CN114694877A - Nano-silver wire composite transparent conductive film - Google Patents
Nano-silver wire composite transparent conductive film Download PDFInfo
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- CN114694877A CN114694877A CN202011574691.8A CN202011574691A CN114694877A CN 114694877 A CN114694877 A CN 114694877A CN 202011574691 A CN202011574691 A CN 202011574691A CN 114694877 A CN114694877 A CN 114694877A
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
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- HTXMGVTWXZBZNC-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonic acid Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S(O)(=O)=O)=C1 HTXMGVTWXZBZNC-UHFFFAOYSA-N 0.000 description 1
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- XEYHWMQDXTVNJW-UHFFFAOYSA-N dihexyl butanedioate Chemical compound CCCCCCOC(=O)CCC(=O)OCCCCCC XEYHWMQDXTVNJW-UHFFFAOYSA-N 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
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- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The invention provides a nano-silver wire composite transparent conductive film, which sequentially consists of a protective adhesive layer, a nano-silver wire layer, a polythiophene conductive layer, a base material, a bottom layer and a hardening layer from top to bottom, wherein the polythiophene conductive layer is formed by coating and drying a polythiophene conductive layer coating liquid; the polythiophene conductive layer coating liquid is prepared from the following raw materials in percentage by mass: 3-15% of polythiophene dispersion liquid, 1-5% of pH regulator, 0.1-15% of modified hydrophilic PET water latex, 4-19% of ethanol, 0.1-10% of surfactant, 1-5% of dimethyl sulfoxide and the balance of deionized water. The polythiophene conducting layer ensures the fastness between the polythiophene conducting layer and the base material and between the polythiophene conducting layer and the nano silver wire layer, the formed conducting surface effectively makes up the defects of a nano silver wire mesh conducting structure, and the conducting performance and the optical performance of the nano silver wire transparent conducting film are greatly improved.
Description
Technical Field
The invention relates to a conductive film, in particular to a nano silver wire composite transparent conductive film.
Background
The transparent conductive film is an electrothermal conversion material which is obtained by compounding metal or metal oxide on a transparent medium through a special process and has high light transmission performance and high electrical conductivity.
The transparent conductive film is a basic material of a photoelectric device and is widely applied to electrodes of liquid crystal displays, touch screens, thin-film solar cells and the like.
Currently, common transparent conductive films on the market are ITO glass (tin-doped indium oxide) and ITO films, which support the great half of the walls of the relevant market.
In recent years, the emerging application market is in a continuous explosion process, and particularly, the development of the emerging application market is accelerated with the arrival of the 5G era, wherein the emerging application market comprises large and medium-sized touch screens, smart homes, OLED flexible displays, OLED lighting and the like. The high requirements of the emerging application markets on the technology far exceed the application limit of the ITO material, and become the restriction factors of the emerging technologies and the market development in China.
As a novel transparent conductive film, the nano silver wire has better optical property, high specific surface area, high light transmittance, better electric and thermal conductivity, flexing resistance and the like, has very vigorous market demand in the electronic field, particularly in the application fields of medium and large touch screens, electronic curtains (PDLC) in intelligent homes, flexible displays and the like, and has wide development prospect.
In the prior art, the principle of the conventional nano silver wire transparent conductive film is that nano silver wire ink is leveled on a substrate in a coating mode, and silver wires are mutually overlapped to form a net structure to form a current path. The hollow part of the network structure of the existing nano silver wire transparent conductive film has larger influence on the conductivity of the hollow part because no conductive substance exists.
Disclosure of Invention
In order to solve the problems, the invention provides the nano silver wire composite transparent conductive film, the polythiophene conductive layer is arranged to ensure the fastness between the polythiophene conductive layer and the base material and between the polythiophene conductive layer and the nano silver wire layer, the formed conductive surface effectively makes up the defects of a nano silver wire mesh-shaped conductive structure, and the conductive performance and the optical performance of the nano silver wire transparent conductive film are greatly improved.
The object of the invention is achieved in the following way: a nano-silver wire composite transparent conductive film is sequentially composed of a protective adhesive layer, a nano-silver wire layer, a polythiophene conductive layer, a base material, a bottom layer and a hardening layer from top to bottom, wherein the polythiophene conductive layer is formed by coating and drying a polythiophene conductive layer coating liquid; the polythiophene conductive layer coating liquid is prepared from the following raw materials in percentage by mass: 3-15% of polythiophene dispersion liquid, 1-5% of pH regulator, 0.1-15% of modified hydrophilic PET water latex, 4-19% of ethanol, 0.1-10% of surfactant, 1-5% of dimethyl sulfoxide and the balance of deionized water.
