CN104637570A - Flexible transparent conductive thin film and preparation method thereof - Google Patents
Flexible transparent conductive thin film and preparation method thereof Download PDFInfo
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- CN104637570A CN104637570A CN201510046325.8A CN201510046325A CN104637570A CN 104637570 A CN104637570 A CN 104637570A CN 201510046325 A CN201510046325 A CN 201510046325A CN 104637570 A CN104637570 A CN 104637570A
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Abstract
The invention relates to a flexible transparent conductive thin film and a preparation method thereof. The flexible transparent conductive thin film comprises a transparent substrate and a conductive layer, wherein the conductive layer is overlapped on the transparent substrate and is made of conductive polymer, silver nanowires and curing resin, the silver nanowires and the curing resin are dispersed in the curing resin, the silver nanowires are mutually overlapped, the silver nanowires and the conductive polymer form a conductive network, and the conductive polymer is at least one of polypyrrole, polypyrrole derivative, polythiophene, polythiophene derivative, polyaniline, polyaniline derivative, polyacetylene, polyacetylene derivative, and poly (sodium 4-styrenesulfonate). The flexible transparent conductive thin film has the advantages that the conductivity is better, and the transparency rate is higher.
Description
Technical field
The present invention relates to electronic devices and components field, particularly relate to a kind of flexible transparent conductive film and preparation method thereof.
Background technology
In recent years, transparent conductive film is widely used in liquid crystal display, contact panel and solar cell aspect.The conductivity that transparent conductive film not only requires, also will have excellent visible light transmittance rate.Although ITO is current investigation and application oxide TCF the most widely, because its raw material resources are day by day rare, the complicated and evaporating deposition technique of costliness, and the crisp characteristic of film matter limits its application at flexible electronic device.
Based on ito thin film application limitation, at present, people constantly seek the new material that can substitute ITO.Market reaction, the proportion shared by film product that application new material technology is produced is improving year by year.And Graphene is still in development, distance volume production also has far distance.CNT (carbon nano-tube) industrial volume production technology is not yet perfect, its film made due to the contact resistance between carbon nano-tube comparatively large, product conductivity can't reach the level of common ito thin film.And this bi-material cannot take into account its excellent conductivity and light transmittance simultaneously.Thus, apply overall merit from technical development and market, the two large leading roles that metal grill and nano-silver thread technology will be recent emerging touch technology.
By contrast, nano-silver thread is excellent conductivity not only, and has good pliability due to the special pattern of its material itself.The nano-silver thread technology that nano silver wire transparent conductive film is innovated with uniqueness, can provide and have more splendid durability than conventional I TO, and high flexibility, low resistance and superior line such as to get ready at the durability, and benefit can reach more than the several times of ITO.For realize flexible touch screen, bent LED shows etc. provides possibility, there is in fields such as flat panel display, luminescent device, flexible display, Foldable solar energy batteries application widely.
But existing nano-silver thread conductive film still exists the poor and problem that light transmittance is poor of conductivity, and the preparation of existing nano-silver thread conductive film all needs two steps coatings to realize, and complicated process of preparation, is unfavorable for prepared by device in large size.
Summary of the invention
Given this, be necessary to provide a kind of conductivity better and the higher flexible transparent conductive film of light transmittance.
In addition, a kind of preparation method preparing comparatively simple flexible transparent conductive film is also provided.
A kind of flexible transparent conductive film, comprise transparent substrates and be laminated in the conductive layer in described transparent substrates, the material of described conductive layer comprises conducting polymer, nano-silver thread and cured resin, described nano-silver thread and described conducting polymer are scattered in described cured resin, and described nano-silver thread overlaps mutually, and jointly form conductive network with described conducting polymer, described conducting polymer is selected from polypyrrole, the derivative of polypyrrole, polythiophene, the derivative of polythiophene, polyaniline, the derivative of polyaniline, polyacetylene, at least one in the derivative of polyacetylene and poly-p styrene sulfonic acid.
Wherein in an embodiment, the diameter of described nano-silver thread is 12 ~ 100 nanometers, and length is 10 ~ 60 microns.
Wherein in an embodiment, described cured resin is selected from the one in epoxy resin, polyurethane resin, acrylic resin, gum arabic, polyvinyl alcohol and organic silica gel.
Wherein in an embodiment, the mass percent of described conducting polymer, nano-silver thread and cured resin is 3 ~ 10:5 ~ 50:18 ~ 25.
Wherein in an embodiment, the material of described transparent substrates is selected from the one in PETG, Merlon, polytetrafluoroethylene and polymethyl methacrylate.
Wherein in an embodiment, the visible light transmittance rate of described transparent substrates is more than 70%.
Wherein in an embodiment, the thickness of described conductive layer is 0.1 ~ 100 micron.
