CN113284647B - High-conductivity transparent conductive film and display curtain wall - Google Patents
High-conductivity transparent conductive film and display curtain wall Download PDFInfo
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- CN113284647B CN113284647B CN202110344879.1A CN202110344879A CN113284647B CN 113284647 B CN113284647 B CN 113284647B CN 202110344879 A CN202110344879 A CN 202110344879A CN 113284647 B CN113284647 B CN 113284647B
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- H—ELECTRICITY
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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
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- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- G09F9/33—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being semiconductor devices, e.g. diodes
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Abstract
The invention provides a high-conductivity transparent conductive film and a display curtain wall, wherein the transparent conductive film comprises the following components: a transparent substrate; a transparent primer layer on the transparent substrate, wherein the transparent primer layer is composed of a mixture comprising epoxy resin and graphene oxide; a transparent conductive layer on the transparent primer layer, wherein the transparent conductive layer is composed of a mixture comprising metal nanowires and cellulose ester polymer. The high-conductivity transparent conductive film and the display curtain wall provided by the invention have the advantages of high conductivity and high transparency, and the manufactured curtain wall integrates the functions of transparency and display.
Description
Technical Field
The invention relates to the technical field of display, in particular to a high-conductivity transparent conductive film and a display curtain wall.
Background
The curtain wall is an outer wall protection of a building, is not bearing, is hung like a curtain, is also called a hanging wall, and is a light wall body with a decoration effect commonly used in modern large-scale and high-rise buildings. At present, the existing glass curtain wall does not have the function of lighting or displaying a screen, but if one surface of a building is made into the displaying screen, the whole wall surface of the building is completely shielded by the displaying screen, and lighting cannot be achieved. Therefore, how to prepare a functional glass curtain wall screen which does not influence the lighting of the curtain wall and can realize display becomes a new subject of the modern glass curtain wall construction technology and the display screen technology.
Currently, transparent conductive films are widely used because they have good electrical conductivity and high transparent light transmittance in the visible light wavelength band. If the transparent conductive film is combined with the design of the LED display screen, the transparent conductive film has the effects of light transmission and display, so that the lighting problem of the wall surface is not affected. Therefore, the display function of the curtain wall can be endowed on the premise of not affecting the lighting of the curtain wall. However, the conventional transparent conductive film has the defects of low light transmission efficiency, poor conductive performance and the like, and cannot meet the requirements of the curtain wall.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a high-conductivity transparent conductive film and a display curtain wall, and the conductive film has the advantages of high conductivity and high transparency, so that the manufactured curtain wall integrates the functions of transparency and display.
The invention provides a high-conductivity transparent conductive film, which comprises the following components:
a transparent substrate;
a transparent primer layer on the transparent substrate, wherein the transparent primer layer is composed of a mixture comprising epoxy resin and graphene oxide;
a transparent conductive layer on the transparent primer layer, wherein the transparent conductive layer is composed of a mixture comprising metal nanowires and cellulose ester polymer.
Preferably, the transparent substrate is transparent polyimide.
Preferably, the epoxy resin is bisphenol a epoxy resin, and the graphene oxide is prepared by a hummers method.
Preferably, the metal nanowires are silver nanowires and the cellulose ester polymer is a cellulose acetate polymer, a cellulose acetate butyrate polymer, or a cellulose acetate propionate polymer.
Preferably, the mass ratio of the epoxy resin to the graphene oxide is 100:1-5.
Preferably, the mass ratio of the metal nanowires to the cellulose ester polymer is 1:1-3.
Preferably, the thickness of the transparent primer layer is 1 to 5 μm, and the thickness of the transparent conductive layer is 0.1 to 1 μm.
Preferably, the transparent primer layer is formed by coating a primer solution comprising epoxy resin and graphene oxide on the transparent substrate and then curing the primer solution; the transparent conductive layer is formed by coating a conductive liquid comprising metal nanowires and cellulose ester polymer on the transparent undercoat layer and then drying.
