity that are blended in nano-silver thread successively.Finally the nano-silver thread after purifying is kept in absolute ethyl alcohol.
(3) modulate TiO 2 sol, adopt sol-gal process, by butyl titanate, ethanol and nitric acid with after the mixing of the mass ratio of 1:10:0.006, under the rotating speed of 800r/min, Keep agitation 120min obtains solution a; Deionized water, ethanol and diethanol amine are obtained solution b to stir 120min after the mixing of the mass ratio of 1:30:0.05 under the rotating speed of 800r/min; Then solution b is added drop-wise in solution a with the speed of 4mL/min, leaves standstill 24h after dripping rear continuation stirring 120min and namely obtain titanium dioxide dispersion sol.
(4) modulate nano-silver thread coating fluid, nano-silver thread suspension is mixed with the volume ratio of TiO 2 sol according to 1:5, makes the nano-silver thread coating fluid needed for the present embodiment.Wherein contain 5g nano-silver thread in 1Kg nano-silver thread coating fluid; The diameter of described nano-silver thread is less than or equal to 35 nanometers, and length is 25 ~ 35 microns, and draw ratio is 500 ~ 1000; Solids content in TiO 2 sol is about 1.5wt%, and the average grain diameter of colloidal sol is 50 ~ 100 nanometers;
(5) modulate silicon dioxide gel, adopt sol-gal process, after being mixed by the mass ratio of 1:10 with propyl alcohol by tetraethoxysilane, under the rotating speed of 800r/min, stir 90min, obtained solution a; Deionized water, ethanol and nitric acid are obtained solution b by stirring 80min after the mass ratio mixing of 1:4:0.05 under the rotating speed of 800r/min; Solution b is added drop-wise in solution a with the speed of 5mL/min, drips rear continuation and stir 120min, the more at room temperature ageing of described mixed solution can be obtained silicon dioxide gel in 24 hours.Described silicon dioxide gel solids content is about 0.6wt%, and average grain diameter is 50 ~ 100 nanometers;
(6) nano-silver thread conductive layer is coated with, by the upper surface even spread nano-silver thread coating fluid of the coating mechanism of first above coating apparatus conveyer belt at transparent glass sheet, after coating, at room temperature natural air drying 50s can obtain nano-silver thread conductive layer, and the thickness being coated on the nano-silver thread coating fluid on transparent glass sheet surface is about 10-25 μm;
(7) coat protective layer, on nano-silver thread conductive layer, be coated with layer of silicon dioxide colloidal sol again as protective layer by the coating mechanism of second above coating apparatus conveyer belt, wherein the thickness of silicon dioxide layer of protection is about 10-20 μm.
(8) solidify, transmit transparent glass sheet by drying baker by conveyer belt, complete in drying baker and dry and drying, baking temperature is 160 DEG C, and baking time is 180min.After dry, the gross thickness of conductive film layer is about 70-150 nanometer.
(9) finished product, makes nano-silver thread transparent conducting glass, and basic mechanical design feature index is as follows: transmitance 86 ~ 88%, mist degree 1 ~ 2%, sheet resistance 20 ~ 50ohm/sq, and case hardness is 7 ~ 8H.
The production method of embodiment 3 one kinds of nano-silver thread conduction TFT
The key step of the present embodiment is identical with embodiment 1 with method, and its difference is:
(1) base material selects specification to be TFT (thin-film transistor) sheet of 670mm × 350mm × 0.1mm.
(2) nano-silver thread coating fluid and oxide sol must be coated on the front of TFT sheet.
(3) baking temperature is 80 ~ 130 DEG C, baking time 150-240min.
(4) the sheet resistance 20 ~ 50ohm/sq of finished product, case hardness 7 ~ 8H.
The production method of embodiment 4 one kinds of electrically conducting transparent PET
The key step of the present embodiment is identical with embodiment 1 with method, and its difference is:
(1) base material selects thickness to be transparent (plastics) PET sheet of 450mm × 550mm × 0.185mm.
(2) baking temperature is 80 ~ 100 DEG C, and baking time is 180 ~ 240min.
(3) transmitance 87 ~ 89% of finished product, mist degree 1 ~ 2%, the sheet resistance 30 ~ 70ohm/sq of finished product, case hardness is 5 ~ 6H.
The transparent production method leading glass of embodiment 5 one kinds of nano-silver threads
The key step of the present embodiment is identical with embodiment 1 with method, and its difference is:
(1) glass substrate is only coated with nano-silver thread coating fluid, is not coated with protective oxide film.
(2) baking temperature is 130 ~ 150 DEG C, and baking time is 80 ~ 120min.
(3) transmitance 89 ~ 91% of finished product, mist degree 1-2%, sheet resistance 20 ~ 50ohm/sq.
(4) case hardness of finished product is 1 ~ 2H.
Claims (15)
1. a production method for nano-silver thread transparent conductive film, comprises the following steps:
(1) by nano-silver thread uniform stirring in TiO 2 sol, obtain nano-silver thread coating fluid; Wherein contain 2g ~ 8g nano-silver thread in 1kg nano-silver thread coating fluid; The diameter of described nano-silver thread is less than or equal to 200 nanometers, and length is 20 microns ~ 200 microns, and draw ratio is 500 ~ 1000; Described TiO 2 sol solids content is 0.5wt% ~ 5wt%, and average grain diameter is 20 nanometer ~ 100 nanometers;
(2) by described nano-silver thread coating solution in substrate sheets, coating thickness is 5 microns ~ 100 microns, after natural drying nano-silver thread conductive coating;
(3) at the upper surface coating oxide sol of described nano-silver thread conductive coating, coating thickness is 5 microns ~ 100 microns, obtains protective oxide film after natural drying; Described oxide sol is silicon dioxide gel or other metal oxide sol;
(4) in described substrate sheets, nano-silver thread transparent conductive film is formed after baking-curing.
