CN104867541A - Transparent conductive film and preparation method thereof - Google Patents
Transparent conductive film and preparation method thereof Download PDFInfo
- Publication number
- CN104867541A CN104867541A CN201510181869.5A CN201510181869A CN104867541A CN 104867541 A CN104867541 A CN 104867541A CN 201510181869 A CN201510181869 A CN 201510181869A CN 104867541 A CN104867541 A CN 104867541A
- Authority
- CN
- China
- Prior art keywords
- water
- conductive film
- transparent conductive
- soluble
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a transparent conductive film and a preparation method thereof. The transparent conductive film comprises that a transparent substrate material is coated with a water-soluble conductive ink composition for a single time. The transparent conductive film is characterized in that square resistance of the film is 5 omegas per square to 500 omegas per square, and the light transmittance is 80%-99.9%. The water-soluble conductive ink composition comprises the following components by weight percentage: 0.05%-1% of conductive dielectric, 0.001%-1% of water-soluble corrosion inhibitor, 0.03%-3% of water-soluble resin, 0.0005%-1% of curing agent, 0.0001%-1% of anti-adsorption agent and 95%-99.9% of solvent. Water can be used to act as the unique solvent so as to reduce environmental pollutions. The operation of single coating is adopted, thereby being capable of improving the productivity, saving the cost, and improving the competitiveness of products. The conductivity is kept under the condition that the haze and the light transmittance are not changed, and the scratch resistance is increased.
Description
Technical field
The invention belongs to transparent conductive film field, be specifically related to a kind of transparent conductive film and preparation method thereof.
Background technology
Transparent conductive film can be applied to touch-screen, display device, the fields such as electromagnetic shielding.Rare metal indium (In) the global reserves that traditional ITO transparent conductive film contains due to it are limited, and due to its resist bending poor performance on flexible substrates, make one of the selection becoming alternative ITO material in a lot of field of nano silver wire transparent conductive film.
Adopt the mode of solution coat to prepare transparent conductive film compared to magnetron sputtering, chemical vapour deposition (CVD), the modes such as physical vapour deposition (PVD) have low cost, adapt to large area and produce, the advantages such as output is large.Adopt the mode of solution coat to prepare transparent conductive film, application frequency and the formula for the conductive ink composition be coated with all can have influence on final cost and performance.
Nano silver wire transparent conductive film in patent US 2012/0107600 A1 has adhesive force and persistence, but this patent adopts organic solvent as the solvent of conductive ink.Water prescription is refer in patent WO 2011/008227 A1, the combination employing water soluble polymer and curing agent in this formula improves the scratch resistance of transparent conductive film, and refer to the suction-operated of macromolecule on nano silver wire surface, this suction-operated is conducive to nano silver wire and disperses in aqueous, but this suction-operated also can make the conductivity of nano silver wire transparent conductive film decline, and the film finally showing as same conductivity has more haze.In patent CN 101292362 B, cambrios company adopts the adhesive force of PU resin tooth nano silver wire on substrate, in patent CN 102834472 A, cambrios company have employed light curing agent cured fiber element, add the solvent stability of nano silver wire, in patent EP2251389 A1, nano silver wire and PEDOT carry out being mixed to get transparent conductive film.But above patent is all realize the weatherability of transparent conductive film by repeatedly coating process, does not directly add the persistence that corrosion inhibiter promotes nano silver wire transparent conductive film in nano silver wire solution.Refer to corrosion inhibiter in patent US 2010/0078602 A1 and US20140170407 can cause nano silver wire to reunite, can not be directly used in combination with nano silver wire.In patent WO2011115603A1, add corrosion inhibiter, but similar in the absorption on nano silver wire surface with the macromolecule such as tackifier, corrosion inhibiter also can at nano silver wire adsorption, need to add the conductivity that suitable anti-adsorbent keeps nano silver wire.But because this patent does not mention the component of anti-adsorbent, prepared film often has higher mist degree and lower light transmittance when same sheet resistance.
In sum, adopt water-based system and single application greatly to reduce costs, enhance productivity, but product when mist degree and light transmittance constant, be difficult to reach desirable scratch resistance, conductivity.
Summary of the invention
The present invention mainly solves the problem existing for prior art, provides a kind of transparent conductive film and preparation method thereof.A kind of transparent conductive film, comprise non-transparent substrate material single application water-soluble conducting composition for ink, the square resistance of described film is 5 Ω/-500 Ω/, light transmittance is 80%-99.9%, described water-soluble conducting composition for ink, said composition is composed of the following components by weight percentage: conducting medium 0.05%-1%; Water soluble rust inhibitor 0.001%-1%; Water-soluble resin 0.03%-3%; Curing agent 0.0005%-1%; Anti-adsorbent 0.0001%-1%; Solvent 95%-99.9%.
