CN110272663A - Transparent conductive film and preparation method thereof - Google Patents
Transparent conductive film and preparation method thereof Download PDFInfo
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- CN110272663A CN110272663A CN201910547828.1A CN201910547828A CN110272663A CN 110272663 A CN110272663 A CN 110272663A CN 201910547828 A CN201910547828 A CN 201910547828A CN 110272663 A CN110272663 A CN 110272663A
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- conductive film
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- 239000008367 deionised water Substances 0.000 claims abstract description 6
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- 238000002834 transmittance Methods 0.000 claims abstract description 5
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- 239000002159 nanocrystal Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- ZOMSMJKLGFBRBS-UHFFFAOYSA-N bentazone Chemical compound C1=CC=C2NS(=O)(=O)N(C(C)C)C(=O)C2=C1 ZOMSMJKLGFBRBS-UHFFFAOYSA-N 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/02—Engraving; Heads therefor
- B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/02—Engraving; Heads therefor
- B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
- B41C1/045—Mechanical engraving heads
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/02—Engraving; Heads therefor
- B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
- B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41F—PRINTING MACHINES OR PRESSES
- B41F13/00—Common details of rotary presses or machines
- B41F13/08—Cylinders
- B41F13/10—Forme cylinders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
- C09D11/105—Alkyd resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/108—Hydrocarbon resins
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Conductive Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a kind of preparation methods of transparent conductive film, it include: to pass through printing equipment, transparent conductive ink is printed to flexible and transparent substrate surface in a manner of roll-to-roll, obtain the transparent conductive film, white space and image-text area is distributed in plate surface in the printing equipment, and the image-text area is opposite depressed portions；The transparent conductive ink includes following component in parts by weight: 30~70 parts of one-dimensional metal nanowire dispersion, 0.1~2 part of resin, 0.1~2 part of thickener, 0.001~0.1 part of levelling agent and 30~70 parts of deionized water.Transparent conductive ink is printed on substrate by roll-to-roll mode of printing and forms transparent conductive film by the present invention, one-pass molding and patterned transparent conductive film can directly be prepared, it does not need subsequent etch or laser cutting parameter is graphical, preparation speed is obviously improved compared with prior art, and obtained transparent conductive film has the characteristics that uniformly, without silk thread, high transmittance, high conductivity, low haze.
Description
Technical field
The present invention relates to production transparent conductive film technical field more particularly to it is a kind of using printing plate printing preparation it is saturating
Bright conductive film and preparation method thereof.
Background technique
Transparent conductive film has hair application extensively in fields such as touch screen, intelligent glass, solar battery, electromagnetic shieldings.
Traditional ITO material have the defects that it is fatal, it is frangible, it is difficult to flexibility；Essential element indium is rare metal, with the increasing of dosage
Add the rapid increase that can bring price, brings huge cost pressure.
As the flexibility of touch screen, demand in large size increase, traditional ito thin film is difficult to meet application demand.
Many panel vendors, research institute, colleges and universities begin one's study the alternative materials of ITO thus.Based on metal nanometer line in numerous materials
Transparent conductive film best performance becomes the most popular material of substitution ITO.
It currently based on the metal nanometer line transparent conductive film overwhelming majority is prepared using the method for coating, is coated with preparation
Transparent conductive film need to could be used for touch screen by etch patterning, and coating head relies primarily on external import charges valuableness,
Eventually lead to the higher cost of silver wire transparent conductive film.
And in existing directly graphical printing technology, such as silk-screen printing, inkjet printing, adagio printing, intaglio printing
Easy Deng, rotogravure printing operation, print speed printing speed is high, and intaglio plate press resistance rate is high, and the layer of ink uniformity of printing is good, is well suited for efficiently preparing
Metal nanometer line transparent conductive film.But printing of the ink cell structure of forme roller relative to coating technique to metal nanometer line ink
Adaptive has higher requirement.Metal nanometer line electrically conductive ink and the maximum shape distinguished in solid particle in the inner of traditional ink
Shape, the particle in traditional ink is all the other tiny spherical particle of submicron order mostly, and the solid in one-dimensional functional form ink
It is that draw ratio reaches several hundred or even thousands of lines.The length of these lines can achieve 40~50 microns even more in one-dimensional ink
It is long, and the size of conventional gravure halftone ink cell generally only has more than ten microns.According to intaglio printing principle analysis, can theoretically push away
There are the following problems in gravure printing process for disconnected one-dimensional ink.One, the solid in one-dimensional ink because its length across
Multiple ink cells, rather than enter inside ink cell, when scraper scraped intaglio plate, forming wire drawing causes ink to be unevenly distributed on halftone
It is even；Two, at drop state when ink is transferred to surface of the stock from ink cell, then merged between drop and drop constitute it is thin
Film is unevenly distributed problem during droplet coalescence after transfer.These are to lead to current intaglio printing metal nanowire thin-films
Electric conductivity and the insufficient major reason of permeability comprehensive performance.Can the linear solid in ink be distributed during these
Uniformly, can be linked to each other formation network has conclusive influence to the performance of last film.In extreme situation, such as net
Wall width is excessive to cause ink drop spacing excessive, and ink even be able to not can merge to form film, affects transparent conductive film
Electric conductivity.And compared to conventional gravure, preparing flexible transparent conductive film also has higher want to printing technology
It asks.Therefore need to find the combination of a kind of ink for being particularly suited for preparing flexible transparent conductive film and technique.