2. the production method of nano-silver thread transparent conductive film according to claim 1, it is characterized in that, the preparation method of step (1) described TiO 2 sol comprises the following steps: by titanium alkoxide, acid catalyst and alcohol titanium alkoxide in mass ratio: acid catalyst: stir 1 ~ 3h, obtained solution a after alcohol=1:0.1 ~ 0.5:8 ~ 25 mix; By deionized water, alcohol and inhibitor according to quality than deionized water: alcohol: inhibitor=1:15 ~ 30:0.03 ~ 0.06 mix and blend 1 ~ 3h obtains solution b; Solution b is added drop-wise in the solution a constantly stirred, drips rear continuation stirring 2 ~ 5h, finally obtained solution is obtained TiO 2 sol after at room temperature ageing 24-48 hour.
3. the production method of nano-silver thread transparent conductive film according to claim 2, it is characterized in that, wherein one or more such as hydrochloric acid, nitric acid, sulfuric acid, glacial acetic acid, gallic acid, acrylic acid chosen by described acid catalyst.
4. the production method of nano-silver thread transparent conductive film according to claim 2, it is characterized in that, wherein one or more such as monoethanolamine, diethanol amine, triethanolamine, triethylamine chosen by described inhibitor.
5. the production method of nano-silver thread transparent conductive film according to claim 2, it is characterized in that, wherein one or more such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol chosen by described alcohol.
6. the production method of nano-silver thread transparent conductive film according to claim 1 or 2, it is characterized in that, step (1) described nano-silver thread is prepared into nano-silver thread suspension in accordance with the following methods and is added in described TiO 2 sol again: by silver-colored source, catalyst, dispersant and solvent hold concurrently reducing agent by silver-colored source: catalyst: dispersant: the hold concurrently mass ratio of reducing agent of solvent is inject reactor after 1:0.0001 ~ 0.0005:0.5 ~ 10:250 ~ 300 mix, reactor homogeneous heating to 160 DEG C ~ 240 DEG C is kept 3 ~ 5h, obtain nano-silver thread, then adopt the method for centrifugation by nano-silver thread purifying, finally the nano-silver thread after purifying is kept in alcoholic solvent, obtain nano-silver thread suspension.
7. the production method of nano-silver thread transparent conductive film according to claim 6, it is characterized in that, described silver-colored source is selected from silver nitrate or silver acetate; Described catalyst is selected from by one or more in sodium chloride, copper chloride, iron chloride or zinc chloride; Described dispersant is selected from the one in polyvinylpyrrolidone, softex kw or aniline; Described solvent is held concurrently one or more that reducing agent is selected from ethylene glycol, propylene glycol, butanediol, pentanediol, glycerol.
8. the production method of nano-silver thread transparent conductive film according to claim 1 or 2, it is characterized in that, step (2) described substrate sheets is selected from transparent glass sheet, transparent PET sheet, transparent organic glass sheet or liquid-crystalline glasses sheet.
9. the production method of nano-silver thread transparent conductive film according to claim 1 or 2, is characterized in that, the thickness >=0.1mm of step (2) described substrate sheets.
10. the production method of nano-silver thread transparent conductive film according to claim 1 or 2, is characterized in that, step (3) other metal oxide sol described is selected from TiO 2 sol, alundum (Al2O3) colloidal sol, zirconia sol or zinc oxide colloidal sol.
11. according to claim 1 or 2 production method of nano-silver thread transparent conductive film, it is characterized in that, the preparation method of step (3) described oxide sol comprises: stir 60 ~ 90min, obtained solution a after siliceous organic substance or metal alkoxide class material being mixed by the mass ratio of 1:8 ~ 15 with alcohol; Deionized water, alcohol and acid catalyst are obtained solution b by stirring 60 ~ 90min after the mass ratio mixing of 1:2 ~ 4:0.04 ~ 0.06; Solution b is added drop-wise in solution a, drips rear continuation stirring 90 ~ 120min, more described mixed solution is obtained oxide sol at room temperature ageing 24-48 hour; Described oxide sol solids content is 0.2wt% ~ 10wt%, and average grain diameter is 10 nanometer ~ 100 nanometers.
12. according to the production method of nano-silver thread transparent conductive film described in claim 11, and it is characterized in that, wherein one or more such as hydrochloric acid, nitric acid, sulfuric acid, glacial acetic acid, gallic acid, acrylic acid chosen by described acid catalyst.
13. according to the production method of nano-silver thread transparent conductive film described in claim 11, and it is characterized in that, wherein one or more such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol chosen by described alcohol.
14. according to claim 1 or 2 production method of nano-silver thread transparent conductive film, it is characterized in that, step (4) described baking temperature is 80 DEG C-180 DEG C.
15. according to claim 1 or 2 production method of nano-silver thread transparent conductive film, it is characterized in that, after step (4) is dry, the gross thickness of described nano-silver thread transparent conductive film is 50 nanometer ~ 300 nanometers.
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