As preferably, described conducting medium is nano silver wire, and the diameter of nano silver wire is 10-100 nanometer, and length is 5-100 micron.Preferred diameter is 15-35nm, and length is 10-80 micron.
As preferably, described water soluble rust inhibitor is one or both mixture in pyridazine and 3-[2-perfluoroalkyl ethylmercapto group] propionic acid lithium.Water soluble rust inhibitor is water-soluble corrosion inhibiter, can adsorb and nano silver wire surface, slow down the aerial oxidation of nano silver wire.But covalent bond can not be formed with nano silver wire again, otherwise nano silver wire reunion in the solution can be caused.Described corrosion inhibiter optionally comprises sulfide based structural, phenyl ring, one or more in assorted nitrogen conjugate ring.In one embodiment, water soluble rust inhibitor is pyridazine.In still another embodiment, water soluble rust inhibitor is FSA.Water soluble rust inhibitor is pyridazine and FSA in still another embodiment.
As preferably, described water-soluble resin is pectin, polyvinyl alcohol, hydroxyethylcellulose, gelatin, in hydroxypropyl methylcellulose any one, two or more mixture.Water-soluble resin can bring scratch resistance and adhesive force for nano silver wire transparent conductive film, and it is also a kind of good film forming agent simultaneously.In order to ensure the resistance to wear of transparent conductive film, it is 0.03%-3% that water-soluble resin accounts for monolithic conductive composition for ink mass fraction.Molecular weight has a significant impact for polysaccharide viscosity in aqueous, make it can be adsorbed in the surface of nano silver wire because polysaccharide contains hydroxyl simultaneously, this character makes polysaccharide can improve nano silver wire dispersiveness in aqueous and stability, but exist simultaneously reduce the potential of nano silver wire conductivity may.In order to eliminate the negative effect reducing nano silver wire conductivity, need to select the molecular weight of water-soluble resin and concentration, the viscosity finally showing as conductive ink composition needs lower than 30cps, preferred lower than 25cps.
As preferably, described curing agent is titanate coupling agent, zirconium ester coupling agent, silane coupler, aziridine derivative, blocked isocyanate, glyoxal, glutaraldehyde, in vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) compounds any one, two or more mixture.Curing agent is used for cross-linked, water-soluble resin, improves the scraping and wiping resistance performance of water-soluble resin, adhesive force.Account for conductive ink composition in its entirety ratio be 0.0005%-1%.For the predecessor of inorganic matter, possess water-soluble simultaneously.Suitable curing agent comprises: aziridine and derivative thereof, blocked isocyanate, titanate coupling agent, zirconium ester coupling agent, silane coupler.
As preferably, described anti-adsorbent is hydrochloric acid, nitric acid, sodium chloride, in KBr any one, two or more mixture.Acting as of described anti-adsorbent stops corrosion inhibiter or thickener to adsorb at conductive material surface, thus eliminates or reduce the harmful effect to conductivity that corrosion inhibiter or thickener bring.The overall viscosity of preferred conductive ink composition is less than 30cps.
As preferably, described solvent is the mixture of water or water and alcohol, wherein alcohol content≤30%.Described alcohol is ethanol or isopropyl alcohol.
As preferably, described transparent substrate is glass, polyolefin, polyether-ketone, polyimides (PI), PETG (PET), polymethyl methacrylate (PMMA), Merlon (PC), polyurethane (PU), PEN (PEN), polystyrene (PS), polypropylene (PP), polyacrylate, silicone, polyethylene, glass resin, fluoropolymer, polyester, a kind of in the macromolecule membrane of inorganic doping, the copolymer of two kinds or two or more material, or mixture, or laminate.
The invention also discloses the preparation method of transparent conductive film as described above, comprise the steps: that (1) carries out hydrophilic treated to transparent substrate, after process, the angle of wetting of water is less than 15 °; (2) by nano silver wire, water-soluble resin, curing agent, water soluble rust inhibitor, anti-adsorbent is configured to solution respectively; (3) by nano silver wire, water-soluble resin, curing agent, water soluble rust inhibitor mixes; (4) dropwise add anti-adsorbent solution, stir while adding, after stirring, obtain water-soluble conducting composition for ink; (5) water-soluble conducting composition for ink is coated on transparent substrate by single application mode; (6) applied after carry out heating, dry and solidifying.Described heating-up temperature is 60 DEG C-150 DEG C, and drying time is 5-10 minute.