Summary of the invention
The main purpose of the present invention is to provide a kind of transparent conductive films and preparation method thereof, to overcome in the prior art
Deficiency.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of preparation methods of transparent conductive film, comprising:
By printing equipment, transparent conductive ink is printed to flexible and transparent substrate surface in a manner of roll-to-roll, obtains institute
White space and image-text area, the image areas is distributed in the transparent conductive film stated, the plate surface in the printing equipment
Domain is opposite depressed portions；
The transparent conductive ink includes following component in parts by weight: one-dimensional metal nanowire dispersion 30~
70 parts, 0.1~2 part of resin, 0.1~2 part of thickener, 0.001~0.1 part of levelling agent and 30~70 parts of deionized water.
The embodiment of the present invention is also provided by the transparent conductive film of the preparation method preparation of the transparent conductive film.
Compared with prior art, the beneficial effect comprise that
(1) transparent conductive ink is printed on the flexible parent metals such as PET by the present invention by roll-to-roll printing plate mode of printing
Transparent conductive film is formed, one-time formed and patterned transparent conductive film can be directly prepared, not need subsequent erosion
It carves or laser cutting parameter is graphical, transparent conductive film has uniformly, without silk thread, high transmittance, high conductivity, low haze etc.
Feature, finished product transmitance (removal substrate) can reach 80~97%, and square resistance is 5~200 Ω/.
(2) present invention uses printing plate printing technology, in flexible and transparent substrate surface by customizing forme roller for dedicated transparent
Electrically conductive ink carries out one or many printings, obtains uniform conductive layer, has in the uniformity for prepare transparent conductive film
Potential advantage, and print speed printing speed is high, equipment cost is low, is very suitable to the large-scale production of transparent conductive film.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
The preparation method of a kind of transparent conductive film provided in an embodiment of the present invention, comprising: by printing equipment, with volume pair
Volume mode, which prints transparent conductive ink, obtains the transparent conductive film to flexible and transparent substrate surface, and the printing is set
Plate surface in standby is distributed with white space and image-text area, and the image-text area is that opposite depressed portions (or can consider
It is formed in the picture and text recess of plate surface)；
The transparent conductive ink includes following component in parts by weight: one-dimensional metal nanowire dispersion 30~
70 parts, 0.1~2 part of resin, 0.1~2 part of thickener, 0.001~0.1 part of levelling agent and 30~70 parts of deionized water.
In some embodiments, the thickener includes hydroxypropyl methyl cellulose, polyurethane thickener and acrylic acid
Any one in thickener or two or more combinations.
Cooperated using other components in the thickener and the transparent conductive ink, it can be by transparent conductive ink
Viscosity is improved to suitable range, to both be conducive to improve the mobility of one-dimensional metal nano wire, is additionally aided and is eliminated printing plate print
Silk thread impression existing for brush transparent conductive film, improves the uniformity of film, and improves the dispersibility and stability of nano-silver thread.
In some embodiments, the resin include aqueous polyurethane, water-based acrylic resin, aqueous alkide resin,
Any one in aqueous epoxy resins and chlorinated polypropylene or two or more combinations.
Cooperated using other components in the resin and the transparent conductive ink, electrically conducting transparent oil can be effectively improved
The adhesive force and scratch resistance of ink.
Levelling agent includes any one or two kinds in polyether-modified dimethyl siloxane and polyacrylate levelling agent
Combination, effect be reduce ink surface tension, improve the printability of ink.
Cooperated using other components in the levelling agent and the transparent conductive ink, electrically conducting transparent can be effectively reduced
The surface tension of ink improves the printability of transparent conductive ink.
In some embodiments, comprising the following steps:
Step is unreeled, the flexible and transparent substrate including will be provided on the unwinding device of printing equipment unreels；
Printing plate print steps print transparent conductive ink to flexible and transparent substrate including the forme roller by printing equipment
Surface obtains transparent conductive film to be processed；
Drying steps, including the transparent conductive film to be processed is dried, make transparent conductive ink flexible saturating
Bright substrate surface is formed by curing patterned transparency conducting layer, obtains transparent conductive film；
Step is wound, including the wrap-up by printing equipment, collects transparent conductive film.
In some more preferred embodiments, before the printing plate print steps further include: by destaticing stick
And pneumatic device is dusted processing to the flexible and transparent substrate.
In some specific embodiments, transparent conductive film use roll-to-roll printing technology, preparation method include with
Lower step:
Unreel step, comprising: by the unwinding device of printing equipment, release transparent substrate flexible；
Dust removal step, comprising: by destaticing stick and pneumatic device, remove the electrostatic in the transparent substrate flexible of releasing
And the dust sticked；
Printing plate print steps, comprising: by customization forme roller by dedicated transparent conductive ink in the flexible of releasing
One or many printings are carried out on bright substrate surface；
Drying steps, comprising: the transparent conductive film flexible being completed for printing is dried in drying tunnel, electrically conducting transparent
Ink is formed by curing patterned transparency conducting layer after drying on substrate.Metal nanometer line is evenly distributed on electrically conducting transparent
In layer, each nano wire is mutually lapped to form network structure, to obtain good electric conductivity.
Wind step, comprising: by the wrap-up of printing equipment, collect and complete dry transparent conductive film.
Further, the preparation method also may include finished product test step comprising: pass through spectrophotometer and four
Probe test equipment tests the transmitance and square resistance of transparent conductive film finished product respectively.
In some more preferred embodiments, the temperature of the drying is 80~150 DEG C, the dry time is 2~
30min。
In some embodiments, the material of the flexible and transparent substrate includes passing through single side cure process or two-sided hardening
Any one in PC, PET and PI polymer of processing or two or more combinations, but not limited to this, other classes also can be selected
Like flexible parent metal.
In some embodiments, the flexible and transparent substrate with a thickness of 25~250 μm.
In some embodiments, the viscosity of the transparent conductive ink is greater than or equal to 20mPa.s and is less than
2000mPa.s。
In some embodiments, the surface tension of the transparent conductive ink is 20~50mN/m.
In some embodiments, in the one-dimensional metal nanowire dispersion one-dimensional metal nano wire length be 1~
100 μm, preferably 15~100 μm, especially preferably 15~35 μm, diameter be 5~200nm, preferably 5~50nm, it is especially excellent
It is selected as 10~50nm, draw ratio is 5~20000, preferably 300~20000, especially preferably 300~3500.By using institute
The one-dimensional metal nano wire stated can make better phase interconnection knot between nano wire, to form electric conductivity when preparing film
Excellent network structure.In the present invention, the length of one-dimensional metal nano wire is longer, and the electric conductivity after film forming is better, but
It is that cost of manufacture can be greatly improved, in addition the stability of its ink can decline, and it is heavy that longer nano wire is easier to reunite
Drop, causes the unstable of ink.And the diameter of one-dimensional metal nano wire is smaller, the transmitance after film forming is higher, mist degree is lower,
But cost can be also increased sharply.When the length of one-dimensional metal nano wire is in 15~100 μ m, form a film electric conductivity
Better than the situation outside the preferred scope, the cost performance that its ink stability and cost etc. integrate in 15~35 μ ms is more
It is good；When one-dimensional metal nanowire diameter is within the scope of 5~50nm, transmitance is higher for film forming, mist degree is lower, 10~
Within the scope of 50nm, cost performance is more preferable.
In some more specifically case study on implementation, the one-dimensional metal nano wire can be with specification are as follows: average line is a length of
30 μm, average diameter 30nm, draw ratio 1000.
In some embodiments, one-dimensional metal nano wire includes nano silver in the one-dimensional metal nanowire dispersion
Any one in line, gold nanowire, NANO CRYSTAL COPPER WIRE, nanometer platinum line and nanometer nickel wire or two or more combinations.
In some embodiments, the concentration of the one-dimensional metal nanowire dispersion is 1~30mg/mL.
In some embodiments, the forme roller of the printing equipment is at least by electronic engraving method, laser
Any one method in engraving method for platemaking, chemical attack method for platemaking and mechanical engraving method for platemaking is prepared.
In some embodiments, the screen frequency of the forme roller of the printing equipment be 10~300 lines/centimetre, preferably
For 30~160 lines/centimetre, the depth (i.e. ink cell depth) of forme roller is 5~100 μm, preferably 20~90 μm, leader width with
The ratio of ink cell width be more than or equal to 1:7 and be less than 1:4 (such as 100 μm of ink cell width, leader width is 14~25 μm,
In contrast, 100 μm of existing ink cell width, leader width are 25 μm, i.e., leader width and ink cell width ratio are 1:4), preferably
For 1:5~1:6 (i.e. 100 μm of ink cell width, leader width are 17~20 μm), the screen angle of forme roller is 30 °~60 °, excellent
It is selected as 35~55 °.With the raising of screen frequency, the transfer amount of ink increases, and the electric conductivity to form a film after single printing improves,
But excessive ink cell be easy to cause the reunion of nano wire, causes film forming uneven；The increase of same ink cell depth, can also increase
The transfer amount of inking up so that the electric conductivity of single printing film forming improves, but be easy to cause stifled version；Conventional leader width with
Ink cell width ratio is printed as the uniformity of film by will affect, and what it is due to printing is one-dimensional nano line, biggish leader width meeting
Lead to apparent silk thread, both formed a film unevenly, and lesser leader width will lead to scraper and have random jump, also result in
Film forming is uneven, and lesser leader width difficulty of processing improves, and cost is increased sharply；The difference of screen angle will lead to print
The uniformity of brush is varied.Screen frequency, roller depth, leader width and ratio, the screen angle of ink cell width etc. are in
When preferred scope, the electric conductivity of film forming rises, improves at film uniformity.
In some embodiments, the dot shape of the forme roller of the printing equipment includes diamond shape, quadrangle, hexagon
Or site TB etc., and it is without being limited thereto.
In some embodiments, the print speed printing speed of the printing equipment is 5~400m/min, preferably 10~200m/
Min, scraper pressure be 0.1~0.5MPa, preferably 0.2~0.4Mpa, coining roller pressure be 0.1~0.5Mpa, preferably 0.2
~0.4Mpa.
Wherein, in the printing plate printing process, ink formulations can be finely adjusted according to print speed printing speed, work as print speed printing speed
When less than 5m/min, required ink performance is printed beyond ink adjusting range, uses by force, can make ink in printing process
Transfer is uneven, can not good filming print required ink performance beyond ink tune when print speed printing speed is greater than 400m/min
Whole range, uses by force, ink can be made to splash in printing process, can not good filming.With the raising of print speed printing speed, oil
Black transfer amount gradually increases, and Thin film conductive performance improves, but as speed increases, uniformity of film is declined, and works as printing
When speed is in aforementioned preferred scope, the performance and uniformity of film can obtain a balance well.
The scraper is also known as doctor, in the printing plate printing process, when its pressure is less than 0.1MPa, then and printing plate
The non-graphic part of roller is easy to scrape not completely, and when doctor pressure is greater than 0.5MPa, then the abrasion of forme roller and doctor
It again can be very serious.When scraper pressure is within the scope of 0.2~0.4Mpa, the uniformity of film is significantly improved.
And for the roller platen, when its pressure is less than 0.1Mpa, it be easy to cause pattern transfer not exclusively, and work as
When imprinting roller pressure greater than 0.5MPa, then pattern is easily deformed.When imprinting roller pressure within the scope of 0.2~0.4Mpa, film
Electric conductivity increase, uniformity can also be significantly improved.
Preparing the technique of metal nanometer line transparent membrane compared with existing crack rubbing method, (highest preparation efficiency only has 20
M/min), the print speed printing speed of metal nanometer line transparent membrane preparation process provided by the invention can be easily reached 200 ms/min
Clock is even higher, and used equipment price is more cheap, meanwhile, existing crack rubbing method technique cannot be carried out directly
Patterning needs to carry out subsequent etch or laser cutting to complete to pattern, and preparation method provided by the invention may be implemented
One-pass molding, without the operation such as etching or laser cutting；Especially, had very using transparent conductive film prepared by crack rubbing method
Apparent edge effect, effective area ratio real area is small, causes the waste of resource, and method provided by the invention is due to net
The presence in cave, uniformity of film are obviously improved.
The embodiment of the invention also provides the transparent conductive films of any method preparation provided by the present invention.
In some embodiments, the transparent conductive film is flexible.
In some embodiments, the visible light transmittance of the transparent conductive film is 80~97%, square resistance 5
~200 Ω/.
Below with reference to several preferred embodiments, further details of the technical solution of the present invention, it is clear that described
Embodiment be only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to the present invention
The range of protection.The implementation condition used in following embodiment can do further adjustment according to actual needs, be not specified
Implementation condition is usually the condition in routine experiment.
Embodiment 1:
Commercially available flexible and transparent PET film is selected to roll up, 125 μm of film thickness therein, film transmission rate 90%.
Using the unreeling of identical parameters, the roll-to-roll printing technology of dedusting, printing, drying, winding, pass through identical printing plate
Difference transparent conductive nano silver wire ink shown in the following table 1 is printed on substrate surface by roller, to prepare flexible and transparent conductive
Film.
Specifically, roll-to-roll printing technology specifically includes:
Step is unreeled, by the unwinding device of printing equipment, releases transparent substrate flexible；
Wherein, transparent substrate, which can be selected, passes through single side cure process or PC, PET or PI polymer of two-sided cure process etc.
Flexible parent metal.Transparent substrate with a thickness of between 25~250 μm.
Dust removal step, by destaticing stick and pneumatic device, removing the electrostatic in the transparent substrate flexible of releasing and sticking
Attached dust；
Printing plate print steps, by customization forme roller by dedicated transparent conductive ink releasing transparent substrate flexible
Carry out one or many printings on surface, the dedicated transparent electrically conductive ink by the isopropanol dispersion liquid of nano-silver thread, thickener,
Resin, levelling agent and deionized water composition.Specifically, the dedicated transparent conductive ink includes following component a: Vygen
Category 30~70 parts by weight of nanowire dispersion, 0.1~2 parts by weight of resin, 0.1~2 parts by weight of thickener, levelling agent 0.001~
30~70 parts by weight of 0.1 parts by weight and deionized water.Wherein one-dimensional metal nanowire dispersion can select the different of nano-silver thread
Propanol dispersion liquor, and the solid content of final ink can change by the ratio for the isopropanol dispersion liquid for adjusting nano-silver thread,
And the ratio by changing thickener can change the viscosity parameter (such as 5~2000mPa.s) of final ink, and, pass through
The ratio for changing levelling agent can change the surface tension parameter (such as 20~50mN/m) of final ink.Wherein silver nanowires
Length be 1~100 μm, preferably 15~100 μm, especially preferably 15~35 μm, diameter be 5~200nm, preferably 5~
50nm, especially preferably 10~50nm, draw ratio be 5~20000, preferably 300~20000, especially preferably 300~
3500.Also, the solvent used in the nano-silver thread dispersion liquid can also select water, ethyl alcohol, normal propyl alcohol, n-butanol, isobutyl
One of alcohol, ethylene glycol, butyl glycol ether, propylene glycol monomethyl ether and ethyl acetate equal solvent or a variety of combinations.The resin,
Thickener, levelling agent can select suitable type known to industry, such as aqueous polyurethane, water-based acrylic resin, aqueous
One of alkyd resin, aqueous epoxy resins and chlorinated polypropylene or a variety of combinations, hydroxypropyl methyl cellulose, polyurethane
One of thickener and acrylic thickener or a variety of combinations, polyether-modified dimethyl siloxane and polyacrylate stream
Any one of flat agent.In some ink specials used in the present embodiment different nano wire parameter selections can refering to table 1,
Drying steps, the transparent conductive film flexible being completed for printing are dried in drying tunnel, transparent conductive ink warp
It crosses after drying and is formed by curing patterned transparency conducting layer on substrate.Metal nanometer line is uniformly distributed in the transparent conductive layer,
Each nano wire is mutually lapped to form network structure, to obtain good electric conductivity.
Step is wound, by the wrap-up of printing equipment, collects and completes dry transparent conductive film.
Table 1
It can be seen that the increase with nanowire diameter, film transmission according to the print result of the 1st~No. 6 ink in table 1
Rate is decreased obviously, and mist degree significantly improves.And outside particularly preferred range, sheet resistance also has a degree of rising,
Even property can also be declined.According to ink 7 as can be seen that the diameter of nano wire is outside claim range, transmitance is anxious
Play decline, mist degree steeply rise, and do not meet market purposes.
It can be seen that the increase with nanowire length, sheet resistance according to the print result of the 9th~No. 15 ink in table 1
Decline is had, in particularly preferred range, the change of sheet resistance is not apparent.But with the increase of nanowire length,
Nano wire is easy to reunite in ink, settle, and causes the unstable of ink.In addition the length of nano wire also will increase its buying at
This.According to ink 8 as can be seen that when nanowire length is less than claim range, film can not be conductive；It can according to ink 16
To find out, when nanowire length is greater than claim range, stable ink can not be formed, the holding time in minutes, no
Meet actual production demand.
Although nano wire diameter is smaller, length longer (both major diameter was bigger) in the case where, the sheet resistance of film forming is lower
And transmitance is higher, but ink can become rather unstable, and the holding time is the 1/10th even shorter of preferred scope,
And its synthesis cost is hundred times of preferred scope or more, therefore is comprehensively considered, the most preferred range of nano wire in the present embodiment
It is 15~35 μm of length, 10~50nm of diameter, draw ratio 300~3500, but the performance outside preferred scope is not represented with regard to certain
It can become poor.
Embodiment 2: the embodiment uses substrate in the same manner as in Example 1, technique and ink formulations, different more special than right
The printing plate print result of the nano wire coating ink of approach buying is disclosed with ink and in the market.
The ink provided in the embodiment 2 can be respectively defined as ink special 1,2,3,4,5,6.And the painting as control
Cloth ink 1,2 and ink for screen printing 1 are obtained from open approach purchase.See Table 2 for details for design parameter.
Table 2
The flexible transparent conductive film that variety classes transparent conductive ink will be used to prepare is visited by spectrophotometer and four
Needle test equipment tests its transmitance and square resistance respectively, and the results are shown in Table 3.
Table 3
The 17th~No. 22 ink is saturating using the nano-silver thread that No. 18 ink is prepared it can be seen from result in table 3
Bright conductive film, has excellent performance, and transmitance reaches 94%, 10 Ω of sheet resistance/；When the solid content of metal nanometer line electrically conductive ink is lower
(such as No. 17 ink), the electric conductivity of transparent conductive film is poor；When the solid content of metal nanometer line electrically conductive ink is higher by (such as
20, No. 21 ink), the transmitance of transparent conductive film sharply declines, and the electric conductivity of film obviously rises.Work as ink surface tension
Higher (such as No. 22 ink) or lower (such as No. 17 ink), the uniformity of film can be declined.
From the result of the 23rd~No. 24 ink can be seen that common nano-silver thread coating ink viscosity and solid content all compared with
It is low, it is not particularly suited for printing plate printing technology.It is conductive reluctantly using the transparent conductive film of the type ink printing plate printing preparation
Performance is bad, and uniformity of film is very poor, or even can not completely form a film.
It can be seen that common nano-silver thread ink for screen printing viscosity from the result of No. 25 ink and solid content be all higher,
It is not particularly suited for printing plate printing technology.It, can not be complete reluctantly using the transparent conductive film of the type ink printing plate printing preparation
Film forming.
It can be seen that in order to print the patterned flexible transparent conductive film of large scale preparation, dedicated print using printing plate
Version printing metal nanometer line ink is necessary, is not that can arbitrarily be replaced with other ink.
Embodiment 3:
Certain brand flexible and transparent PET film is selected to roll up, 125 μm of film thickness, film transmission rate 90%.
Using the unreeling of parameter same as Example 1, the roll-to-roll printing technology of dedusting, printing, drying, winding, pass through
Dedicated transparent electrical-conductive nanometer silver wire ink (with ink 18 in table 2) is printed on substrate surface by different forme rollers, to make
Standby flexible transparent conductive film.Roll-to-roll printing technology is the same as embodiment 2.
The present embodiment is from the difference of embodiment 2 according to as shown in table 4 below using different printing screen plates.
Table 4
The flexible transparent conductive film of different gravure halftone preparations will be used, is set by spectrophotometer and the test of four probes
Back-up does not test its transmitance and square resistance, and the results are shown in Table 5.
Table 5
It can be seen that leader width according to the result of the 26th~No. 29 sample and the ratio of ink cell width be excessive, will lead to
The electric conductivity of film is declined, and uniformity has certain decline, and main cause, which is that leader is wide, leads to subtracting for inking amount
It is small, and nano wire can be hung on leader, cause film forming uneven.And ratio it is too small when, leader subtracts the supporting role of scraper
Weak, the case where scraper is easy lifts, uniformity can also be deteriorated.When the ratio of leader width and ink cell width is in preferred model
When enclosing interior, electric conductivity and uniformity have a balance well.
It can be seen that becoming larger with screen frequency according to the result of the 30th~No. 37 sample, under the electric conductivity of film
Drop.When screen frequency is less than threshold value, ink cell is excessive, and nano wire is easily reunited in ink cell, causes film forming extremely uneven, can not
Meet application conditions；And screen frequency be greater than threshold value when, electric conductivity sharply declines, and is unsatisfactory for application requirement.Work as screen frequency
When in preferred scope, electric conductivity and uniformity have a balance well.
It can be seen that the increase with halftone depth according to the result of the 38th~No. 43 sample, the electric conductivity of film is aobvious
It writes and improves.When depth is less than threshold value, inking amount is too low, and film can not be conductive；But when depth is greater than threshold value, halftone blocks up version
It is extremely serious, it can not good filming.When halftone depth is when preferred scope is interior, the stability of electric conductivity and printing has obtained one
A preferable balance.
It is excessive or too small can all lead to the uniform of film to can be seen that screen angle according to the result of the 44th~No. 50 sample
Property decline, when being more than or less than threshold value, the deviation of sheet resistance is even more than 50%, and since it is uneven, causes to put down
Equal sheet resistance can also become larger, and have exceeded adaptable range.And when screen angle is in preferred scope, the uniformity of film has
Larger promotion.
For traditional gravure halftone, the halftone that the present invention uses, especially preferred scope, screen frequency compared with
Greatly, depth is deeper, and it is of particular importance that the halftone that the present invention uses, leader width and the ratio of ink cell width are smaller,
The result finally printed is significantly increased.It can be seen that the customization gravure halftone that the present invention uses is more compared to common gravure halftone
Add the printing for being suitable for metal nanometer line electrically conductive ink.
Embodiment 4: using substrate in the same manner as in Example 1, technique, and the ink centainly finely tuned has been used (to guarantee
The solid content of ink is consistent, and viscosity, surface tension are roughly the same), compare different print speed printing speeds, scraper pressure and roller platen
Print result under pressure.Wherein the parameter different from embodiment 1 is shown in Table 6.
Table 6
Different print speed printing speeds, scraper pressure will be used or imprint flexible transparent conductive film prepared by roller pressure, led to
It crosses spectrophotometer and four probe test equipments tests its transmitance and square resistance respectively, the results are shown in Table 7.
Table 7
It can be seen that the raising with print speed printing speed, the electric conductivity of film according to the test result of the 51st~No. 57 sample
It improves, but uniformity can be declined, the reason is that the rising of speed is so that inking amount improves.Speed
When degree is lower than threshold value, even if ink is finely tuned, halftone also can not uniformly roll ink, lead to not completely form a film.
And speed be higher than threshold value when, due to the limitation of experimental facilities, verifying work can not be carried out.When print speed printing speed is in preferred scope,
The electric conductivity of film is excellent, and uniformity is also fine, and print result is relatively stable.
It can be seen that according to the test result of the 58th~No. 64 sample when scraper pressure is lower than threshold value, scraper can not incite somebody to action
The ink of non-pattern portion is scraped completely, causes uniformity of film very poor, is not suitable for practical use.When scraper pressure is higher than threshold value
When, blade wears are extremely serious, and the uniformity of film is caused to have received certain influence；And frequently replacement scraper will lead to compared with
The time of more shutdown, again commissioning device has greatly production loss.And scraper pressure is in preferred scope, scraper
Extent of deterioration is lower, and Thinfilm pattern and non-pattern portion sharpness of border are suitble to prolonged presswork.
It can be seen that according to the test result of the 65th~No. 71 sample when imprinting roller pressure lower than threshold value, ink can not
Transfer completely, causes Thinfilm pattern incomplete, can not practical application；And when imprinting roller pressure higher than threshold value, pattern has relatively tight
The deformation of weight, also can not practical application.With the increase of coining roller pressure, the electric conductivity of film is significantly improved, the reason is that
The transfer amount of ink increases.When imprinting roller pressure in preferred scope, the electric conductivity of film is preferable, and uniformity is preferable.
The present invention utilizes printing equipment, and the transparent conductive film prepared using roll-to-roll mode of printing is had uniformly, without silk
The features such as line, high transmittance, high conductivity, low haze, fast process velocity, and the transparent conductive film can direct figure
Change, without laser cutting.Its finished product transmitance (removal substrate) is 80~97%, and square resistance is 5~200 Ω/.
In addition, inventor also utilizes the alternate embodiments such as listed other raw materials and other process conditions above
Various raw materials and corresponding process conditions in 1-4 have carried out corresponding test, the content of required verifying and with embodiment 1-4 product
It is close.So do not explained one by one to the verifying content of each embodiment, only using embodiment 1-4 as representative explanation herein
The excellent place of the present patent application.
It should be appreciated that above-described is only some embodiments of the present invention, it is noted that for the common of this field
For technical staff, under the premise of not departing from concept of the invention, other modification and improvement can also be made, these are all
It belongs to the scope of protection of the present invention.
Claims (11)
1. a kind of preparation method of transparent conductive film, characterized by comprising:, will be saturating in a manner of roll-to-roll by printing equipment
Bright electrically conductive ink, which is printed, obtains the transparent conductive film to flexible and transparent substrate surface, the printing plate in the printing equipment
White space and image-text area is distributed in surface, and the image-text area is opposite depressed portions；
The transparent conductive ink includes following component in parts by weight: one-dimensional metal nanowire dispersion 30~70
Part, 0.1~2 part of resin, 0.1~2 part of thickener, 0.001~0.1 part of levelling agent and 30~70 parts of deionized water.
2. the preparation method of transparent conductive film as described in claim 1, it is characterised in that the following steps are included:
Step is unreeled, the flexible and transparent substrate including will be provided on the unwinding device of printing equipment unreels；
Printing plate print steps print transparent conductive ink to flexible and transparent substrate table including the forme roller by printing equipment
Face obtains transparent conductive film to be processed；
Drying steps, including the transparent conductive film to be processed is dried, make transparent conductive ink in flexible and transparent base
Material surface cure forms patterned transparency conducting layer, obtains transparent conductive film；
Step is wound, including the wrap-up by printing equipment, collects transparent conductive film.
3. the preparation method of transparent conductive film as claimed in claim 2, it is characterised in that further include: carrying out the printing plate
Before print steps, processing is dusted to the flexible and transparent substrate by destaticing stick and pneumatic device.
4. the preparation method of transparent conductive film as claimed in claim 2, it is characterised in that: the drying steps use dry
Dry temperature is 80~150 DEG C, and drying time is 2~30min.
5. the preparation method of transparent conductive film as described in claim 1, it is characterised in that: the material of the flexible and transparent substrate
Matter include by PC, PET and PI polymer of single side cure process or two-sided cure process any one or it is two or more
Combination；And/or the flexible and transparent substrate with a thickness of 25~250 μm.
6. the preparation method of transparent conductive film as described in claim 1, it is characterised in that: the transparent conductive ink is glued
Degree is more than or equal to 20mPa.s and less than 2000mPa.s；And/or the surface tension of the transparent conductive ink be 20~
50mN/m。
7. the preparation method of transparent conductive film as described in claim 1, it is characterised in that: the one-dimensional metal nano wire point
The length of one-dimensional metal nano wire is 1~100 μm in dispersion liquid, preferably 15~100 μm, especially preferably 15~35 μm, diameter
For 5~200nm, preferably 5~50nm, especially preferably 10~50nm, draw ratio is 5~20000, preferably 300~
20000, especially preferably 300~3500；And/or one-dimensional metal nano wire includes in the one-dimensional metal nanowire dispersion
Any one in nano-silver thread, gold nanowire, NANO CRYSTAL COPPER WIRE, nanometer platinum line and nanometer nickel wire or two or more combinations.
8. the preparation method of transparent conductive film as described in claim 1, it is characterised in that: the one-dimensional metal nano wire point
The concentration of dispersion liquid is 1~30mg/mL.
9. the preparation method of transparent conductive film as described in claim 1, it is characterised in that: the forme roller of the printing equipment
At least by electronic engraving method, laser engraving method for platemaking, chemical attack method for platemaking and mechanical engraving plate-making side
Any one method in method is prepared.
10. the preparation method of transparent conductive film as described in claim 1, it is characterised in that: the printing plate of the printing equipment
The screen frequency of roller be 10~300 lines/centimetre, preferably 30~160 lines/centimetre, ink cell depth be 5~100 μm, preferably 20
~90 μm, leader width and the ratio of ink cell width more than or equal to 1:7 and are less than 1:4, preferably 1:5~1:6, forme roller
Screen angle is 30 °~60 °, preferably 35~55 °；And/or the dot shape of the forme roller of the printing equipment includes water chestnut
Shape, quadrangle, hexagon or the site TB；And/or the print speed printing speed of the printing equipment is 5~400m/min, scraper pressure is
0.1~0.5MPa, coining roller pressure are 0.1~0.5MPa.
11. the transparent conductive film prepared by any one of claim 1-10 the method；Preferably, the electrically conducting transparent is thin
Film is flexible；Preferably, the visible light transmittance of the transparent conductive film is 80~97%, and square resistance is 5~200
Ω/□。
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Application publication date: 20190924 |