CN106229036B - A kind of transparent conductive film and preparation method thereof - Google Patents
A kind of transparent conductive film and preparation method thereof Download PDFInfo
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- CN106229036B CN106229036B CN201610599325.5A CN201610599325A CN106229036B CN 106229036 B CN106229036 B CN 106229036B CN 201610599325 A CN201610599325 A CN 201610599325A CN 106229036 B CN106229036 B CN 106229036B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Abstract
The invention discloses a kind of transparent conductive film, including electrically conducting transparent ink and base material, according to parts by weight, the electrically conducting transparent ink gathers including 0.5 ~ 50 part of nano-silver thread dispersion liquid, 15 ~ 35 parts（3,4 Ethylenedioxy Thiophenes）It is poly-（Styrene sulfonic acid）, 5 ~ 40 parts of organic solvent, 5 ~ 40 parts of deionized waters, 1 ~ 8 part of dimethyl sulfoxide (DMSO), 0.1 ~ 5 part of viscosity modifier, 0.01 ~ 1 part of pH adjusting agent, 0.01 ~ 2 part of surfactant, 0.01 ~ 1 part of levelling agent, 0.1 ~ 0.5 part of adhesion promoter.The invention also discloses the preparation method of the transparent conductive film.The transparent conductive film of the present invention has the characteristics of optical transmittance is high, mist degree is low, sheet resistivity is low；And low production cost.
Description
Technical field
The invention belongs to conductive film field, specifically a kind of transparent conductive film and preparation method thereof.
Background technology
With the increasingly raising of levels of substance, requirement of the consumer to electronic product is toward lightening and flexibility, visualization
Aspect it is fast-developing.Flexible display technologies, which have display, can bend or be curled into the characteristic of arbitrary shape, there is light, thin
And the features such as be convenient for carrying.Personal consumption electronic product on existing market mainly uses the hard such as tin indium oxide (ITO)
Inorganic oxide material as handset touch panel, solar energy, electromagnetic shielding, light-emitting diode display, electroluminescent device, thin film switch,
The core of the products such as cold light film.Tin indium oxide is because its fragility is big and is difficult to the defect of bending, it is difficult in flexible optoelectronic
Applied in device.High processing costs, energy consumption plus tin indium oxide are big, graphically need by mask, exposure, development, etching,
The cumbersome processing steps such as washing.Therefore nearly many decades, around substituting the research of transparent conductive film, using emerging in an endless stream.Most
Typically have CNT, graphene, nano-silver thread, metal grill transparent conductive film, wherein cost, performance, can volume production
Aspect most advantage is nano-silver thread transparent conductive film.
The existing multinomial patent application of transparent conductive film of nano-silver thread is currently based on, but actual graphical electrically conducting transparent is thin
Membrane process still follows ITO subtractive process techniques, first on base material full version coating, be dried to obtain nesa coating, then by mask,
The steps such as exposure, development, etching, washing, final obtained patterned transparent conducting film.Because process is complicated, yield is low, cost is high
High, the performance of the final conductive film of gained also has much room for improvement, therefore significantly limit the process that nano-silver thread substitutes ITO.