A preparation method for flexible transparent conductive film, comprises the steps:
Conducting polymer, nano-silver thread and cured resin are mixed in solvent, form electrically conductive ink, wherein, described conducting polymer is selected from least one in polypyrrole, the derivative of polypyrrole, polythiophene, the derivative of polythiophene, polyaniline, the derivative of polyaniline, polyacetylene, the derivative of polyacetylene and poly-p styrene sulfonic acid; And
By described conductive ink application in transparent substrates, through solidification, described transparent substrates forms conductive layer, obtain described flexible transparent conductive film, wherein, in described conductive layer, described nano-silver thread and described conducting polymer are scattered in described cured resin, and described nano-silver thread mutually overlaps and jointly forms conductive network with described conducting polymer.
Wherein in an embodiment, before by the step of described conductive ink application in described transparent substrates, also comprise the step of described transparent substrates being carried out to Ultrasonic Cleaning process, the step of described Ultrasonic Cleaning is specially: by each ultrasonic cleaning 10 ~ 15 minutes in deionized water, acetone and alcohol successively of described transparent substrates.
Wherein in an embodiment, the step that described conducting polymer, nano-silver thread and cured resin mix in described solvent is specially: described conducting polymer is mixed with described cured resin in described solvent, then adds described nano-silver thread.
Above-mentioned flexible transparent conductive film conductive layer is by adding at least one in polypyrrole, the derivative of polypyrrole, polythiophene, the derivative of polythiophene, polyaniline, the derivative of polyaniline, polyacetylene, the derivative of polyacetylene, poly-p styrene sulfonic acid as conducting polymer, conducting polymer relies on the delocalizedπelectron of carrying throughout in molecule to realize the transmission of electric current, and nano-silver thread mutually overlaps and jointly forms conductive network with conducting polymer, thus add the mobility of charge carrier, then add the electric conductivity of flexible transparent conductive film; And by adding above-mentioned conducting polymer, under the prerequisite obtaining equal conductivity, decreasing the content of nano-silver thread, thus improving the light transmittance of flexible transparent conductive film.
Accompanying drawing explanation
Fig. 1 is the structural representation of the flexible transparent conductive film of an execution mode;
Fig. 2 is preparation method's flow chart of the flexible transparent conductive film of an execution mode;
Fig. 3 is the scanning electron microscope (SEM) photograph of the flexible transparent conductive film of embodiment 2;
Fig. 4 is the scanning electron microscope (SEM) photograph of the flexible transparent conductive film of comparative example 1;
Fig. 5 is the light transmittance figure of the flexible transparent conductive film of transparent substrates, embodiment 2 and comparative example 1.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments flexible transparent conductive film and preparation method thereof is described in further detail below.
As shown in Figure 1, the square resistance of the flexible transparent conductive film 100 of an execution mode mostly is 82 Ω/sq most; And this flexible transparent conductive film 100 reaches more than 84% in the spectral region iuuminting rate of 350 ~ 700 nanometers.
This flexible transparent conductive film 100 comprises transparent substrates 110 and is laminated in the conductive layer 120 in transparent substrates 110.
Transparent substrates 110 is flexible and transparent substrate.Wherein, the thickness of transparent substrates 110 is 0.1 ~ 2 millimeter.
Preferably, the visible light transmittance rate of transparent substrates 110 is more than 70%.
Preferably, the material of transparent substrates 110 is selected from the one in PETG, Merlon, polytetrafluoroethylene and polymethyl methacrylate, and above-mentioned material in heating or cooling procedure, obvious variable color, crystallization or decomposing phenomenon can not occur; And adopt the light transmittance of the transparent substrates 110 of above-mentioned material all more than 70%.
The thickness of conductive layer 120 is 0.1 ~ 100 micron.
The material of conductive layer 120 comprises conducting polymer, nano-silver thread and cured resin.Wherein, the mass percent of conducting polymer, nano-silver thread and cured resin is 3 ~ 10:5 ~ 50:18 ~ 25.Preferred, the mass percent of conducting polymer, nano-silver thread and cured resin is 5:18:23.
Nano-silver thread and conducting polymer are scattered in cured resin, and nano-silver thread mutually overlaps and jointly forms conductive network with conducting polymer, thus form the conductive path of random overlap joint.Namely conducting polymer is filled between nano-silver thread, thus increases the electric conductivity of conductive layer 120.Wherein, the electric conductivity by regulating the loading of nano-silver thread to change conductive film.
Conducting polymer can increase the migration of charge carrier, thus increases the conductivity of flexible transparent conductive film 100.
Conducting polymer is selected from least one in polypyrrole, the derivative of polypyrrole, polythiophene, the derivative of polythiophene, polyaniline, the derivative of polyaniline, polyacetylene, the derivative of polyacetylene and poly-p styrene sulfonic acid.These conducting polymers are mostly structural type macromolecule, rely on the delocalizedπelectron of carrying throughout in molecule can realize the transmission of electric current, therefore, the mobility of charge carrier can be increased by adding above-mentioned conducting polymer, then adding the conductivity of flexible transparent conductive film 100.