As preferably, described coating method is the coating of slit extruded type, the coating of comma shaft type, rod paintings, micro-web coatable, dip coated, spin coating, spraying, scraper type is coated with or silk screen printing, intaglio printing, any one in hectographic printing.
Transparent conductive film of the present invention realizes by forming transparency conducting layer on a transparent substrate, wherein transparency conducting layer is by obtaining film with the mode drying of heating after single application water-soluble conducting composition for ink, the square resistance of the transparency conducting layer that described transparent substrates is formed is 5 Ω/-500 Ω/, the square resistance Rs of the light transmittance T and transparent conductive film that simultaneously comprise substrate meets T>93%-82/Rs, and the square resistance Rs of the mist degree H and transparent conductive film that do not comprise substrate meets H<65/Rs.And after film can test 10 times by adhesive force, resistance added value is that 20%-100%, 20N load rubbing machine scratch-resistant tests 50 times, and resistance added value is 10%-20%, and hot and humid placement is after 120 hours, and its sheet resistance rate of change is 20%-100%.
The beneficial effect brought of the present invention is:
1. can use water as exclusive solvents, reduce VOC, reduce solvent cost, reduce environmental pollution, improve the fail safe of electrically conducting transparent ink, although the solvent in formula does not participate in last reaction, but because consumption is huge, if employing organic solvent, VOC (VOC) can be caused to discharge, and VOC is acknowledged as one of primary pollution source of current global atmosphere pollution, so not only make the inadequate environmental protection of the production process of whole film, and belong to inflammable and explosive chemicals due to most of organic solvent, make the preparation of ink, transport, the fail safe of depositing and use reduces, in addition, after adopting organic solvent coating, cleaning equipment also can bring harmful effect to the health of operator, and adopt water color ink after coating completes, the cleaning of machine can become and be more prone to, cleaning cost is also cheaper, the health of operator is had no adverse effects.
2. still can realize required performance when using single application technique, adopting single application can improve production capacity significantly, improving equipment operation efficiency, compression process cost, improving the competitiveness of product;
3., by the overall viscosity of restriction conductive ink composition, reduce the impact that water-base resin reduces conductivity.When mist degree and light transmittance constant, keep conductivity, increase scratch resistance.
4., by adding anti-adsorbent, eliminate the impact that corrosion inhibiter reduces conductivity.When mist degree and light transmittance constant, make transparent conductive film place after stable conductivity.
5. adopt hydrophilic substrate, make nano silver wire be adsorbed in substrate, improve conductivity, improve the addition of water-soluble resin, increase scratch resistance.
Accompanying drawing explanation
Accompanying drawing 1 is frictional testing machine schematic diagram in the present invention.
101 loadings; 102 friction papers; 103 friction pieces; 104 samples; 105 press strips; 106 rubbing table.
Embodiment
Below by embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.
Material
Nano silver wire is from Zhejiang Kechuang New Material Technology Co., Ltd..Deionized water, pyridazine, titanate esters, polyvinyl alcohol, ethanol, sodium chloride, KBr is from Aladdin reagent.
Conductivity
Conductivity refers to the ability of film conduction current, in conductive film field, generally characterizes it with square resistance, and unit is Ω/.Transparent conductive film in the present invention is invented in order to electrooptical device.The design at the design of single conductive layer and fusion junction point is in a network all to improve planar direction and plane foreign side conductivity upwards simultaneously.Finally, the sheet resistance of described conductive film reduces greatly.
In another embodiment of the invention, the square resistance of described transparent conductive film is adjustable in the scope of 0.1 Ω/ to 1000 Ω/.
Adhesive force
Transparent conductive film is subject to tape test further.More specifically, scribble 3M Scotch 600 adhesive tape securely on the surface of the substrate and then remove.The nano silver wire of any pine is removed together with adhesive tape.After tape test, the measured and result of the electrical and optical properties of transparent conductor illustrates in table 2.