Preferably, the primer further comprises a curing agent, and the amount of the curing agent is 5-20wt% of the epoxy resin.
The invention provides a display curtain wall which comprises the transparent conductive film and an LED luminous group positioned on the transparent conductive film.
In the transparent conductive film, a transparent base coat layer and a transparent conductive layer are arranged on a transparent substrate, wherein the transparent base coat layer is formed by a mixture comprising epoxy resin and graphene oxide, and the transparent conductive layer is formed by a mixture comprising metal nanowires and cellulose ester polymer. By compounding the graphene oxide with the epoxy resin, not only can the interface bonding strength between the epoxy resin and the transparent substrate be improved, but also more importantly, a large number of hydroxyl groups and carboxyl groups contained on the surface of the graphene oxide can form stronger affinity to the metal nanowires, so that the dispersion and stability of the metal nanowires in the transparent conductive layer are promoted. Meanwhile, the cellulose ester polymer contained in the transparent conductive layer has nitrogen and oxygen groups on the surface, which can form good coordination for the metal nanowires, and can stabilize the dispersion and coating of the metal nanowires in the polymer solution. Finally, the conductive film has the advantages of improving the conductivity and maintaining the high transparency, and the defect that the existing curtain wall cannot have the light transmission or display function at the same time is effectively overcome.
Detailed Description
The technical scheme of the present invention will be described in detail by means of specific examples, which should be explicitly set forth for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A highly conductive transparent conductive film, which is prepared by the following method:
1g of crystalline flake graphite was added to 100mL of concentrated H 2 SO 4 In the process, 6g of KMnO was slowly added under stirring 4 Stirring in ice bath for 60min, heating in water bath to 40deg.C, stirring for 3 hr, and slowly adding 8mLH 2 O 2 Stirring the solution (30 wt%) for reaction for 10min, adding hydrochloric acid for centrifugal washing, repeatedly washing with deionized water until the pH value is neutral, filtering, and drying to obtain graphene oxide;
adding 50g of epoxy resin 618 (E-51) into 100mL of acetone, completely dissolving, adding 5g of polyether amine D-2000 curing agent, stirring and mixing uniformly, and then adding 1g of graphene oxide, heating, stirring and mixing uniformly to obtain a primer solution;
coating the primer on a polyimide film (CPI, thickness of about 50 μm, light transmittance of about 90%) as the surface of a transparent substrate, and heating and curing at 120 ℃ for 60min to form a transparent primer with thickness of 3 μm on the transparent substrate;
adding 5g of polyvinylpyrrolidone into 20mL of ethylene glycol, stirring and dissolving completely, adding 2g of silver nitrate, mixing and stirring at 160 ℃ for reaction for 3 hours, centrifuging after finishing, washing twice with ethanol, and drying to obtain silver nanowires;
1.5g of silver nanowires are firstly added into 50mL of isopropanol solution for ultrasonic dispersion uniformly, then 3g of cellulose acetate butyrate polymer CAB 381-20 is added for stirring and mixing uniformly, and a conductive liquid is obtained;
and (3) coating the conductive liquid on the transparent base coat, heating and curing for 5min at 150 ℃, and forming a transparent conductive layer with the thickness of 0.5 mu m on the surface of the transparent base coat to obtain the high-conductivity transparent conductive film.