Wherein, the derivative of polypyrrole is poly-3,4-ethyl dioxypyrrole, poly-(in 3-acyl group) pyrroles-[2,5-bis-(p-nitrophenyl methylene)] etc.
Wherein, the derivative of polythiophene is poly-3,2-bromo thiophenes, gathers 3,2-methoxybenzene thiophene, poly-3,4-rthylene dioxythiophene etc.
Wherein, the derivative of polyaniline is poly-m-anisidine, poly-omethylaniline etc.
Wherein, the derivative of polyacetylene is polyphenylacetylene, polyphenylacetylene acid amides etc.
Preferably, the diameter of nano-silver thread is 12 ~ 100 nanometers, and length is 10 ~ 60 microns.
Mechanical property and the switching performance of flexible transparent conductive film 100 determine primarily of cured resin.Cured resin adds the adhesive force of silver-colored line transparent substrates 110, makes the unlikely landing of silver-colored line.Cured resin is selected from the one in epoxy resin, polyurethane resin, acrylic resin, gum arabic, polyvinyl alcohol and organic silica gel.These cured resins, all containing active group, are easy to solidification.
Wherein, epoxy resin is selected from least one in bisphenol A type epoxy resin and novolac epoxy resin.
The material of the conductive layer 120 of above-mentioned flexible transparent conductive film 100 comprises conducting polymer, nano-silver thread and cured resin, wherein, nano-silver thread is scattered in cured resin, and overlap joint forms conductive network mutually, thus formation conductive path, and by nano-silver thread, conducting polymer and cured resin are mixed to form conductive layer 120, add the adhesive force of nano-silver thread in transparent substrates 110, thus ensure that in use, the electric conductivity of flexible transparent conductive film 100 can not change; By adding at least one in polypyrrole, the derivative of polypyrrole, polythiophene, the derivative of polythiophene, polyaniline, the derivative of polyaniline, polyacetylene, the derivative of polyacetylene, poly-p styrene sulfonic acid as conducting polymer, nano-silver thread mutually overlaps and jointly forms conductive network with conducting polymer, add the mobility of charge carrier, thus add the electric conductivity of flexible transparent conductive film 100; And add above-mentioned conducting polymer, while increase electric conductivity, decrease the content of nano-silver thread, thus improve the light transmittance of flexible transparent conductive film 100.
As shown in Figure 2, the preparation method of the flexible transparent conductive film of an execution mode, can be used for preparing above-mentioned flexible transparent conductive film.The preparation method of this flexible transparent conductive film comprises the steps:
Step S210: conducting polymer, nano-silver thread and cured resin are mixed in solvent, forms electrically conductive ink.
Wherein, the mass percent of conducting polymer, nano-silver thread and cured resin is 3 ~ 10:5 ~ 50:18 ~ 25.Preferred, the mass percent of conducting polymer, nano-silver thread and cured resin is 5:18:23.
Conducting polymer is selected from least one in polypyrrole, the derivative of polypyrrole, polythiophene, the derivative of polythiophene, polyaniline, the derivative of polyaniline, polyacetylene, the derivative of polyacetylene and poly-p styrene sulfonic acid.
Wherein, the derivative of polypyrrole is poly-3,4-ethyl dioxypyrrole, poly-(in 3-acyl group) pyrroles-[2,5-bis-(p-nitrophenyl methylene)] etc.
Wherein, the derivative of polythiophene is poly-3,2-bromo thiophenes, gathers 3,2-methoxybenzene thiophene, poly-3,4-rthylene dioxythiophene etc.
Wherein, the derivative of polyaniline is poly-m-anisidine, poly-omethylaniline etc.
Wherein, the derivative of polyacetylene is polyphenylacetylene, polyphenylacetylene acid amides etc.
Preferably, the diameter of nano-silver thread is 12 ~ 100 nanometers, and length is 10 ~ 60 microns.
Mechanical property and the switching performance of flexible transparent conductive film determine primarily of cured resin.Cured resin adds the adhesive force of silver-colored line transparent substrates, makes the unlikely landing of silver-colored line.Cured resin is selected from the one in epoxy resin, polyurethane resin, acrylic resin, gum arabic, polyvinyl alcohol and organic silica gel.These cured resins, all containing active group, are easy to solidification.
Wherein, epoxy resin is selected from least one in bisphenol A type epoxy resin and novolac epoxy resin.
Wherein, solvent is at least one in butyl glycidyl acid, dibutyl phthalate, NVP, glycerine, ethyl acetate, toluene, terpinol, deionized water, ethylene glycol, butyl acetate and cyclohexanone.