After 10 tests, resistance added value is less than 100% for excellent,
After 5 tests, resistance added value is less than 100% for good,
After 3 tests, resistance added value is less than 100% and is,
After 1 test, resistance added value 100%-200% is for poor,
After 1 test, resistance added value is 200%-500% is extreme difference,
After 1 test, conductive layer is all peeled off, for without adhesive force
Mist degree
With a branch of directional light vertical irradiation of standard " c " light source on transparent or semitransparent film, sheet material, sheet material, because scattering is caused on material internal and surface, the percentage making part directional light depart from incident direction to be greater than the scatter light flux Td of 2.5 ° and the ratio of the luminous flux T of permeable material, that is:
Mist degree computing formula
H＝Td/T*100％
The mist degree of transparent conductive film represents with H%.Square resistance Rs represents,
When mist degree H and square resistance Rs meets H<55/Rs, be defined as excellent
When mist degree H and square resistance Rs meets 55/Rs<H<65/Rs, be defined as good
When mist degree H and square resistance Rs meets 65/Rs<H<75/Rs, in being defined as
When mist degree H and square resistance Rs meets 75/Rs<H<85/Rs, be defined as difference
When mist degree H and square resistance Rs meets H>85/Rs, be defined as extreme difference
Light transmittance
Light transmittance refers to the percentage of luminous flux through transparent or semitransparent body and its incident flux.The light transmittance of the transparent conductive film in the present invention adopts cary300 ultraviolet-uisible spectrophotometer to test.
When the main individual layer of described net metal nano wire has preferred thickness, described transparency conductive electrode has excellent optical clarity.
In an example, described transparency conductive electrode have at least be greater than 80% light transmission in the wave-length coverage of 380nm-780nm.
In a preferred embodiment, described transparency conductive electrode have at least be greater than 90% light transmission in the wave-length coverage of 380nm-780nm nanometer.
In a preferred embodiment, described transparency conductive electrode have at least be greater than 95% light transmission in the wave-length coverage of 380nm-780nm.
When light transmittance T and square resistance Rs meets T>93%-70/Rs, be defined as excellent
When light transmittance T and square resistance Rs meets 93%-70/Rs>T>93%-82/Rs, be defined as good
When light transmittance T and square resistance Rs meets 93%-82/Rs>T>93%-94/Rs, in being defined as
When light transmittance T and square resistance Rs meets 93%-94/Rs>T>93%-106/Rs, be defined as difference
When light transmittance T and square resistance Rs meets T>93%-106/Rs, be defined as extreme difference
Persistence
Transparent conductive film is subject to tape test further.More specifically, the transparent conductive film hot and humid environment of preparation is placed, observe the change of its conductivity.
For the transparent conductive film not with protective layer,
120 hours resistance variations be less than 100% be designated as excellent
80 hours resistance variations be less than 100% be designated as good
40 hours resistance variations are less than in 100% be designated as
20 hours resistance variations are less than 100% and are designated as difference
20 hours resistance variations are greater than 100% and are designated as extreme difference
Scratch resistance
As shown in Figure 1, rubbing table 106 adopts surface roughness to be not less than the hard plastic body of 1.6 μm to frictional testing machine, and has press strip 105 to fix the device of sample; Friction piece 103 adopts two pieces of thick 8mm, hardness 50Hs-53Hs, and size is the rubber of 25mm × 50mm, at a distance of 45mm inside two piece 103.
Friction papers 102 adopts the cleaning rubber millboard of 80g/m2, and width is 50mm.101 load are 20N, and the friction velocity of frictional experiment should reach 43 times/min ± 2 time/min, stroke 60mm.
The sample 104 cutting certain size is fixed in rubbing table 106, and the area of sample 104 layer to be measured is greater than the area of frictional layer.Measure the square resistance of area to be measured.Measure and average for 5 times, be designated as R.Friction papers 102 is fixed on friction piece 103.Open frictional testing machine, double rubs 50 times.Sample 104 is taken off in shutdown, and the square resistance of test test zone, tests and average for five times, be designated as Re.
As＝R/Re*100％
As-transparent conductive film resistance to wear
Square resistance before R-test
Square resistance after Rs-test
As>90% is designated as excellent
As>70% is designated as good
During As>50% is designated as
As>30% is designated as difference
As<30% is designated as extreme difference
Embodiment:
The impact of each component in the present invention is described below by embodiment and comparative example, and table 1 illustrates the formula of embodiment 1-6 and comparative example 1-4.