Example 2
A highly conductive transparent conductive film, which is prepared by the following method:
1g of crystalline flake graphite was added to 100mL of concentrated H 2 SO 4 In the process, 6g of KMnO was slowly added under stirring 4 Stirring and reacting for 60min in ice bath after completion, heating in water bath to 40 ℃, continuously stirring for 3H, and slowly adding 8mL of H 2 O 2 Stirring the solution (30 wt%) for reaction for 10min, adding hydrochloric acid for centrifugal washing, repeatedly washing with deionized water until the pH value is neutral, filtering, and drying to obtain graphene oxide;
adding 50g of epoxy resin 618 (E-51) into 100mL of acetone, completely dissolving, adding 5g of polyether amine D-2000 curing agent, stirring and mixing uniformly, and then adding 0.5g of graphene oxide, heating, stirring and mixing uniformly to obtain a primer solution;
coating the primer on a polyimide film (CPI, thickness of about 50 μm, light transmittance of about 90%) as the surface of a transparent substrate, and heating and curing at 120 ℃ for 60min to form a transparent primer with thickness of 3 μm on the transparent substrate;
adding 5g of polyvinylpyrrolidone into 20mL of ethylene glycol, stirring and dissolving completely, adding 2g of silver nitrate, mixing and stirring at 160 ℃ for reaction for 3 hours, centrifuging after finishing, washing twice with ethanol, and drying to obtain silver nanowires;
1.5g of silver nanowires are firstly added into 50mL of isopropanol solution for ultrasonic dispersion uniformly, and then 4.5g of cellulose acetate butyrate polymer CAB 381-20 is added for stirring and mixing uniformly, so as to obtain a conductive liquid;
and (3) coating the conductive liquid on the transparent base coat, heating and curing for 5min at 150 ℃, and forming a transparent conductive layer with the thickness of 0.5 mu m on the surface of the transparent base coat to obtain the high-conductivity transparent conductive film.
Example 3
A highly conductive transparent conductive film, which is prepared by the following method:
2.5g of crystalline flake graphite was added to 200mL of concentrated H 2 SO 4 In the process, 15g of KMnO was slowly added under stirring 4 Stirring and reacting for 60min in ice bath after completion, heating in water bath to 40 ℃, continuously stirring for 3H, and slowly adding 20mL of H 2 O 2 Stirring the solution (30 wt%) for reaction for 10min, adding hydrochloric acid for centrifugal washing, repeatedly washing with deionized water until the pH value is neutral, filtering, and drying to obtain graphene oxide;
adding 50g of epoxy resin 618 (E-51) into 100mL of acetone, completely dissolving, adding 5g of polyether amine D-2000 curing agent, stirring and mixing uniformly, and then adding 2.5g of graphene oxide, heating, stirring and mixing uniformly to obtain a primer solution;
coating the primer on a polyimide film (CPI, thickness of about 50 μm, light transmittance of about 90%) as the surface of a transparent substrate, and heating and curing at 120 ℃ for 60min to form a transparent primer with thickness of 3 μm on the transparent substrate;
adding 5g of polyvinylpyrrolidone into 20mL of ethylene glycol, stirring and dissolving completely, adding 2g of silver nitrate, mixing and stirring at 160 ℃ for reaction for 3 hours, centrifuging after finishing, washing twice with ethanol, and drying to obtain silver nanowires;
1.5g of silver nanowires are firstly added into 50mL of isopropanol solution for ultrasonic dispersion uniformly, then 1.5g of cellulose acetate butyrate polymer CAB 381-20 is added for stirring and mixing uniformly, and a conductive liquid is obtained;
and (3) coating the conductive liquid on the transparent base coat, heating and curing for 5min at 150 ℃, and forming a transparent conductive layer with the thickness of 0.5 mu m on the surface of the transparent base coat to obtain the high-conductivity transparent conductive film.
Comparative example 1
A transparent conductive film prepared by the following method:
adding 50g of epoxy resin 618 (E-51) into 100mL of acetone, completely dissolving, adding 5g of polyether amine D-2000 curing agent, and uniformly stirring and mixing to obtain a primer solution;
coating the primer on a polyimide film (CPI, thickness of about 50 μm, light transmittance of about 90%) as the surface of a transparent substrate, and heating and curing at 120 ℃ for 60min to form a transparent primer with thickness of 3 μm on the transparent substrate;
adding 5g of polyvinylpyrrolidone into 20mL of ethylene glycol, stirring and dissolving completely, adding 2g of silver nitrate, mixing and stirring at 160 ℃ for reaction for 3 hours, centrifuging after finishing, washing twice with ethanol, and drying to obtain silver nanowires;
1.5g of silver nanowires are firstly added into 50mL of isopropanol solution for ultrasonic dispersion uniformly, then 3g of cellulose acetate butyrate polymer CAB 381-20 is added for stirring and mixing uniformly, and a conductive liquid is obtained;
and (3) coating the conductive liquid on the transparent base coat, heating and curing for 5min at 150 ℃, and forming a transparent conductive layer with the thickness of 0.5 mu m on the surface of the transparent base coat to obtain the transparent conductive film.
Comparative example 2
A transparent conductive film prepared by the following method:
1g of crystalline flake graphite was added to 100mL of concentrated H 2 SO 4 In the process, 6g of KMnO was slowly added under stirring 4 Stirring and reacting for 60min in ice bath after completion, heating in water bath to 40 ℃, continuously stirring for 3H, and slowly adding 8mL of H 2 O 2 Stirring the solution (30 wt%) for reaction for 10min, adding hydrochloric acid for centrifugal washing, repeatedly washing with deionized water until the pH value is neutral, filtering, and drying to obtain graphene oxide;
adding 50g of epoxy resin 618 (E-51) into 100mL of acetone, completely dissolving, adding 5g of polyether amine D-2000 curing agent, stirring and mixing uniformly, and then adding 1g of graphene oxide, heating, stirring and mixing uniformly to obtain a primer solution;
coating the primer on a polyimide film (CPI, thickness of about 50 μm, light transmittance of about 90%) as the surface of a transparent substrate, and heating and curing at 120 ℃ for 60min to form a transparent primer with thickness of 3 μm on the transparent substrate;
adding 5g of polyvinylpyrrolidone into 20mL of ethylene glycol, stirring and dissolving completely, adding 2g of silver nitrate, mixing and stirring at 160 ℃ for reaction for 3 hours, centrifuging after finishing, washing twice with ethanol, and drying to obtain silver nanowires;
1.5g of silver nanowires are firstly added into 50mL of isopropanol solution to be uniformly dispersed by ultrasonic, so as to obtain conductive liquid;
and (3) coating the conductive liquid on the transparent base coat, heating and curing for 5min at 150 ℃, and forming a transparent conductive layer with the thickness of 0.5 mu m on the surface of the transparent base coat to obtain the transparent conductive film.
Comparative example 3
A transparent conductive film prepared by the following method:
adding 50g of epoxy resin 618 (E-51) into 100mL of acetone, completely dissolving, adding 5g of polyether amine D-2000 curing agent, stirring and mixing uniformly, and then adding 1g of crystalline flake graphene, heating, stirring and mixing uniformly to obtain primer liquid;
coating the primer on a polyimide film (CPI, thickness of about 50 μm, light transmittance of about 90%) as the surface of a transparent substrate, and heating and curing at 120 ℃ for 60min to form a transparent primer with thickness of 3 μm on the transparent substrate;
adding 5g of polyvinylpyrrolidone into 20mL of ethylene glycol, stirring and dissolving completely, adding 2g of silver nitrate, mixing and stirring at 160 ℃ for reaction for 3 hours, centrifuging after finishing, washing twice with ethanol, and drying to obtain silver nanowires;
1.5g of silver nanowires are firstly added into 50mL of isopropanol solution for ultrasonic dispersion uniformly, then 3g of cellulose acetate butyrate polymer CAB 381-20 is added for stirring and mixing uniformly, and a conductive liquid is obtained;
and (3) coating the conductive liquid on the transparent base coat, heating and curing for 5min at 150 ℃, and forming a transparent conductive layer with the thickness of 0.5 mu m on the surface of the transparent base coat to obtain the transparent conductive film.
The properties of the transparent conductive films prepared in the above examples and comparative examples were tested, and the results are shown in table 1.
Sheet resistance: and (3) performing a sheet resistance test by adopting an RTS-9 type double-electric-measurement four-probe tester.
Transmittance: and the light transmittance is tested by using an Shimadzu UV-2450 ultraviolet-visible spectrophotometer, and the wavelength test range is 200-800nm.
Table 1 test results of transparent conductive films obtained in examples and comparative examples
| Square resistance (omega/≡) | Transmittance (%) | |
| Example 1 | 8 | 87.71 |
| Example 2 | 10 | 88.33 |
| Example 3 | 13 | 86.93 |
| Comparative example 1 | 107 | 82.89 |
| Comparative example 2 | 264 | 79.71 |
| Comparative example 3 | 169 | 80.10 |
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (7)
1. A highly conductive transparent conductive film, comprising:
a transparent substrate;
a transparent primer layer on the transparent substrate, wherein the transparent primer layer is composed of a mixture comprising epoxy resin and graphene oxide;
a transparent conductive layer on the transparent primer layer, the transparent conductive layer comprising a mixture of metal nanowires and cellulose ester polymer;
the transparent substrate is transparent polyimide;
the mass ratio of the epoxy resin to the graphene oxide is 100:1-5;
the transparent base coat is formed by coating a base coat liquid comprising epoxy resin and graphene oxide on the transparent substrate and then curing; the transparent conductive layer is formed by coating a conductive liquid comprising metal nanowires and cellulose ester polymer on the transparent undercoat layer and then drying.
2. The highly conductive transparent conductive film according to claim 1, wherein the epoxy resin is bisphenol a type epoxy resin, and the graphene oxide is prepared by a hummers method.
3. The highly conductive transparent conductive film according to claim 1 or 2, wherein the metal nanowires are silver nanowires, and the cellulose ester polymer is a cellulose acetate polymer, a cellulose acetate butyrate polymer, or a cellulose acetate propionate polymer.
4. The highly conductive transparent conductive film according to claim 1 or 2, wherein the mass ratio of the metal nanowires to cellulose ester polymer is 1:1-3.
5. The highly conductive transparent conductive film according to claim 1 or 2, wherein the thickness of the transparent undercoat layer is 1 to 5 μm and the thickness of the transparent conductive layer is 0.1 to 1 μm.
6. The highly conductive transparent conductive film according to claim 1, wherein the primer further comprises a curing agent in an amount of 5 to 20wt% of the epoxy resin.
7. A display curtain wall comprising the transparent conductive film of any one of claims 1-6 and an LED light emitting group on the transparent conductive film.
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| CN108962437A (en) * | 2018-07-25 | 2018-12-07 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of graphene oxide composite conductive film |
| WO2020139070A1 (en) * | 2018-12-28 | 2020-07-02 | Mimos Berhad | Method of synthesizing solvent-free silver reduced graphene oxide hybrid conductive ink |
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| KR20120051645A (en) * | 2009-07-17 | 2012-05-22 | 케어스트림 헬스 인코포레이티드 | Transparent conductive film comprising cellulose esters |
| US10483104B2 (en) * | 2012-03-30 | 2019-11-19 | Kabushiki Kaisha Toshiba | Method for producing stacked electrode and method for producing photoelectric conversion device |
| KR20160102783A (en) * | 2015-02-23 | 2016-08-31 | 한국교통대학교산학협력단 | Method for preparing flexible transparent conductive film and flexible transparent conductive film manufactured thereby |
| CN110634622A (en) * | 2019-11-05 | 2019-12-31 | 高俊葵 | Preparation method of silver-containing nanowire high-weather-resistance transparent conductive film |
| CN111048902A (en) * | 2019-12-23 | 2020-04-21 | 浙江大学 | Transparent antenna and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108962437A (en) * | 2018-07-25 | 2018-12-07 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of graphene oxide composite conductive film |
| WO2020139070A1 (en) * | 2018-12-28 | 2020-07-02 | Mimos Berhad | Method of synthesizing solvent-free silver reduced graphene oxide hybrid conductive ink |
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