The weight of the polythiophene in the polythiophene dispersion liquid is 1% -2%, and the conductivity of the polythiophene dispersion liquid is 300-500S/m.
The pH regulator is at least one of ethylenediamine and triethylamine.
The preparation method of the polythiophene conductive layer comprises the following steps: weighing deionized water, dimethyl sulfoxide, polythiophene dispersion liquid, a pH regulator, modified hydrophilic PET water latex, ethanol and a surfactant according to the formula ratio, and stirring at the stirring speed of 100-700 r/min for 5-30 min to obtain a polythiophene conductive layer coating liquid;
and coating the polythiophene conductive layer coating liquid on the non-hardened layer surface of the base material, and drying to obtain the polythiophene conductive layer.
The wet coating amount of the polythiophene conductive layer coating liquid is 5-50ml per square meter.
The drying condition of the polythiophene conductive layer coating liquid is 80-140 ℃, and the drying time is 1-5 min.
The surfactant is at least one of sodium diisooctyl succinate sulfonate or dihexyl succinate sulfonate.
The base material is a PET base material, and the thickness of the base material is 12-150 micrometers.
The main components of the polythiophene distribution solution are water-soluble polyelectrolyte polystyrene sulfonic acid and polyethylene dioxythiophene.
The modified hydrophilic PET water latex is water emulsion of modified hydrophilic polyethylene terephthalate.
The bottom layer is a polyurethane resin layer, a modified hydrophilic polyethylene terephthalate layer or an acrylic resin layer; the hardening layer is formed by coating hardening liquid and then drying; the hardening liquid mainly comprises the following components in percentage by weight: 2.5-7% of pure acrylic resin, 7.5-18% of ten-functional polyurethane polymer, 16-26% of difunctional polyurethane polymer, 5-10% of reactive diluent, 1-4% of photoinitiator and 45-55% of solvent.
The thickness of the bottom layer is 1-10um, the thickness of the hardening layer is 1-5um, and the thickness of the protective adhesive layer is 50-500 nm.
Compared with the prior art, the nano silver wire composite transparent conductive film provided by the invention has the advantages that the firmness between the nano silver wire composite transparent conductive film and the substrate is ensured due to the arrangement of the polythiophene conductive layer, the formed conductive surface effectively makes up the defect of a nano silver wire mesh-shaped conductive structure, and the conductive performance and the optical performance of the nano silver wire transparent conductive film are greatly improved.
Drawings
FIG. 1 is a schematic structural view of the present invention;
the figure is as follows: 1. the protective adhesive layer, 2, the nano silver wire layer, 3, the polythiophene conductive layer, 4, the base material, 5, the bottom layer and 6, the hardening layer.
Detailed Description
As shown in fig. 1, the composite transparent conductive film of the nano silver wire is sequentially composed of a protective adhesive layer 1, a nano silver wire layer 2, a polythiophene conductive layer 3, a substrate 4, a bottom layer 5 and a hardening layer 6 from top to bottom, wherein the polythiophene conductive layer 3 is formed by coating and drying a polythiophene conductive layer coating liquid; the polythiophene conductive layer coating liquid is prepared from the following raw materials in percentage by mass: 3-15% of polythiophene dispersion liquid, 1-5% of pH regulator, 0.1-15% of modified hydrophilic PET water latex, 4-19% of ethanol, 0.1-10% of surfactant, 1-5% of dimethyl sulfoxide and the balance of deionized water.
The weight of the polythiophene in the polythiophene dispersion liquid is 1% -2%, and the conductivity of the polythiophene dispersion liquid is 300-500S/m.
The pH regulator is at least one of ethylenediamine and triethylamine.
The preparation method of the polythiophene conductive layer comprises the following steps: weighing deionized water, dimethyl sulfoxide, polythiophene dispersion liquid, a pH regulator, modified hydrophilic PET water latex, ethanol and a surfactant according to the formula ratio, and stirring at the stirring speed of 100-700 r/min for 5-30 min to obtain a polythiophene conductive layer coating liquid;
and coating the polythiophene conductive layer coating liquid on the non-hardened layer surface of the base material, and drying to obtain the polythiophene conductive layer. The coating mode can be a mode of micro-concave coating, and the drying condition can be heating drying at 30-130 ℃. Under the same other conditions, the effective content of thiophene accumulated on a unit surface in the bottom layer directly influences the conductivity of the conductive film, and generally, the higher the content of polythiophene is, the better the conductivity is; and vice versa.