Embodiment 1
First by divinyl sulfone, pyridazine, nano silver wire, sodium chloride is configured to the aqueous solution of 1% concentration, pectin is configured to the aqueous solution of 10% concentration.By the 77g nano silver wire aqueous solution, the 40g pyridazine aqueous solution, the 20g titanate esters aqueous solution, 40g aqueous pectin solution mixes.Add 803g water, stir 1 minute, dropwise add 20g sodium-chloride water solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 30 micro wire rods, drying 10 minutes for 120 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Embodiment 2
First by titanate esters, FSA, nano silver wire, sodium chloride is configured to the aqueous solution of 1% concentration, polyvinyl alcohol 400 is configured to the aqueous solution of 10% concentration.By the 77g nano silver wire aqueous solution, the 40gFSA aqueous solution, the 5g titanate esters aqueous solution, 40g polyvinyl alcohol 400 aqueous solution.Add 818g water, stir 1 minute, dropwise add 20g sodium-chloride water solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 30 micro wire rods, drying 10 minutes for 60 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Table 1
Embodiment 3
First by glutaraldehyde, FSA, nano silver wire, sodium chloride is configured to the aqueous solution of 1% concentration, gelatin is configured to the aqueous solution of 10% concentration.By the 200g nano silver wire aqueous solution, the 10gFSA aqueous solution, 50g glutaraldehyde water solution, 20g aqueous gelatin solution mixes.Add 700g water, stir 1 minute, dropwise add 20g sodium-chloride water solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 30 micro wire rods, drying 10 minutes for 150 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Embodiment 4
First by silane coupler, FSA, pyridazine, nano silver wire is configured to the aqueous solution of 1% concentration, and by KBr, polyvinyl alcohol 400, gelatin is configured to the aqueous solution of 10% concentration respectively.By the 77g nano silver wire aqueous solution, the 100gFSA aqueous solution, the 100g pyridazine aqueous solution, the 50g silane coupler aqueous solution, 200g polyvinyl alcohol 400 aqueous solution, 200g aqueous gelatin solution mixes.Add 223g water, stir 1 minute, dropwise add 50g kbr aqueous solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 30 micro wire rods, drying 5 minutes for 120 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Embodiment 5
First by glyoxal, nano silver wire, KBr is configured to the aqueous solution of 1% concentration, and by pyridazine, pectin, polyvinyl alcohol 400 is configured to the aqueous solution of 10% concentration, nano silver wire is configured to 2% concentration of aqueous solution.By the 500g nano silver wire aqueous solution, the 50g pyridazine aqueous solution, 50g glyoxal water solution, 10g polyvinyl alcohol 400 aqueous solution, 30g aqueous pectin solution mixes.Add 340g water, stir 1 minute, dropwise add 20g kbr aqueous solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 30 micro wire rods, drying 5 minutes for 120 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Embodiment 6
First by blocked isocyanate, FSA, pyridazine, nano silver wire, KBr is configured to the aqueous solution of 2% concentration, polyvinyl alcohol 400 is configured to the aqueous solution of 10% concentration.By the 25g nano silver wire aqueous solution, the 150gFSA aqueous solution, the 10g pyridazine aqueous solution, the 10g blocked isocyanate aqueous solution, 200g polyvinyl alcohol 400 aqueous solution.Add 285 water, add 300g ethanol, stir 1 minute.Dropwise add 20g kbr aqueous solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 50 micro wire rods, drying 5 minutes for 120 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Embodiment 7
First by silane coupler, pyridazine, sodium chloride, gelatin is configured to the aqueous solution of 10% concentration, nano silver wire is configured to 2% concentration of aqueous solution.By the 500g nano silver wire aqueous solution, the 50g pyridazine aqueous solution, the 100g silane coupler aqueous solution, 300g aqueous gelatin solution mixes, and stirs 1 minute.Dropwise add 50g sodium-chloride water solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 30 micro wire rods, drying 5 minutes for 120 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Embodiment 8
First by silane coupler, pyridazine, nano silver wire, KBr is configured to the aqueous solution of 1% concentration, gelatin is configured to the aqueous solution of 10% concentration.By the 40g nano silver wire aqueous solution, the 10g pyridazine aqueous solution, the 5g silane coupler aqueous solution, 40g aqueous gelatin solution mixes.Add 900g water, stir 1 minute, dropwise add 5g kbr aqueous solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 75 micro wire rods, drying 5 minutes for 120 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Comparative example 1
First by pyridazine, nano silver wire, sodium chloride is configured to the aqueous solution of 1% concentration, pectin is configured to the aqueous solution of 10% concentration.By the 77g nano silver wire aqueous solution, the 50g pyridazine aqueous solution, 400g aqueous pectin solution mixes, and stirs 1 minute, adds 453g water.Dropwise add 20g kbr aqueous solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 30 micro wire rods, drying 5 minutes for 120 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Comparative example 2