Concrete, the step that conducting polymer, nano-silver thread and cured resin mix in solvent is specially: conducting polymer is mixed with cured resin in solvent, then adds nano-silver thread.
Wherein, in the step mix conducting polymer, nano-silver thread and cured resin in solvent, the auxiliary agents such as plasticizer, coupling agent, defoamer, surfactant are also added.
Wherein, plasticizer is phthalate, such as, and dioctyl phthalate, diisooctyl phthalate or dibutyl phthalate; Coupling agent can be butyl titanate or alkene acyloxy silane; Defoamer is tributyl phosphate, n-butanol or octanol; Surfactant is lecithin, oleic acid, polyethylene glycol or zinc naphthenate.
Step S220: by conductive ink application in transparent substrates, through solidification, form conductive layer on a transparent substrate, obtain flexible transparent conductive film, wherein, in the conductive layer, nano-silver thread and conducting polymer are scattered in cured resin, and nano-silver thread mutually overlaps and jointly forms conductive network with conducting polymer.
Wherein, by the step of conductive ink application in transparent substrates, the method for coating is roll coating process, spraying process, liquid level sedimentation, silk screen print method or ink-jet printing process.
Concrete, before by the step of conductive ink application in transparent substrates, also comprise the step of transparent substrates being carried out to Ultrasonic Cleaning process.Wherein, the step that transparent substrates carries out Ultrasonic Cleaning process is specially: by transparent substrates each ultrasonic cleaning 10 ~ 15 minutes in deionized water, acetone and alcohol successively.
Wherein, transparent substrates is flexible and transparent substrate.Wherein, the thickness of transparent substrates is 0.1 ~ 2 millimeter.
Preferably, the visible light transmittance rate of transparent substrates is more than 70%.
The material of transparent substrates is selected from the one in PETG, Merlon, polytetrafluoroethylene and polymethyl methacrylate.
Wherein, the step of solidification is specially: solidify under room temperature or heating condition.
Wherein, the thickness of conductive layer is 0.1 ~ 100 micron.
The square resistance of flexible transparent conductive film mostly is 82 Ω/sq most; And this flexible transparent conductive film reaches more than 84% in the spectral region iuuminting rate of 350 ~ 700 nanometers.
Above-mentioned flexible transparent conductive film, by first conducting polymer, nano-silver thread and cured resin being mixed in solvent, is then coated in transparent substrates, through solidifying and get final product, only needs primary coating, and preparation process is comparatively simple, is conducive to enhancing productivity.
Be below specific embodiment part:
Embodiment 1
The preparation process of the flexible transparent conductive film of the present embodiment is as follows:
(1) conducting polymer, cured resin, solvent, plasticizer, coupling agent, defoamer and surfactant are placed in homogenizer and stir mixing, after mixing, add nano-silver thread, continue to be uniformly mixed and to disperse, form electrically conductive ink, wherein, the mass percent of conducting polymer, nano-silver thread and cured resin is 5:16:20, conducting polymer is poly-3,4-ethyl dioxypyrrole, cured resin is bisphenol A type epoxy resin and F-51 novolac epoxy resin, and the diameter of nano-silver thread is 20 ~ 65 nanometers, and length is 10 ~ 30 microns; Solvent is butyl glycidyl acid and dibutyl phthalate, and the mass percent of solvent and cured resin is 3:1; Plasticizer is dioctyl phthalate, and the mass percent of plasticizer and cured resin is 1:18; Coupling agent is butyl titanate, and the mass percent of coupling agent and cured resin is 0.5:18; Defoamer is tributyl phosphate, and the mass percent of defoamer and cured resin is 0.1:18; Surfactant is lecithin, and the mass percent of lecithin and cured resin is 1:9.
(2) thickness is provided to be the transparent substrates of 0.1mm, the material of transparent substrates is Merlon, and transparent substrates visible light transmittance rate be 70%, to transparent substrates successively in deionized water, each Ultrasonic Cleaning 15 minutes in acetone and alcohol, then adopt roll coating process by conductive ink application in transparent substrates, solidify 3 hours at 120 DEG C, form the conductive layer that thickness is 25 microns on a transparent substrate, wherein, in the conductive layer, nano-silver thread and conducting polymer are scattered in cured resin, and nano-silver thread overlaps mutually, and jointly form conductive network with conducting polymer, obtain flexible transparent conductive film.
The square resistance of the flexible transparent conductive film adopting FOUR-POINT PROBE METER test test the present embodiment to obtain.
Ultraviolet-uisible spectrophotometer is adopted to test the light transmittance of the flexible transparent conductive film of the present embodiment.
Using the flexible transparent conductive film of cross-cut tester to the present embodiment do lattice card pattern cut and penetrate, testing the conductive layer of the flexible transparent conductive film of the present embodiment and the adhesive force of transparent substrates by leaving number of squares.
The square resistance of the flexible transparent conductive film of the present embodiment, light transmittance and adhesive force, in table 1.
Embodiment 2
The preparation process of the flexible transparent conductive film of the present embodiment is as follows:
(1) by conducting polymer, cured resin, solvent, plasticizer, coupling agent, defoamer and surfactant are placed in homogenizer and stir mixing, after mixing, add nano-silver thread, continue to be uniformly mixed and to disperse, form electrically conductive ink, wherein, conducting polymer, the mass percent of nano-silver thread and cured resin is 5:18:23, conducting polymer is poly-m-anisidine and poly-(in 3-acyl group) pyrroles-[2, 5-bis-(p-nitrophenyl methylene)], cured resin is polyurethane resin (buying in the Xianyang essence bright Chemical Co., Ltd. of mail transfer), the diameter of nano-silver thread is 12 ~ 45 nanometers, length is 25 ~ 40 microns, solvent is NVP and glycerine, and the mass percent of solvent and cured resin is 2.5:1, plasticizer is diisooctyl phthalate, and the mass percent of plasticizer and cured resin is 0.8:23, coupling agent is butyl titanate, and the mass percent of coupling agent and cured resin is 0.8:23, defoamer is n-butanol, and the mass percent of defoamer and cured resin is 0.1:23, surfactant is lecithin, and the mass percent of surfactant and cured resin is 2:23.
(2) thickness is provided to be the transparent substrates of 1mm, the material of transparent substrates is PETG, and transparent substrates visible light transmittance rate be more than 80%, to transparent substrates successively in deionized water, each Ultrasonic Cleaning 10 minutes in acetone and alcohol, adopt ink-jet printing process by the transparent substrates of conductive ink application after hydrophilic treated, in 90 DEG C of solidifications 4 hours, form the conductive layer that thickness is 100 microns on a transparent substrate, wherein, in the conductive layer, nano-silver thread and conducting polymer are scattered in cured resin, and nano-silver thread overlaps mutually, and jointly form conductive network with conducting polymer, obtain flexible transparent conductive film.
The square resistance of the flexible transparent conductive film of the present embodiment, light transmittance and adhesive force, in table 1.
Embodiment 3
The preparation process of the flexible transparent conductive film of the present embodiment is as follows:
(1) conducting polymer, cured resin, solvent, plasticizer, coupling agent, defoamer and surfactant are placed in homogenizer and stir mixing, after mixing, add nano-silver thread, continue to be uniformly mixed and to disperse, form electrically conductive ink, wherein, the mass percent of conducting polymer, nano-silver thread and cured resin is 10:20:25, conducting polymer is poly-3,2-bromo thiophene, polythiophene and polyaniline, cured resin is polyester acrylate resin (MR-200), and the diameter of nano-silver thread is 18 ~ 45 nanometers, and length is 23 ~ 35 microns; Solvent is ethyl acetate and toluene, and the mass percent of solvent and cured resin is 3:1; Plasticizer is dibutyl phthalate, and the mass percent of plasticizer and cured resin is 1.2:20; Coupling agent is alkene acyloxy silane, and the mass percent of coupling agent and cured resin is 1:10; Defoamer is n-butanol, and the mass percent of defoamer and cured resin is 0.3:20; Surfactant is polyethylene glycol, and the mass percent of surfactant and cured resin is 3:20.
(2) thickness is provided to be the transparent substrates of 2mm, the material of transparent substrates is polytetrafluoroethylene, and transparent substrates visible light transmittance rate be more than 75%, to transparent substrates successively in deionized water, each Ultrasonic Cleaning 10 minutes in acetone and alcohol, adopt silk screen print method by conductive ink application in transparent substrates, in ambient temperature curing 24 hours, form the conductive layer that thickness is 50 microns on a transparent substrate, wherein, in the conductive layer, nano-silver thread and conducting polymer are scattered in cured resin, and nano-silver thread overlaps mutually, and jointly form conductive network with conducting polymer, obtain flexible transparent conductive film.
The square resistance of the flexible transparent conductive film of the present embodiment, light transmittance and adhesive force, in table 1.
Embodiment 4
The preparation process of the flexible transparent conductive film of the present embodiment is as follows:
(1) conducting polymer, cured resin, solvent, plasticizer, coupling agent, defoamer and surfactant are placed in homogenizer and stir mixing, after mixing, add nano-silver thread, continue to be uniformly mixed and to disperse, form electrically conductive ink, wherein, the mass percent of conducting polymer, nano-silver thread and cured resin is 3:15:21, conducting polymer is poly-p styrene sulfonic acid and poly-3,4-ethene dioxythiophene, cured resin is gum arabic, and the diameter of nano-silver thread is 50 ~ 83 nanometers, and length is 20 ~ 40 microns; Solvent is terpinol, and the mass percent of solvent and cured resin is 2.5:1; Plasticizer is dioctyl phthalate, and the mass percent of plasticizer and cured resin is 2:25; Coupling agent is alkene acyloxy silane, and the mass percent of coupling agent and cured resin is 0.3:25; Defoamer is tributyl phosphate, and the mass percent of defoamer and cured resin is 0.1:25; Surfactant is polyvinylpyrrolidone, and the mass percent of surfactant and cured resin is 0.1:1.
(2) thickness is provided to be the transparent substrates of 1.5mm, the material of transparent substrates is plexiglass, and transparent substrates visible light transmittance rate be 85%, to transparent substrates successively in deionized water, each Ultrasonic Cleaning 15 minutes in acetone and alcohol, adopt liquid level sedimentation by conductive ink application in transparent substrates, in 120 DEG C of solidifications 3 hours, form the conductive layer that thickness is 5 microns on a transparent substrate, wherein, in the conductive layer, nano-silver thread and conducting polymer are scattered in cured resin, and nano-silver thread overlaps mutually, and jointly form conductive network with conducting polymer, obtain flexible transparent conductive film.
The square resistance of the flexible transparent conductive film of the present embodiment, light transmittance and adhesive force, in table 1.
Embodiment 5
The preparation process of the flexible transparent conductive film of the present embodiment is as follows:
(1) conducting polymer, cured resin, solvent, plasticizer, coupling agent, defoamer and surfactant are placed in homogenizer and stir mixing, after mixing, add nano-silver thread, continue to be uniformly mixed and to disperse, form electrically conductive ink, wherein, the mass percent of conducting polymer, nano-silver thread and cured resin is percentage is 10:5:18, conducting polymer is polyphenylacetylene, polyacetylene and poly-omethylaniline, cured resin is polyvinyl alcohol, the diameter of nano-silver thread is 75 ~ 100 nanometers, and length is 38 ~ 60 microns; Solvent is deionized water and ethylene glycol, and the mass percent of solvent and cured resin is 3.2:1; Plasticizer is dibutyl phthalate, and the mass percent of plasticizer and cured resin is 2:25; Coupling agent is alkene acyloxy silane, and the mass percent of coupling agent and cured resin is 1:25; Defoamer is octanol, and the mass percent of defoamer and cured resin is 0.2:25; Surfactant is lecithin, and the mass percent of surfactant and cured resin is 3:25.
(2) thickness is provided to be the transparent substrates of 1mm, the material of transparent substrates is polymethacrylate resin, and transparent substrates visible light transmittance rate be 90%, to transparent substrates successively in deionized water, each Ultrasonic Cleaning 15 minutes in acetone and alcohol, adopt spraying process by the transparent substrates of conductive ink application after hydrophilic treated, in 100 DEG C of solidifications 4 hours, form the conductive layer that thickness is 1 micron on a transparent substrate, wherein, in the conductive layer, nano-silver thread and conducting polymer are scattered in cured resin, and nano-silver thread overlaps mutually, and jointly form conductive network with conducting polymer, obtain flexible transparent conductive film.
The square resistance of the flexible transparent conductive film of the present embodiment, light transmittance and adhesive force, in table 1.
Embodiment 6
The preparation process of the flexible transparent conductive film of the present embodiment is as follows:
(1) conducting polymer, cured resin, solvent, plasticizer, coupling agent, defoamer and surfactant are placed in homogenizer and stir mixing, after mixing, add nano-silver thread, continue to be uniformly mixed and to disperse, form electrically conductive ink, wherein, the mass percent of conducting polymer, nano-silver thread and cured resin is 5:50:20, conducting polymer is polypyrrole, poly-3, the mixture of 2-methoxybenzene thiophene and polyphenylacetylene acid amides, cured resin is organic silica gel, and the diameter of nano-silver thread is 30 ~ 60 nanometers, and length is 12 ~ 32 microns; Solvent is butyl acetate, toluene and cyclohexanone, and the mass percent of solvent and cured resin is 3:1; Plasticizer is dibutyl phthalate, and the mass percent of plasticizer and cured resin is 1.2:20; Coupling agent is alkene acyloxy silane, and the mass percent of coupling agent and cured resin is 1:10; Defoamer is n-butanol, and the mass percent of defoamer and cured resin is 0.3:20; Surfactant is polyethylene glycol, and the mass percent of surfactant and cured resin is 3:20.
(2) thickness is provided to be the transparent substrates of 2mm, the material of transparent substrates is polytetrafluoroethylene, and transparent substrates visible light transmittance rate be more than 75%, to transparent substrates successively in deionized water, each Ultrasonic Cleaning 10 minutes in acetone and alcohol, adopt silk screen print method by conductive ink application in transparent substrates, in ambient temperature curing 24 hours, form the conductive layer that thickness is 0.1 micron on a transparent substrate, wherein, in the conductive layer, nano-silver thread and conducting polymer are scattered in cured resin, and nano-silver thread overlaps mutually, and jointly form conductive network with conducting polymer, obtain flexible transparent conductive film.
The square resistance of the flexible transparent conductive film of the present embodiment, light transmittance and adhesive force, in table 1.
Comparative example 1
The preparation process of the flexible transparent conductive film of comparative example 1 is as follows:
(1) cured resin, solvent, plasticizer, coupling agent, defoamer and surfactant are placed in homogenizer and stir mixing, after mixing, add nano-silver thread, continue to be uniformly mixed and to disperse, form electrically conductive ink, wherein, the mass percent of nano-silver thread and cured resin is 18:23, cured resin is polyurethane resin (buying in the Xianyang essence bright Chemical Co., Ltd. of mail transfer), and the diameter of nano-silver thread is 12 ~ 45 nanometers, and length is 25 ~ 40 microns; Solvent is NVP and glycerine, and the mass percent of solvent and cured resin is 2.5:1; Plasticizer is diisooctyl phthalate, and the mass percent of plasticizer and cured resin is 0.8:23; Coupling agent is butyl titanate, and the mass percent of coupling agent and cured resin is 0.8:23; Defoamer is n-butanol, and the mass percent of defoamer and cured resin is 0.1:23; Surfactant is lecithin, and the mass percent of surfactant and cured resin is 2:23.
(2) thickness is provided to be the transparent substrates of 1mm, the material of transparent substrates is PETG, and transparent substrates visible light transmittance rate be more than 80%, to transparent substrates successively in deionized water, each Ultrasonic Cleaning 10 minutes in acetone and alcohol, adopt ink-jet printing process by the transparent substrates of conductive ink application after hydrophilic treated, in 90 DEG C of solidifications 4 hours, form the conductive layer that thickness is 100 microns on a transparent substrate, wherein, in the conductive layer, nano-silver thread is scattered in cured resin, and nano-silver thread overlaps formation conductive network mutually, obtain flexible transparent conductive film.
The square resistance of the flexible transparent conductive film of comparative example 1, light transmittance and adhesive force, in table 1.
Comparative example 2
The preparation process of the flexible transparent conductive film of comparative example 2 is as follows:
(1) cured resin, solvent, plasticizer, coupling agent, defoamer and surfactant are placed in homogenizer and stir mixing, after mixing, add nano-silver thread, continue to be uniformly mixed and to disperse, form electrically conductive ink, wherein, the mass percent of nano-silver thread and cured resin is 50:23, cured resin is polyurethane resin (buying in the Xianyang essence bright Chemical Co., Ltd. of mail transfer), and the diameter of nano-silver thread is 12 ~ 45 nanometers, and length is 25 ~ 40 microns; Solvent is NVP and glycerine, and the mass percent of solvent and cured resin is 2.5:1; Plasticizer is diisooctyl phthalate, and the mass percent of plasticizer and cured resin is 0.8:23; Coupling agent is butyl titanate, and the mass percent of coupling agent and cured resin is 0.8:23; Defoamer is n-butanol, and the mass percent of defoamer and cured resin is 0.1:23; Surfactant is lecithin, and the mass percent of surfactant and cured resin is 2:23.
(2) thickness is provided to be the transparent substrates of 1mm, the material of transparent substrates is PETG carbonic ester, and transparent substrates visible light transmittance rate be greater than 80%, to transparent substrates ultrasonic cleaning 15 minutes in deionized water, acetone, alcohol; Adopt ink-jet printing process by the transparent substrates of conductive ink application after cleaning process, solidify 4 hours at 90 DEG C, form the conductive layer that thickness is about 30 microns on a transparent substrate, wherein, in the conductive layer, nano-silver thread is scattered in cured resin, and nano-silver thread overlaps formation conductive network mutually, obtains flexible transparent conductive film.
The square resistance of the flexible transparent conductive film of comparative example 2, light transmittance and adhesive force, in table 1.
Fig. 3 and Fig. 4 is respectively the scanning electron microscope (SEM) photograph of the flexible transparent conductive film of embodiment 2 and comparative example 1, as can be seen from the figure adds the formation that conducting polymer does not affect nano-silver thread conductive network in conductive film.
The light transmittance figure of Fig. 5 to be material be flexible transparent conductive film of the transparent substrates of PETG, the flexible transparent conductive film of embodiment 2 and comparative example 1, as can be seen from the figure the conductivity that conducting polymer can increase film is added, and under the basis of equal conductive condition, add the content that conducting polymer can lower nano-silver thread in conductive layer, and then add the light transmittance of film.
The square resistance of flexible transparent conductive film of the embodiment 1 ~ 6 that table 1 represents and comparative example 1 ~ 2, light transmittance and adhesive force.
Table 1
| Square resistance (Ω/sq) | Light transmittance (%) | Adhesive force | |
| Embodiment 1 | 64 | 84 | 87/100 |
| Embodiment 2 | 57 | 88 | 89/100 |
| Embodiment 3 | 60 | 85 | 91/100 |
| Embodiment 4 | 70 | 88 | 84/100 |
| Embodiment 5 | 78 | 92 | 88/100 |
| Embodiment 6 | 82 | 90 | 88/100 |
| Comparative example 1 | 77 | 82 | 89/100 |
| Comparative example 2 | 70 | 80 | 90/100 |
As can be seen from Table 1, the square resistance of the flexible transparent conductive film of embodiment 1 ~ 6 is relevant with the content of the nano-silver thread in conductive layer and the thickness of conductive layer, by the square resistance of embodiment 2 with comparative example 1, the interpolation of conducting polymer can significantly improve the conductivity of flexible transparent conductive film, therefore, the flexible transparent conductive film of embodiment 1 ~ 6 has good electric conductivity.
It can also be seen that from table 1, the light transmittance of the flexible transparent conductive film of embodiment 1 ~ 6 is at least 84%, namely more than 84%, and comparative example 1 be only 82%, far below the light transmittance of the flexible transparent conductive film of embodiment 1 ~ 6, meanwhile, comparative example 2 reaches the square resistance with embodiment 2 almost indifference by improving nano-silver thread content in the conductive layer, but light transmittance but obviously declines.Therefore, add the conductivity that conducting polymer not only can improve film, also can increase the light transmittance of film.
It can also be seen that from table 1, adhesive force between the conductive layer of the adhesive force between the conductive layer of the flexible transparent conductive film of embodiment 1 ~ 6 and transparent substrates and comparative example 1, comparative example 2 and transparent substrates is suitable, therefore, conducting polymer interpolation on the adhesive force between conductive layer and transparent substrates almost without impact.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a flexible transparent conductive film, it is characterized in that, comprise transparent substrates and be laminated in the conductive layer in described transparent substrates, the material of described conductive layer comprises conducting polymer, nano-silver thread and cured resin, described nano-silver thread and described conducting polymer are scattered in described cured resin, and described nano-silver thread overlaps mutually, and jointly form conductive network with described conducting polymer, described conducting polymer is selected from polypyrrole, the derivative of polypyrrole, polythiophene, the derivative of polythiophene, polyaniline, the derivative of polyaniline, polyacetylene, at least one in the derivative of polyacetylene and poly-p styrene sulfonic acid.
2. flexible transparent conductive film according to claim 1, is characterized in that, the diameter of described nano-silver thread is 12 ~ 100 nanometers, and length is 10 ~ 60 microns.
3. flexible transparent conductive film according to claim 1, is characterized in that, described cured resin is selected from the one in epoxy resin, polyurethane resin, acrylic resin, gum arabic, polyvinyl alcohol and organic silica gel.
4. flexible transparent conductive film according to claim 1, is characterized in that, the mass percent of described conducting polymer, nano-silver thread and cured resin is 3 ~ 10:5 ~ 50:18 ~ 25.
5. flexible transparent conductive film according to claim 1, is characterized in that, the material of described transparent substrates is selected from the one in PETG, Merlon, polytetrafluoroethylene and polymethyl methacrylate.
6. flexible transparent conductive film according to claim 1, is characterized in that, the visible light transmittance rate of described transparent substrates is more than 70%.
7. flexible transparent conductive film according to claim 1, is characterized in that, the thickness of described conductive layer is 0.1 ~ 100 micron.
8. a preparation method for flexible transparent conductive film, is characterized in that, comprises the steps:
Conducting polymer, nano-silver thread and cured resin are mixed in solvent, form electrically conductive ink, wherein, described conducting polymer is selected from least one in polypyrrole, the derivative of polypyrrole, polythiophene, the derivative of polythiophene, polyaniline, the derivative of polyaniline, polyacetylene, the derivative of polyacetylene and poly-p styrene sulfonic acid; And
By described conductive ink application in transparent substrates, through solidification, described transparent substrates forms conductive layer, obtain described flexible transparent conductive film, wherein, in described conductive layer, described nano-silver thread and described conducting polymer are scattered in described cured resin, and described nano-silver thread mutually overlaps and jointly forms conductive network with described conducting polymer.
9. the preparation method of flexible transparent conductive film according to claim 8, it is characterized in that, before by the step of described conductive ink application in described transparent substrates, also comprise the step of described transparency carrier being carried out to Ultrasonic Cleaning process, the step of described Ultrasonic Cleaning is specially: by each ultrasonic cleaning 10 ~ 15 minutes in deionized water, acetone and alcohol successively of described transparent substrates.
10. the preparation method of flexible transparent conductive film according to claim 8, it is characterized in that, the step that described conducting polymer, nano-silver thread and cured resin mix in described solvent is specially: described conducting polymer is mixed with described cured resin in described solvent, then adds described nano-silver thread.
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