The wet coating amount of the polythiophene conductive layer coating liquid is 5-50ml per square meter.
Preferably, the drying condition of the polythiophene conductive layer coating liquid is 80-140 ℃ and the drying time is 1-5 min.
The surfactant is at least one of 2-sodium sulfonate-diisooctyl succinate (sodium diisooctyl succinate sulfonate) and 2-sodium sulfonate-dihexyl succinate (sodium dihexyl succinate sulfonate).
The substrate is PET, COP or PI transparent film material.
The base material is a PET base material, and the thickness of the base material is 12-150 micrometers.
The main components of the polythiophene dispersion liquid are water-soluble polyelectrolyte polystyrene sulfonic acid and polyethylene dioxythiophene. The polythiophene dispersion may specifically be purchased from shanghai lier spring chemical company ltd, model QTA 02.
The modified hydrophilic latex is modified hydrophilic polyethylene glycol terephthalate water latex and aqueous emulsion of modified hydrophilic polyethylene glycol terephthalate, and the modified hydrophilic polyethylene glycol terephthalate is obtained by reacting polybasic acid or polybasic acid ester with hydrophilic groups with polyhydric alcohol. The hydrophilic group is one or more of isophthalic acid sulfonate and dimethyl isophthalate-5-sulfonate; the polybasic acid is terephthalic acid and isophthalic acid; the polybasic acid ester is one or more of dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate and diethyl isophthalate; the polyalcohol is ethylene glycol, polyethylene glycol, polyether glycol, bisphenol A, bisphenol S.
The modified hydrophilic polyethylene terephthalate is prepared into an aqueous emulsion with the polyester content of 20-40 percent by mass by using a phase inversion method or an emulsification method which are well known in the art, namely the aqueous latex, and the polyester content is preferably 25-35 percent.
The nano silver wire layer has the length of 10-50 micrometers and the diameter of 10-50 nanometers. Preferably, the nano-silver wire has a length of 15 to 40 micrometers and a diameter of 15 to 40 nanometers.
The preparation method of the nano silver wire composite transparent conductive film is a slit type extrusion coating method.
The bottom layer is a polyurethane resin layer, a modified hydrophilic polyethylene terephthalate layer or an acrylic resin layer. The function is to hold the upper part and the lower part and connect the base material and the hardening layer.
The hardened layer functions to increase light transmittance, reduce haze, and enhance scratch resistance and hardness. The hardening layer is formed by coating hardening liquid and then drying; the hardening liquid mainly comprises the following components in percentage by weight: 2.5-7% of pure acrylic resin, 7.5-18% of ten-functional polyurethane polymer, 16-26% of difunctional polyurethane polymer, 5-10% of reactive diluent, 1-4% of photoinitiator and 45-55% of solvent.
The protective glue layer is a silicon dioxide layer, a metal oxide layer, a thermosetting hardening resin layer or a photocuring hardening resin layer. The transparent protective layer may be formed by coating a thermosetting or photo-curing hardening resin on the nano silver wire layer.
The thickness of the bottom layer is 1-10um, the thickness of the hardening layer is 1-5um, and the thickness of the protective adhesive layer is 50-500 nm.
The conductive principle of the nano silver wire composite transparent conductive film provided by the invention is that the advantages of the conductive surface formed by the polythiophene conductive layer and the mesh conductive structure of the nano silver wire layer are complementary, so that the conductive performance of the conductive film is greatly improved.
The present invention is described in detail below with reference to specific embodiments, it should be noted that the embodiments are only used for further illustration of the present invention, and should not be construed as limiting the scope of the present invention, and those skilled in the art can make modifications and adaptations of the present invention based on the above-mentioned disclosure.
In the embodiments of the present application: the pet water latex is sexual hydrophilic polyethylene glycol terephthalate water latex, and is concretely Eastek resin Eastek 1300 (with the solid content of 30%) of Eastman chemical company for illustration; the polythiophene dispersion was obtained from shanghai lier spring chemical limited under model number QTA 02.