First by aziridine, pyridazine, nano silver wire, sodium chloride is configured to the aqueous solution of 1% concentration, polyvinyl alcohol 2000 is configured to the aqueous solution of 10% concentration.By the 77g nano silver wire aqueous solution, the 40g pyridazine aqueous solution, the 20g aziridine aqueous solution, 200g polyvinyl alcohol 2000 aqueous solution, stirs 1 minute.Add 643g water, dropwise add 20g sodium-chloride water solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 30 micro wire rods, drying 5 minutes for 120 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Comparative example 3
First by zirconate, pyridazine, nano silver wire, KBr is configured to the aqueous solution of 1% concentration, ethyl cellulose (30000cps) is configured to the aqueous solution of 10% concentration.By the 77g nano silver wire aqueous solution, the 200g pyridazine aqueous solution, the 20g zirconate aqueous solution, 200g ethyl cellulose (30000cps) aqueous solution, adds 683g water, stirs 1 minute.Dropwise add 20g kbr aqueous solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 30 micro wire rods, drying 5 minutes for 120 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Comparative example 4
First by pyridazine, sodium chloride is configured to the aqueous solution of 1% concentration, polyvinyl alcohol 400 is configured to the aqueous solution of 10% concentration.By the 77g nano silver wire aqueous solution, the 100g pyridazine aqueous solution, 400g polyvinyl alcohol 400 aqueous solution, stirs 1 minute.Add 403g water, dropwise add 20g sodium-chloride water solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 30 micro wire rods, drying 5 minutes for 120 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Comparative example 5
First by blocked isocyanate, FSA, pyridazine, nano silver wire, KBr is configured to the aqueous solution of 2% concentration, polyvinyl alcohol 400 is configured to the aqueous solution of 10% concentration.By the 25g nano silver wire aqueous solution, the 150gFSA aqueous solution, the 10g pyridazine aqueous solution, the 10g blocked isocyanate aqueous solution, 200g polyvinyl alcohol 400 aqueous solution.Add 85 water, add 500g ethanol, stir 1 minute.Dropwise add 20g kbr aqueous solution, do not stop in the process added to stir.After being configured to conductive ink composition, on PET, being coated with wet film with 50 micro wire rods, drying 5 minutes for 120 DEG C.Carry out conductivity test subsequently, light transmittance is tested, and mist degree is tested, and adhesive force is tested, and scratch resistance is tested, and persistence is tested.
Test the result obtained as shown in table 2, contrast known hydrophilic substrate by embodiment 1 and embodiment 2 and can bring higher light transmittance and lower mist degree.Comparative example 1 illustrates that curing agent can promote adhesive force and the scraping and wiping resistance performance of transparent conductive film.Comparative example 2 and comparative example 3 illustrate that full-bodied HPMC significantly can reduce the conductivity of transparent conductive film.Comparative example 4 illustrates that the HPMC of excessive concentrations significantly can reduce the conductivity of transparent conductive film.Comparative example 5 illustrates in solvent and transparent conductive film can be made to have larger mist degree and lower light transmittance when identical conductivity containing ethanol.
| Scratch resistance | Adhesive force | Persistence | Mist degree | Light transmittance | |
| Embodiment 1 | Excellent | Excellent | Excellent | Excellent | Excellent |
| Embodiment 2 | Excellent | Excellent | Excellent | Good | Good |
| Embodiment 3 | Excellent | Excellent | Excellent | Good | Good |
| Embodiment 4 | Excellent | Excellent | Excellent | Good | Good |
| Embodiment 5 | Excellent | Excellent | Excellent | Good | Good |
| Embodiment 6 | Excellent | Excellent | Excellent | Good | Good |
| Embodiment 7 | Excellent | Excellent | Excellent | Good | Good |
| Embodiment 8 | Good | Good | Good | Excellent | Excellent |
| Comparative example 1 | Extreme difference | Extreme difference | Excellent | Excellent | Good |
| Comparative example 2 | Excellent | Excellent | Excellent | Difference | Difference |
| Comparative example 3 | Excellent | Excellent | Excellent | Extreme difference | Extreme difference |
| Comparative example 4 | Difference | Difference | Excellent | Extreme difference | Difference |
| Comparative example 5 | Excellent | Excellent | Excellent | In | In |
Table 2
Above-mentioned embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection range of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (10)
1. a transparent conductive film, comprise non-transparent substrate material single application water-soluble conducting composition for ink, it is characterized in that the square resistance of described film is 5 Ω/-500 Ω/, light transmittance is 80%-99.9%, described water-soluble conducting composition for ink, said composition is composed of the following components by weight percentage:
Conducting medium 0.05%-1%;
Water soluble rust inhibitor 0.001%-1%;
Water-soluble resin 0.03%-3%;
Curing agent 0.0005%-1%;
Anti-adsorbent 0.0001%-1%;
Solvent 95%-99.9%.