The mode of printing of current main flow has intaglio printing, letterpress, lithographic printing, silk-screen printing etc..Silk-screen is to refer to silk-screen printing,
Pass through the extruding of scraper plate during printing so that ink is transferred on stock by areas, screen printing apparatus is simple, operation
Facilitate, print, simple and with low cost, flexible or rigid base material of making a plate can print.Chinese patent application
201110058431.X discloses patterned flexible transparent conductive film and its preparation method, and the invention proposes base material impressing, so
The technology realization such as blade coating conductive ink prepares nesa coating afterwards, but the technology is not suitable for rigid substrate, and knifing process non-depressed
Easily there is ink residue in print part.Chinese patent application 201510096067.4 discloses a kind of electrically conducting transparent ink, its system
The production method of Preparation Method and nesa coating.This method be also as after silk-screen printing carry out photocuring obtained by, but due to set
Fat content is high, ink solid content is high (more than 60%), and the film layer for carrying out silk-screen printing acquisition according to current screen thickness is thicker,
Ultimately result in that sheet resistance is bigger than normal, light transmittance is relatively low, mist degree is higher.Chinese patent application 201510526785.0 discloses a kind of transparent
The preparation method of electrical-conductive nanometer silver wire ink and nesa coating, is directly coated with Nano Silver by coating machine on base material and is coated with
Liquid, it is impossible to realize graphical.There is the characteristics of light transmittance is relatively low, mist degree is higher in the nesa coating, and transparency conducting layer is used
Coating process, it is impossible to graphical.The meaning of patterned transparent conductive film is that conventional ITO production firms can only provide full version and lead
The film of electricity, downstream client need to voluntarily etch desired pattern.And the conventional frame is jumped out, allow customization pattern, and
Corresponding transparent conductive film is printed, the links such as mask, exposure, development, etching, the washing of production and processing can be saved, not only ring
Protect and save, efficiently, and its stability can be ensured to greatest extent.Therefore exploitation is realized by easy, efficient silk-screen printing technique
The preparation method of patterned transparent conductive film, and the transparent conductive film of excellent performance just seem very urgently and again
Will.
The content of the invention
It is an object of the invention to provide with a kind of optical transmittance is high, the transparent conductive film that mist degree is low, sheet resistivity is low.
Another object of the present invention provides the preparation method of the transparent conductive film.
To reach one of above-mentioned purpose, the present invention uses following technical scheme：
A kind of transparent conductive film, including electrically conducting transparent ink and base material, according to parts by weight, the electrically conducting transparent ink
Including 0.5~50 part of nano-silver thread dispersion liquid, 15~35 parts of poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acids), 5~
40 parts of organic solvents, 5~40 parts of deionized waters, 1~8 part of dimethyl sulfoxide (DMSO), 0.1~5 part of viscosity modifier, 0.01~1 part of pH
Conditioning agent, 0.01~2 part of surfactant, 0.01~1 part of levelling agent, 0.1~0.5 part of adhesion promoter.
Further, the nano-silver thread dispersion liquid is that nano-silver thread is scattered in methanol, ethanol, isopropanol, normal propyl alcohol, second
Glycol, propane diols, glycerine, water, propylene glycol monomethyl ether, dipropylene glycol methyl ether or propandiol butyl ether and obtain.
Further, the draw ratio of the nano-silver thread is 50~5000.
Further, the concentration of the nano-silver thread dispersion liquid is 1~100mg/mL.
It is preferred that nano-silver thread specification be：
Specification 1：Average line footpath is 30nm, a length of 30 μm of average line, draw ratio 1000；
Specification 2：Average line footpath is 40nm, a length of 40 μm of average line, draw ratio 1000；
Specification 3：Average line footpath is 70nm, a length of 40 μm of average line, draw ratio about 570.
With the raising of nano-silver thread draw ratio, the mist degree of transparent conductive film is reduced, and electric conductivity makes moderate progress.Nano Silver
Line functions as conductive filler, passes through the conductive network that nano-silver thread is overlapped, and assigns ink film good electric conductivity.
Further, the solid content of poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) be 1.0~
1.5%, electrical conductivity is 50~1000S/cm, and solvent is deionized water.It is the electric conductivity for improving ink that it, which is acted on, while playing tune
The effect of whole viscosity.
Further, the organic solvent be methanol, ethanol, isopropanol, normal propyl alcohol, ethylene glycol, propane diols, glycerine,
At least one of propylene glycol monomethyl ether, dipropylene glycol methyl ether, propandiol butyl ether, isophorone and terpinol.It is reduction that it, which is acted on,
There is provided more extensive dissolubility, levelability for ink surface tension.
Further, the viscosity modifier is hydroxypropyl methyl cellulose, hydroxypropyl cellulose, methylcellulose, second
The non-poly- ammonia of base cellulose, hydroxyethyl cellulose, xanthans, guar gum, polyurethane thickener, alkali solubility thickener, hydrophobically modified
At least one of ester thickener, poly-methyl pyrrole alkanone, aerosil and organobentonite.It is to improve ink that it, which is acted on,
Viscosity, improve printing adaptability.