Example 1
The invention provides a composite nano silver wire transparent conductive film and a preparation method thereof, which sequentially comprises a protective adhesive layer, a nano silver wire layer, a polythiophene conductive layer, a base material, a bottom layer and a hardening layer from top to bottom, wherein the polythiophene conductive layer is prepared from the following raw materials in percentage by mass: 3% of polythiophene dispersion liquid, 1% of triethylamine, 0.5% of modified hydrophilic PET water latex, 5% of ethanol, 1% of 2-sodium sulfonate-diisooctyl succinate, 2% of dimethyl sulfoxide and the balance of deionized water. The polythiophene dispersion liquid in the polythiophene conducting layer has the polythiophene solid content of 1% and the conductivity of 300S/m; the pH regulator is ethylenediamine.
The preparation method of the nano silver wire composite transparent conductive film comprises the following steps:
(1) bottom layer
Firstly, coating a polyurethane resin solution on the pet surface by using a micro-concave coating mode, and heating at 30-130 ℃ to obtain the pet with a bottom layer; the thickness was 3 μm.
The polyurethane resin solution comprises the following raw materials in percentage by weight, the content of polyurethane resin is 1-15%, the surfactant is 0.5-10%, and the balance is deionized water, wherein the surfactant is one or a combination of more of 2-sodium sulfonate-diisooctyl succinate and 2-sodium sulfonate-dihexyl succinate; in this example, in the polyurethane resin solution, the content of the polyurethane resin is 7%, the content of the surfactant 2-sodium sulfonate-diisooctyl succinate is 5%, and the balance is deionized water.
(2) Hardened layer
Then, according to the following proportion, 7% of pure acrylic resin, 11% of decafunctional group polyurethane resin, 20% of difunctional group polyurethane resin, 6% of lauric acid acrylate, 6% of methyl benzoylformate and 50% of butanone are sequentially stirred uniformly, and then the mixture is coated on the bottom layer in a micro-concave coating or strip-seam type extrusion coating mode, and a hardened layer is prepared through heating at 20-100 ℃ and UV curing; the thickness of the hardened layer is 3 μm;
(3) polythiophene conductive layers
The preparation method of the polythiophene conductive layer coating liquid comprises the following steps: weighing deionized water, dimethyl sulfoxide, polythiophene dispersion liquid, a pH regulator, modified hydrophilic poly PET water latex, ethanol and a surfactant according to the formula ratio, sequentially adding into a container, and stirring for 10min at a stirring speed of 100 r/min; the wet coating amount of the polythiophene conductive layer is 5ml per square meter; drying the polythiophene conductive layer for 1min under the drying condition of 80 ℃; the substrate was a 100 micron thick PET substrate.
(4) Preparation of nano silver wire layer and protective adhesive layer
Except that the length of the nano silver wire is 10-50 microns and the diameter is 10-50 nanometers, the preparation of the nano silver wire layer and the protective adhesive layer is respectively according to the preparation of the nano silver wire conductive coating and the oxide protective layer in the embodiment 1 of the patent CN201510419011.8, the nano silver wire coating liquid is coated on the polythiophene conductive layer to obtain the nano silver wire layer, and then the protective adhesive layer coating liquid is coated on the nano silver wire layer by layer to obtain the protective adhesive layer. The thickness of the protective glue layer is 150 nm.
Finally, the nano silver wire composite transparent conductive film is prepared.
And (3) conducting film performance test:
the resistance detection method comprises the following steps: four-probe sheet resistance tester, suzhou lattice electronics ltd.
Transmittance tester: hangzhou recipe science and technology CS 810.
The surface resistance of the finished product is 96ohm/sq, the transmittance is 89.0 percent, and the conductivity is improved.
Comparative example: the nano silver wire transparent conductive film does not contain a polythiophene conductive layer and consists of a protective adhesive layer, a nano silver wire layer, a bottom layer, a base material, a bottom layer and a hardening layer from top to bottom in sequence. Compared with example 1, the protective adhesive layer, the nano silver wire layer, the substrate and the hardened layer of the comparative example are the same except for the difference of the polythiophene conductive layer. The comparative example had a surface resistance of 100ohm/sq and a transmittance of 89.5%.
Examples 2-25 polythiophene conductive layer formulations, PET substrate thickness and finished product properties are shown in tables 1-4, with the remainder being the same as in example 1.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
The coating weights in the above table are wet coating weights.
While the preferred embodiments of the present invention have been described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A compound transparent conducting film of nanometer silver line which characterized in that: the polythiophene conductive layer is formed by coating and drying polythiophene conductive layer coating liquid; the polythiophene conductive layer coating liquid is prepared from the following raw materials in percentage by mass: 3-15% of polythiophene dispersion liquid, 1-5% of pH regulator, 0.1-15% of modified hydrophilic PET water latex, 4-19% of ethanol, 0.1-10% of surfactant, 1-5% of dimethyl sulfoxide and the balance of deionized water.
2. The silver nanowire composite transparent conductive film of claim 1, wherein: the weight of the polythiophene in the polythiophene dispersion liquid is 1% -2%, and the conductivity of the polythiophene dispersion liquid is 300-500S/m.
3. The silver nanowire composite transparent conductive film of claim 1, wherein: the pH regulator is at least one of ethylenediamine and triethylamine.
4. The silver nanowire composite transparent conductive film of claim 1, wherein: the preparation method of the polythiophene conductive layer comprises the following steps: weighing deionized water, dimethyl sulfoxide, polythiophene dispersion liquid, a pH regulator, modified hydrophilic PET water latex, ethanol and a surfactant according to the formula ratio, and stirring at the stirring speed of 100-700 r/min for 5-30 min to obtain a polythiophene conductive layer coating liquid; and coating the polythiophene conductive layer coating liquid on the non-hardened layer surface of the base material, and drying to obtain the polythiophene conductive layer.
5. The silver nanowire composite transparent conductive film of claim 1, wherein: the wet coating amount of the polythiophene conductive layer coating liquid is 5-50ml per square meter.
6. The silver nanowire composite transparent conductive film of claim 1, wherein: the drying condition of the polythiophene conductive layer coating liquid is 80-140 ℃, and the drying time is 1-5 min.
7. The silver nanowire composite transparent conductive film of claim 1, wherein: the surfactant is at least one of sodium diisooctyl succinate sulfonate and sodium dihexyl succinate sulfonate.
8. The silver nanowire composite transparent conductive film of claim 1, wherein: the base material is a PET base material, and the thickness of the base material is 12-150 micrometers.
9. The silver nanowire composite transparent conductive film of claim 1, wherein: the bottom layer is a polyurethane resin layer, a modified hydrophilic polyethylene terephthalate layer or an acrylic resin layer; the hardening layer is formed by coating hardening liquid and then drying; the hardening liquid mainly comprises the following components in percentage by weight: 2.5-7% of pure acrylic resin, 7.5-18% of ten-functional polyurethane polymer, 16-26% of difunctional polyurethane polymer, 5-10% of reactive diluent, 1-4% of photoinitiator and 45-55% of solvent.
10. The nanosilver wire composite transparent conductive film of any one of claims 1 to 9, wherein: the thickness of the bottom layer is 1-10um, the thickness of the hardening layer is 1-5um, and the thickness of the protective adhesive layer is 50-500 nm.
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070257235A1 (en) * | 2006-03-16 | 2007-11-08 | Dongjin Semichem Co., Ltd. | Conductive coating composition for protective film and method for producing coating layer using the same |
| CN101512681A (en) * | 2006-09-05 | 2009-08-19 | 帝人杜邦薄膜日本有限公司 | Conductive film |
| CN101689568A (en) * | 2007-04-20 | 2010-03-31 | 凯博瑞奥斯技术公司 | Composite transparent conductors and methods of forming the same |
| CN101944437A (en) * | 2010-08-31 | 2011-01-12 | 中国乐凯胶片集团公司 | Flexible photo-anode for flexible dye-sensitized solar battery and preparation method thereof |
| CN102754055A (en) * | 2010-02-09 | 2012-10-24 | 王子制纸株式会社 | Conductive laminate and touch panel using same |
| CN103338882A (en) * | 2010-12-07 | 2013-10-02 | 罗地亚管理公司 | Electrically conductive nanostructures, method for making such nanostructures, electrically conductive polymer films containing such nanostructures, and electronic devices containing such films |