2. a kind of transparent conductive film according to claim 1, is characterized in that described conducting medium is nano silver wire, and the diameter of nano silver wire is 10-100 nanometer, and length is 5-100 micron.
3. a kind of transparent conductive film according to claim 1, is characterized in that described water soluble rust inhibitor is one or both the mixture in pyridazine and 3-[2-perfluoroalkyl ethylmercapto group] propionic acid lithium.
4. a kind of transparent conductive film according to claim 1, is characterized in that described water-soluble resin is pectin, polyvinyl alcohol, hydroxyethylcellulose, gelatin, in hydroxypropyl methylcellulose any one, two or more mixture.
5. a kind of transparent conductive film according to claim 1, it is characterized in that described curing agent is titanate coupling agent, zirconium ester coupling agent, silane coupler, aziridine derivative, blocked isocyanate, glyoxal, glutaraldehyde, a kind of, two or more mixture in vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) compounds.
6. a kind of transparent conductive film according to claim 1, is characterized in that described anti-adsorbent is hydrochloric acid, nitric acid, sodium chloride, a kind of, two or more mixture in KBr.
7. a kind of transparent conductive film according to claim 1, is characterized in that described solvent is the mixture of water or water and alcohol, wherein alcohol content≤30%.
8. a kind of transparent conductive film according to claim 1, is characterized in that described transparent substrate is a kind of in the macromolecule membrane of glass, polyolefin, polyether-ketone, polyimides, PETG, polymethyl methacrylate, Merlon, polyurethane, PEN, polystyrene, polypropylene, polyacrylate, silicone, polyethylene, glass resin, fluoropolymer, polyester, inorganic doping copolymer of, two kinds or two or more material or mixture or laminate.
9. the preparation method of the transparent conductive film as described in any one of claim 1-8, is characterized in that comprising the steps: that (1) carries out hydrophilic treated to transparent substrate, and after process, the angle of wetting of water is less than 15 °; (2) by nano silver wire, water-soluble resin, curing agent, water soluble rust inhibitor, anti-adsorbent is configured to solution respectively; (3) by nano silver wire, water-soluble resin, curing agent, water soluble rust inhibitor mixes; (4) dropwise add anti-adsorbent solution, stir while adding, after stirring, obtain water-soluble conducting composition for ink; (5) water-soluble conducting composition for ink is coated on transparent substrate by single application mode; (6) applied after carry out heating, dry and solidifying.
10. the preparation method of a kind of transparent conductive film according to claim 9, it is characterized in that described coating method is the coating of slit extruded type, the coating of comma shaft type, rod paintings, micro-web coatable, dip coated, spin coating, spraying, scraper type is coated with or silk screen printing, intaglio printing, any one in hectographic printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510181869.5A CN104867541B (en) | 2015-04-16 | 2015-04-16 | A kind of transparent conductive film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510181869.5A CN104867541B (en) | 2015-04-16 | 2015-04-16 | A kind of transparent conductive film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104867541A true CN104867541A (en) | 2015-08-26 |
| CN104867541B CN104867541B (en) | 2017-12-15 |
Family
ID=53913320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510181869.5A Active CN104867541B (en) | 2015-04-16 | 2015-04-16 | A kind of transparent conductive film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104867541B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108603064A (en) * | 2016-03-11 | 2018-09-28 | 昭和电工株式会社 | Metal nanometer line ink, transparent conductive substrate and transparent anti static substrate |
| CN108899278A (en) * | 2018-06-30 | 2018-11-27 | 昆山国显光电有限公司 | The manufacturing method of patterned nano-silver thread film and touch panel |
| CN113593750A (en) * | 2021-06-18 | 2021-11-02 | 西湖未来智造(杭州)科技发展有限公司 | Water-soluble nano metal slurry and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100078602A1 (en) * | 2008-09-30 | 2010-04-01 | Fujifilm Corporation | Metal nanowire-containing composition, and transparent conductor |
| CN102460600A (en) * | 2009-05-05 | 2012-05-16 | 凯博瑞奥斯技术公司 | Reliable and durable conductive films comprising metal nanostructures |
| CN102481757A (en) * | 2009-07-17 | 2012-05-30 | 卡尔斯特里姆保健公司 | Transparent conductive film comprising water soluble binders |