Polyurethane thickener chemical composition be polyurethane resin, the Bermodol PUR 2102 of such as Akzo Nobel,
Bermodol PUR2110, Bermodol PUR2130, Bermodol PUR2150, the ACRYSOLRM-8 of ROHM AND HAAS,
ACRYSOLRM-8W, ACRYSOLRM-2020MPR, Tego Viscoplus 3000, the Tego Viscoplus of Di Gao companies
3030、Tego Viscoplus 3060。
Alkali solubility thickener is generally acrylic resin, such as ROHM AND HAAS AP-10, AP-50, ASE-60, TT-615, TT-
935；The modest Rheolate 125 of this moral of hamming, Rheolate 150, Rheolate 425, Rheolate450.
The non-polyurethane thickener of hydrophobically modified is generally hydrophobically modified polyethers, such as DSX2000 of German section peaceful (Cognis),
DSX3000, DSX3075, DSX3220, L100, L150, M200, H600 of Lockwood (Rockwood).
Further, the pH adjusting agent be ammoniacal liquor, sodium hydroxide, diethanol amine, triethanolamine, 2- amino-2-methyls-
1- propyl alcohol or ethylenediamine.
Further, the surfactant is Tego dispers740w, Tego dispers750w, Tego
Dispers760w, BYK-151, BYK-180, BYK-181, BYK-190, BYK-194, TRITON (x45, x100, x140) and
At least one of FSO-100.Surfactant is used to adjust surface tension, plays humidification.
TRITON (x45, x100, x140) is that U.S.'s Qula leads to the polyethylene glycol produced to isooctyl phenyl ether, from Guangzhou
Xi Lu Chemical Co., Ltd.s buy；FSO-100 is the ethyoxyl fluorocarbon surfactant that E.I.Du Pont Company develops, and is converged from Guangzhou and applies trade
Easy Co., Ltd's purchase.
Further, the levelling agent is BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, Tego
At least one of Glid110, Tego Glid410, Tego Glid450, the modest W-461 of this moral of hamming and the modest FS-444 of moral.Stream
Flat agent is used to improve printing levelability, prevents shrinkage cavity, grows dim.
Further, the adhesion promoter be aqueous polyurethane, it is water-based acrylic resin, polyvinyl alcohol, aqueous poly-
Ester, aqueous alkide resin, polyacrylamide, polyethylene glycol oxide, styrenemaleic acid resin, aqueous epoxy resins and melamine
At least one of resin.It is to improve ink film scratch resistance, adhesive force that it, which is acted on, and improves nano-silver thread dispersiveness and stability.
Further, the electrically conducting transparent ink is prepared in accordance with the following methods：At room temperature by nano-silver thread dispersion liquid, poly-
(3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid), organic solvent, deionized water, dimethyl sulfoxide (DMSO), viscosity modifier,
Surfactant, levelling agent, adhesion promoter are sequentially added under 100~1000r/min stirrings in beaker, disperse 25
~35min, then adds pH value regulator, and electrically conducting transparent ink is made in regulation pH value between 8~9, that is,.
Further, the base material is polyethylene terephthalate, makrolon, polyimides, glass, polypropylene
Or polyethylene.
A kind of method for preparing above-mentioned transparent conductive film, be specifically：Electrically conducting transparent ink is printed in silk-screen mode
On base material, then base material is put in 90~180 DEG C of 1~10min of vacuum drying chamber, treats that solvent volatilization is complete, ink film solidification, i.e.,
Transparent conductive film is made.
The process of silk-screen is：20mL electrically conducting transparents ink is taken in silk-screen half tone, starts screen printer, by scraper ink
It is printed on base material.All types of patterns (lines, square, circular, point-like etc.), silk-screen half tone mesh number can be made in advance for silk-screen half tone
It can be 200 mesh, 250 mesh, 300 mesh, 350 mesh, 400 mesh, be formed using nylon, terylene, braided steel wire exposure imaging, thickness 40
~100 μm.
The invention has the advantages that：
1st, transparent conductive film of the invention has the characteristics of optical transmittance is high, mist degree is low, sheet resistivity is low.It is transparent to lead
In the formula of electric ink, dimethyl sulfoxide (DMSO) can significantly improve the electrical conductivity of product as high bp polar solvent.PEDOT/
PSS and nano-silver thread are as main conductive materials, and the situation of film forming can cause electric conductivity to have very big difference.PEDOT/PSS into
Film unfolds that degree is higher, and electric conductivity is better, and vice versa；And the electric conductivity of nano-silver thread depends on what is overlapped between line and line
Probability, this probability can be improved by increasing the concentration of nano-silver thread.Dimethyl sulfoxide (DMSO) can effectively improve a ball of string
PEDOT/PSS macromolecular chains unfold degree, while improving the overlap joint probability of line and line after nano-silver thread film forming, reduce rough surface
Degree, so as to effectively improve the electrical conductivity of PEDOT/PSS and nano-silver thread compound system.
2nd, transparent conductive film of the invention possesses good adhesive force, electric conductivity, environmental stability, properties
Substitute traditional ITO conductive films.
3rd, the solid content of traditional silk-screened conductive ink is more than 60%, and electrically conducting transparent ink solid content of the invention is no more than
2%；Available for any transparent conductive pattern of design and printing, one layer of 100~800nm transparent conductive film is formed after silk-screen, it is low
Solid content can reduce the production cost of transparent conductive film.
4th, need that the subtractive process etched by justifying is different from tradition ITO transparent conductive film, the present invention passes through silk-screen
Typography can a step addition process directly prepare patterned transparent conductive film, technique is simple, production efficiency is improved, cost significantly
Degree reduction.
5th, when the present invention is using flexible parent metals such as PET, polyimides, flexible touch screen requirement is met, can arbitrarily bend, turn round
It is bent.
In summary, transparent conductive film production cost of the invention is low, excellent performance, and electrically conducting transparent ink passes through silk-screen
Mode prepares conductive film, makes it possible a patterned flex electronic device, generally possesses screen printing device in electronics industry
In the case of, without adding other equipment, so that it may carry out technological transformation, product up-gradation.For promoting China in new touch-control skill
The development in art field, the situation for breaking away from Japan's monopolization continental market on high-end ITO, grasp independent intellectual property right, with long-range
Economic benefit and social benefit.
Brief description of the drawings
Fig. 1 is 10,000 times of enlarged drawings of ESEM of nano-silver thread used in embodiment 1；
Fig. 2 is 100,000 times of enlarged drawings of ESEM of nano-silver thread used in embodiment 1；
Fig. 3 is the transparent conductive film after the silk-screen printing of embodiment 1；
Fig. 4 is 100 times of enlarged drawings of microscope of the transparent conductive film of embodiment 1；
Fig. 5 is 800 times of enlarged drawings of microscope of the transparent conductive film of embodiment 1；
Fig. 6 is 2000 times of enlarged drawings of microscope of the transparent conductive film of embodiment 1.
Embodiment
With reference to specific embodiment, the present invention is described further：
Embodiment 1
Electrically conducting transparent ink is prepared in accordance with the following methods：
Take 250gPEDOT/PSS (Germany congratulates Li Shi PH1000) in 2000mL beakers, add under 500r/min stirring
Entering the aqueous isopropanols of 250g nano-silver threads, (wherein nano-silver thread concentration is 10mg/mL, and average line footpath is 40nm, average line length
For 40 μm, draw ratio 1000, Fig. 1 is 10,000 times of enlarged drawings of ESEM of nano-silver thread, and Fig. 2 is the ESEM of nano-silver thread
100000 times of enlarged drawings), disperse after 10min, sequentially add dimethyl sulfoxide (DMSO) 50g, alkali solubility thickener 20g (ROHM AND HAAS ASE-
60), surfactant (Tego dispers740w) 5g, levelling agent (Tego Glid410) 5g, aqueous polyurethane 5g, continue to divide
10min is dissipated, isopropanol is then added: deionized water=1: 1 mixed solvent 415g, continues scattered 10min, then adds 5g ammonia
Silk-screen electrically conducting transparent ink is made after being well mixed between 8~9 in water, regulation pH value.
Transparent conductive film is prepared in accordance with the following methods：
Using PET as flexible parent metal (light transmittance 92%, mist degree 0.3%, 100 μm of thickness), by it is above-mentioned prepare transparent lead
Electric ink is printed on PET with semi-automatic silk-screen machine in silk-screen mode, is then put the base material for being printed on silk-screen electrically conducting transparent ink
In 130 DEG C of vacuum drying chamber 3min, treat that solvent volatilization is complete, ink film solidification is made patterned transparent conductive film, such as schemes
Shown in 3~6, Fig. 4 is 100 times of enlarged drawings of microscope, and Fig. 5 is 800 times of enlarged drawings of microscope, and Fig. 6 is 2000 times of amplifications of microscope
Figure.
Embodiment 2
Electrically conducting transparent ink is prepared in accordance with the following methods：
Take 350gPEDOT/PSS (Germany congratulates Li Shi PH1000) in 2000mL beakers, add under 500r/min stirring
Entering the aqueous isopropanols of 150g nano-silver threads, (wherein nano-silver thread concentration is 10mg/mL, and average line footpath is 30nm, average line length
For 30 μm, draw ratio 1000), disperse after 10min, sequentially add dimethyl sulfoxide (DMSO) 50g, hydroxypropyl methyl cellulose 20g, surface
Activating agent (TRITONx100) 5g, levelling agent (Tego Glid410) 5g, water-based acrylic resin 5g, continue scattered 10min, so
Isopropanol is added afterwards: deionized water=1: 1 mixed solvent 415g, continues scattered 10min, then adds 4g diethanol amine, adjust
PH value is saved between 8~9, silk-screen electrically conducting transparent ink is made after being well mixed in ultrasonic vibration 5min.
Transparent conductive film is prepared in accordance with the following methods：
Using PET as flexible parent metal (light transmittance 92%, mist degree 0.3%, 100 μm of thickness), by it is above-mentioned prepare transparent lead
Electric ink is printed on PET with semi-automatic silk-screen machine in silk-screen mode, is then put the base material for being printed on silk-screen electrically conducting transparent ink
In 120 DEG C of vacuum drying chamber 5min, treat that solvent volatilization is complete, ink film solidification is made patterned transparent conductive film.
Embodiment 3
Electrically conducting transparent ink is prepared in accordance with the following methods：
350gPEDOT/PSS (being purchased from Shanghai Chun Yuan Phytochemistry Co., Ltd) is taken in 2000mL beakers, in 500r/
(wherein nano-silver thread concentration is 10mg/mL, average line to the propylene glycol monomethyl ether solution of addition 150g nano-silver threads under min stirring
Footpath is 30nm, a length of 30 μm of average line, draw ratio 1000), disperse after 10min, sequentially add dimethyl sulfoxide (DMSO) 50g, hydrophobic change
Non- polyurethane thickener (the Lockwood Rockwood L100) 20g of property, surfactant (BYK-151) 5g, levelling agent (Tego
Glid410) 5g, water-based acrylic resin 5g, continue scattered 10min, then add ethylene glycol: deionized water=1: 1 mixing
Solvent 415g, continues scattered 10min, then adds 5g triethanolamines, regulation pH value is between 8~9, ultrasonic vibration 5min is mixed
Close uniform rear obtained silk-screen electrically conducting transparent ink.
Transparent conductive film is prepared in accordance with the following methods：
Using PET as flexible parent metal (light transmittance 91%, mist degree 0.3%, 100 μm of thickness), by it is above-mentioned prepare transparent lead
Electric ink is printed on PET with semi-automatic silk-screen machine in silk-screen mode, is then put the base material for being printed on silk-screen electrically conducting transparent ink
In 150 DEG C of vacuum drying chamber 10min, treat that solvent volatilization is complete, ink film solidification is made patterned transparent conductive film.
Embodiment 4
Electrically conductive ink is prepared in accordance with the following methods：
Take 350gPEDOT/PSS (Germany congratulates Li Shi PH1000) in 2000mL beakers, add under 500r/min stirring
Entering the propylene glycol monomethyl ether solution of 150g nano-silver threads, (wherein nano-silver thread concentration is 10mg/mL, and average line footpath is 70nm, average
Line length is 40 μm, and about 600) draw ratio, disperses after 10min, sequentially add dimethyl sulfoxide (DMSO) 50g, organobentonite 20g, surface
Activating agent (BYK-190) 5g, levelling agent (BYK-333) 5g, water-based acrylic resin 5g, continue scattered 10min, then add second
Glycol: deionized water=1: 1 mixed solvent 415g, continues scattered 10min, then adds 1g sodium hydroxides, regulation pH value is 8
Between~9, silk-screen electrically conducting transparent ink is made after being well mixed in ultrasonic vibration 5min.
Transparent conductive film is prepared in accordance with the following methods：
Using polycarbonate as flexible parent metal (125 μm of light transmittance 92%, thickness), the above-mentioned electrically conductive ink prepared is used
Semi-automatic silk-screen machine is printed on PET in silk-screen mode, and the base material for being printed on silk-screen electrically conducting transparent ink then is put in into 150 DEG C
Vacuum drying chamber 10min, treats that solvent volatilization is complete, and ink film solidification is made patterned transparent conductive film.
Embodiment 5
Electrically conducting transparent ink is prepared in accordance with the following methods：
Take 150gPEDOT/PSS (Germany congratulates Li Shi PH1000) in 2000mL beakers, add under 500r/min stirring
Entering the propylene glycol monomethyl ether solution of 350g nano-silver threads, (wherein nano-silver thread concentration is 10mg/mL, and average line footpath is 70nm, average
Line length is 40 μm, and about 600) draw ratio, disperses after 10min, sequentially add the non-polyurethane of dimethyl sulfoxide (DMSO) 50g, hydrophobically modified
Thick dose of (L100 of Lockwood) 20g, surfactant (TRITONx140) 5g, levelling agent (BYK-345) 5g, water soluble acrylic acid
5g, continues scattered 10min, then adds ethylene glycol: deionized water=1: 1 mixed solvent 415g, continues scattered 10min, so
2g 2-amino-2-methyl-1-propanols are added afterwards, regulation pH value is between 8~9, ultrasonic vibration 5min, be made after being well mixed
Silk-screen electrically conducting transparent ink.
Transparent conductive film is prepared in accordance with the following methods：
Using glass as rigid substrate (light transmittance 90%, thickness 3mm), the above-mentioned electrically conducting transparent ink prepared is used half certainly
Dynamic screen printer is printed on glass in silk-screen mode, and the base material for being printed on silk-screen electrically conducting transparent ink then is put in into 150 DEG C true
Empty drying box 10min, treats that solvent volatilization is complete, and ink film solidification is made patterned transparent conductive film.
Embodiment 6
Electrically conducting transparent ink is prepared in accordance with the following methods：
Take 250gPEDOT/PSS (solid content is 1.3%, and electrical conductivity is 1000S/cm, and solvent is deionized water) in
In 2000mL beakers, glycerin solution (the wherein nano-silver thread concentration of 100g nano-silver threads is added under 400r/min stirring
For 5mg/mL, average line footpath is 70nm, a length of 40 μm of average line, draw ratio 570), disperse after 10min, sequentially add dimethyl
Sulfoxide 30g, xanthans 1g, surfactant (BYK-194) 1g, levelling agent (Tego Glid450) 1g, melmac 1g,
Continue scattered 10min, then add 200g propandiol butyl ethers, 200g deionized waters, continue scattered 5min, then add 1g ammonia
Silk-screen electrically conducting transparent ink is made after being well mixed between 8~9 in water, regulation pH value.
Transparent conductive film is prepared in accordance with the following methods：
Using polyimides as flexible parent metal, by the above-mentioned electrically conducting transparent ink semi-automatic silk-screen machine prepared with silk-screen side
Formula is printed on polyimides, and then the base material for being printed on silk-screen electrically conducting transparent ink is put in 180 DEG C of vacuum drying chamber 1min,
Treat that solvent volatilization is complete, ink film solidification is made patterned transparent conductive film.
Embodiment 7
Electrically conducting transparent ink is prepared in accordance with the following methods：
Take 200gPEDOT/PSS (solid content is 1.3%, and electrical conductivity is 1000S/cm, and solvent is deionized water) in
In 2000mL beakers, ethylene glycol solution (the wherein nano-silver thread concentration of 450g nano-silver threads is added under 600r/min stirring
For 20mg/mL, average line footpath is 80nm, a length of 40 μm of average line, draw ratio 500), disperse after 10min, sequentially add dimethyl
Sulfoxide 40g, aerosil 5g, surfactant (Tego dispers750w) 2g, levelling agent (the modest W-461 of this moral of hamming)
2g, aqueous alkide resin 4g, continue scattered 15min, then add 400g terpinols, 400g deionized waters, continue scattered
10min, then adds 3g ethylenediamines, and silk-screen electrically conducting transparent ink is made after being well mixed between 8~9 in regulation pH value.
Transparent conductive film is prepared in accordance with the following methods：
Using polyethylene as base material, the above-mentioned electrically conducting transparent ink prepared is printed with semi-automatic silk-screen machine in silk-screen mode
In on polyethylene, then the base material for being printed on silk-screen electrically conducting transparent ink is put in 90 DEG C of vacuum drying chamber 8min, treats that solvent is waved
Complete, ink film solidification is distributed, that is, patterned transparent conductive film is made.
Embodiment 8
Electrically conducting transparent ink is prepared in accordance with the following methods：
200gPEDOT/PSS is taken in 2000mL beakers, the third of 200g nano-silver threads is added under 500r/min stirring
(wherein nano-silver thread concentration is 12mg/mL to glycol butyl ether solution, and average line footpath is 50nm, a length of 40 μm of average line, draw ratio
800), disperse after 10min, sequentially add dimethyl sulfoxide (DMSO) 30g, ethyl cellulose 10g, surfactant (Tego
Dispers760w) 4g, levelling agent (Tego Glid110) 3g, polyethylene glycol oxide 2g, continue scattered 10min, then add 300g
Dipropylene glycol methyl ether, 350g deionized waters, continue scattered 10min, then add 3g ammoniacal liquor, and regulation pH value is mixed between 8~9
Close uniform rear obtained silk-screen electrically conducting transparent ink.
Transparent conductive film is prepared in accordance with the following methods：
Using polypropylene as base material, the above-mentioned electrically conducting transparent ink prepared is printed with semi-automatic silk-screen machine in silk-screen mode
In on polypropylene, then the base material for being printed on silk-screen electrically conducting transparent ink is put in 100 DEG C of vacuum drying chamber 3min, treats that solvent is waved
Complete, ink film solidification is distributed, that is, patterned transparent conductive film is made.
Performance test
Comparative example 1：Dimethyl sulfoxide (DMSO) in the electrically conducting transparent ink formulations of embodiment 1 is removed, other components and deal are protected
Hold constant, according to the preparation method of embodiment 1, transparent conductive film is made.
For the product of embodiment 1~8 and comparative example 1, using four-point probe resolution chart transparent conductive film
Sheet resistance, photoelectricity haze meter resolution chart transparent conductive film light transmittance, mist degree, uses 3M610 adhesive tape test adhesive force, pencil
Hardometer tests hardness, the results are shown in Table 1.
The performance test results of table 1
| Base material | Sheet resistance (Ω/) | Light transmittance (%) | Mist degree (%) | Adhesive force | Hardness | |
| Embodiment 1 | PET | 50 | 90 | 1.5 | 5B | H |
| Embodiment 2 | PET | 60 | 91 | 0.7 | 5B | H |
| Embodiment 3 | PET | 45 | 92 | 1.5 | 5B | H |
| Embodiment 4 | PC | 100 | 94 | 2.0 | 5B | H |
| Embodiment 5 | Glass | 10 | 83 | 4 | 5B | H |
| Embodiment 6 | PI | 80 | 80 | 3.5 | 5B | H |
| Embodiment 7 | PE | 100 | 90 | 12 | 5B | H |
| Embodiment 8 | PP | 60 | 90 | 1.8 | 5B | H |
| Comparative example 1 | PET | 80 | 82 | 3.0 | 5B | H |
When as seen from the above table, using same substrate, transparent obtained by the electrically conducting transparent ink containing dimethyl sulfoxide (DMSO) is led
Conductive film, with higher optical transmittance, and lower mist degree and sheet resistivity.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in, all should
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (8)
1. a kind of transparent conductive film, including electrically conducting transparent ink and base material, it is characterised in that described according to parts by weight
Bright electrically conductive ink includes 0.5~50 part of nano-silver thread dispersion liquid, 15~35 parts of poly- (3,4- Ethylenedioxy Thiophene)-poly- (benzene second
Alkene sulfonic acid), 5~40 parts of organic solvents, 5~40 parts of deionized waters, 1~8 part of dimethyl sulfoxide (DMSO), 0.1~5 portion of viscosity modifier,
0.01~1 part of pH adjusting agent, 0.01~2 part of surfactant, 0.01~1 part of levelling agent, 0.1~0.5 part of adhesion promoter；
The viscosity modifier is hydroxypropyl methyl cellulose, hydroxypropyl cellulose, methylcellulose, ethyl cellulose, ethoxy fibre
Tie up element, xanthans, guar gum, alkali solubility thickener, the non-polyurethane thickener of hydrophobically modified, poly-methyl pyrrole alkanone, gas phase two
At least one of silica and organobentonite；The adhesion promoter is water-based acrylic resin, polyvinyl alcohol, aqueous
Polyester, aqueous alkide resin, polyacrylamide, polyethylene glycol oxide, styrenemaleic acid resin, aqueous epoxy resins and melamine
At least one of polyimide resin.
2. transparent conductive film according to claim 1, it is characterised in that the nano-silver thread dispersion liquid is nano-silver thread
It is scattered in methanol, ethanol, isopropanol, normal propyl alcohol, ethylene glycol, propane diols, glycerine, water, propylene glycol monomethyl ether, dipropylene glycol methyl ether
Or propandiol butyl ether and obtain.
3. transparent conductive film according to claim 2, it is characterised in that the draw ratio of the nano-silver thread is 50~
5000。
4. transparent conductive film according to claim 1, it is characterised in that the organic solvent is methanol, ethanol, isopropyl
The positive fourth of alcohol, normal propyl alcohol, ethylene glycol, propane diols, glycerine, n-butanol, ethyl acetate, n-propyl acetate, isopropyl acetate, acetic acid
Ester, sec-butyl acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether, propandiol butyl ether, propylene glycol methyl ether acetate, isophorone and
At least one of terpinol.
5. transparent conductive film according to claim 1, it is characterised in that the pH adjusting agent be ammoniacal liquor, sodium hydroxide,
Diethanol amine, triethanolamine, 2-amino-2-methyl-1-propanol or ethylenediamine.
6. transparent conductive film according to claim 1, it is characterised in that the electrically conducting transparent ink is in accordance with the following methods
Prepare：At room temperature by nano-silver thread dispersion liquid, poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid), organic solvent,
Deionized water, dimethyl sulfoxide (DMSO), viscosity modifier, surfactant, levelling agent, adhesion promoter are in 400~600r/min
Sequentially added under stirring in beaker, disperse 25~35min, then add pH value regulator, adjust pH value between 8~9,
Electrically conducting transparent ink is made.
7. transparent conductive film according to claim 1, it is characterised in that the base material is polyethylene terephthalate
Ester, makrolon, polyimides, glass, polypropylene or polyethylene.
8. a kind of method of the transparent conductive film prepared described in claim 1, it is characterised in that by electrically conducting transparent ink with silk
India side formula is printed on base material, and then base material is put in 90~180 DEG C of 1~10min of vacuum drying chamber, treats that solvent is evaporated completely
Entirely, ink film solidifies, that is, transparent conductive film is made.
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| CN106910568A (en) * | 2017-03-31 | 2017-06-30 | 苏州思创源博电子科技有限公司 | A kind of utilization electrically conductive ink prepares the preparation method of conductive film |
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| EP3017107B1 (en) * | 2013-07-02 | 2023-11-29 | The University of Connecticut | Electrically conductive synthetic fiber and fibrous substrate, method of making, and use thereof |
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| CN105304164B (en) * | 2015-10-09 | 2017-10-27 | 重庆文理学院 | A kind of water base nano silver wire ink and its method for manufacturing thin film easily post-processed |
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