| CN104053256A (en) * | 2014-05-14 | 2014-09-17 | 中国科学院合肥物质科学研究院 | Heater based on transparent silver nanowire conducting thin film and preparation method thereof |
| DE102013005763A1 (en) * | 2013-04-05 | 2014-10-09 | Heraeus Precious Metals Gmbh & Co. Kg | Transparent layers with high conductivity and high efficiency in OLEDs and process for their preparation |
| CN104637570A (en) * | 2015-01-29 | 2015-05-20 | 深圳市东丽华科技有限公司 | Flexible transparent conductive thin film and preparation method thereof |
| CN104813498A (en) * | 2012-10-03 | 2015-07-29 | 哈钦森公司 | Transparent electrode and associated production method |
| CN106893456A (en) * | 2017-04-05 | 2017-06-27 | 潍坊海通新材料科技有限公司 | A kind of antistatic coating fluid of high stability polythiophene and preparation method thereof |
| CN106928847A (en) * | 2015-12-30 | 2017-07-07 | 乐凯华光印刷科技有限公司 | A kind of silver halide image exports film bottom antistatic coating fluid and its preparation method and application |
| CN107384025A (en) * | 2017-08-10 | 2017-11-24 | 珠海纳金科技有限公司 | One kind spraying electrically conducting transparent ink and its preparation method and application |
| CN108250469A (en) * | 2016-12-29 | 2018-07-06 | 乐凯华光印刷科技有限公司 | A kind of production technology of nano-silver thread transparent conductive film |
| CN207947080U (en) * | 2018-02-11 | 2018-10-09 | 江阴通利光电科技有限公司 | A kind of high nano-silver thread conductive film |
| CN111161906A (en) * | 2020-01-19 | 2020-05-15 | 惠州达祺光电科技有限公司 | Low-resistance transparent conductive film and preparation method thereof |
-
2020
- 2020-12-28 CN CN202011574691.8A patent/CN114694877A/en active Pending
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070257235A1 (en) * | 2006-03-16 | 2007-11-08 | Dongjin Semichem Co., Ltd. | Conductive coating composition for protective film and method for producing coating layer using the same |
| CN101512681A (en) * | 2006-09-05 | 2009-08-19 | 帝人杜邦薄膜日本有限公司 | Conductive film |
| CN101689568A (en) * | 2007-04-20 | 2010-03-31 | 凯博瑞奥斯技术公司 | Composite transparent conductors and methods of forming the same |
| CN102754055A (en) * | 2010-02-09 | 2012-10-24 | 王子制纸株式会社 | Conductive laminate and touch panel using same |
| CN101944437A (en) * | 2010-08-31 | 2011-01-12 | 中国乐凯胶片集团公司 | Flexible photo-anode for flexible dye-sensitized solar battery and preparation method thereof |
| CN103338882A (en) * | 2010-12-07 | 2013-10-02 | 罗地亚管理公司 | Electrically conductive nanostructures, method for making such nanostructures, electrically conductive polymer films containing such nanostructures, and electronic devices containing such films |
| CN104813498A (en) * | 2012-10-03 | 2015-07-29 | 哈钦森公司 | Transparent electrode and associated production method |
| DE102013005763A1 (en) * | 2013-04-05 | 2014-10-09 | Heraeus Precious Metals Gmbh & Co. Kg | Transparent layers with high conductivity and high efficiency in OLEDs and process for their preparation |
| CN104053256A (en) * | 2014-05-14 | 2014-09-17 | 中国科学院合肥物质科学研究院 | Heater based on transparent silver nanowire conducting thin film and preparation method thereof |
| CN104637570A (en) * | 2015-01-29 | 2015-05-20 | 深圳市东丽华科技有限公司 | Flexible transparent conductive thin film and preparation method thereof |
| CN106928847A (en) * | 2015-12-30 | 2017-07-07 | 乐凯华光印刷科技有限公司 | A kind of silver halide image exports film bottom antistatic coating fluid and its preparation method and application |
| CN108250469A (en) * | 2016-12-29 | 2018-07-06 | 乐凯华光印刷科技有限公司 | A kind of production technology of nano-silver thread transparent conductive film |
| CN106893456A (en) * | 2017-04-05 | 2017-06-27 | 潍坊海通新材料科技有限公司 | A kind of antistatic coating fluid of high stability polythiophene and preparation method thereof |
| CN107384025A (en) * | 2017-08-10 | 2017-11-24 | 珠海纳金科技有限公司 | One kind spraying electrically conducting transparent ink and its preparation method and application |
| CN207947080U (en) * | 2018-02-11 | 2018-10-09 | 江阴通利光电科技有限公司 | A kind of high nano-silver thread conductive film |
| CN111161906A (en) * | 2020-01-19 | 2020-05-15 | 惠州达祺光电科技有限公司 | Low-resistance transparent conductive film and preparation method thereof |
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