| CN102481758A (en) * | 2009-07-17 | 2012-05-30 | 卡尔斯特里姆保健公司 | Transparent conductive film comprising cellulose esters |
| CN102939346A (en) * | 2010-03-19 | 2013-02-20 | 卡尔斯特里姆保健公司 | Anti-corrosion agents for transparent conductive film |
| CN104204111A (en) * | 2012-03-23 | 2014-12-10 | 富士胶片株式会社 | Conductive composition, conductive member, conductive member manufacturing method, touch panel, and solar cell |
-
2015
- 2015-04-16 CN CN201510181869.5A patent/CN104867541B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100078602A1 (en) * | 2008-09-30 | 2010-04-01 | Fujifilm Corporation | Metal nanowire-containing composition, and transparent conductor |
| CN102460600A (en) * | 2009-05-05 | 2012-05-16 | 凯博瑞奥斯技术公司 | Reliable and durable conductive films comprising metal nanostructures |
| CN102481757A (en) * | 2009-07-17 | 2012-05-30 | 卡尔斯特里姆保健公司 | Transparent conductive film comprising water soluble binders |
| CN102481758A (en) * | 2009-07-17 | 2012-05-30 | 卡尔斯特里姆保健公司 | Transparent conductive film comprising cellulose esters |
| CN102939346A (en) * | 2010-03-19 | 2013-02-20 | 卡尔斯特里姆保健公司 | Anti-corrosion agents for transparent conductive film |
| CN104204111A (en) * | 2012-03-23 | 2014-12-10 | 富士胶片株式会社 | Conductive composition, conductive member, conductive member manufacturing method, touch panel, and solar cell |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108603064A (en) * | 2016-03-11 | 2018-09-28 | 昭和电工株式会社 | Metal nanometer line ink, transparent conductive substrate and transparent anti static substrate |
| CN108899278A (en) * | 2018-06-30 | 2018-11-27 | 昆山国显光电有限公司 | The manufacturing method of patterned nano-silver thread film and touch panel |
| CN113593750A (en) * | 2021-06-18 | 2021-11-02 | 西湖未来智造(杭州)科技发展有限公司 | Water-soluble nano metal slurry and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104867541B (en) | 2017-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109181498B (en) | Environment-friendly coating for electronic products | |
| CN109251636B (en) | Preparation process of high-light-transmittance aqueous conductive coating | |
| WO2015074611A1 (en) | Protective film having high transparency and impact resistance, preparation method therefor | |
| CN106128564B (en) | The preparation method of PET/ nano-silver thread nesa coatings through illumination sintering processes | |
| CN105778608B (en) | A kind of graphene composite coating and preparation method thereof | |
| CN105542641A (en) | Carbon nanotube antistatic film with strong adhesion, high light transmittance and low surface resistance, and production technology thereof | |
| KR20120021451A (en) | Method for manufacturing transparent conductive layer and transparent conductive layer manufactured by the method | |
| CN202904046U (en) | Optical diffusion barrier | |
| CN106497391A (en) | Ultraviolet light polymerization Weather-proof self-cleaning coating composition | |
| CN105304164B (en) | A kind of water base nano silver wire ink and its method for manufacturing thin film easily post-processed | |
| CN106700961B (en) | Electromagnetic wave shielding film and highly transparent strong electromagnetic wave shielding adhesive tape based on same | |
| CN111057414B (en) | Crosslinkable chemically-sinterable strong-adhesion silver nanowire conductive ink and conductive film prepared from same | |
| CN104867541A (en) | Transparent conductive film and preparation method thereof | |
| CN106279740B (en) | A kind of resin compound, transparent conductive film and preparation method thereof | |
| JP2015146127A (en) | Transparent conductive film and manufacturing method of the same, information input device, and electronic apparatus | |
| TWI251239B (en) | Transparent conductive film and process for producing the same | |
| CN207367619U (en) | There is the composite construction conducting film of high adhesion force based on graphene | |
| CN108250469B (en) | Production process of nano silver wire transparent conductive film | |
| CN108417294A (en) | Flexible and transparent conductive electrode | |
| CN102602118B (en) | Transfer printing method of carbon nanotube thin film | |
| CN108774474B (en) | PET (polyethylene terephthalate) protective film and preparation method thereof | |
| CN101551483A (en) | Optical film and forming method thereof | |
| CN104064282A (en) | Production method for high-transmittance transparent rigid nanocrystalline metal conductive films | |
| CN104129128A (en) | Antistatic release film | |
| CN101548202B (en) | Optical filter for display panel and method of manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |