WO2011049347A2 - Procédé de fabrication d'un film conducteur à nanotubes de carbone - Google Patents

Procédé de fabrication d'un film conducteur à nanotubes de carbone Download PDF

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Publication number
WO2011049347A2
WO2011049347A2 PCT/KR2010/007153 KR2010007153W WO2011049347A2 WO 2011049347 A2 WO2011049347 A2 WO 2011049347A2 KR 2010007153 W KR2010007153 W KR 2010007153W WO 2011049347 A2 WO2011049347 A2 WO 2011049347A2
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WO
WIPO (PCT)
Prior art keywords
substrate
carbon nanotube
conductive film
nanotube conductive
coating
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Application number
PCT/KR2010/007153
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English (en)
Korean (ko)
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WO2011049347A3 (fr
Inventor
황성홍
임정혁
정다정
Original Assignee
주식회사 탑나노시스
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Publication of WO2011049347A2 publication Critical patent/WO2011049347A2/fr
Publication of WO2011049347A3 publication Critical patent/WO2011049347A3/fr

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    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • 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
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon

Definitions

  • the present invention relates to a carbon nanotube conductive film and a manufacturing method thereof, and can be applied to various display fields, antistatic products, touch panel fields, and various fields including a transparent heating element.
  • the transparent conductive film may include a plasma display panel (PDP), a liquid crystal display (LCD) device, a light emitting diode (LED), an organic light emitting diode (OLED), and an organic light emitting diode (OLED). ), And is used as electrodes of various light receiving elements and light emitting elements in touch panels or solar cells.
  • PDP plasma display panel
  • LCD liquid crystal display
  • LED light emitting diode
  • OLED organic light emitting diode
  • OLED organic light emitting diode
  • OLED organic light emitting diode
  • OLED organic light emitting diode
  • OLED organic light emitting diode
  • OLED organic light emitting diode
  • OLED organic light emitting diode
  • it is used as a transparent electromagnetic shielding agent such as an antistatic film and an electromagnetic shielding film used in automobile window glass or building window glass, and a transparent heating element such as a heat ray reflecting film and a frozen showcase.
  • the carbon nanotube is evaluated as an ideal material capable of realizing conductivity while maintaining optical properties because the theoretical percolation concentration is only 0.04%. Therefore, when the carbon nanotubes are coated with a thin film on a specific base layer, light is transmitted through the visible light region, indicating transparency, and maintaining electrical properties, which are inherent characteristics of the carbon nanotubes, to be used as transparent electrodes.
  • a conductive film using carbon nanotubes as an electrode is formed by coating a carbon nanotube dispersion liquid on a base layer.
  • the transparent electrode In order to use such a conductive film formed of carbon nanotubes, the transparent electrode should have a lower sheet resistance value and excellent transparency.
  • the manufactured carbon nanotube conductive film should have excellent dispersibility of the carbon nanotubes. In addition, no separate impurities such as dispersants should be left.
  • the present invention has been made to solve various problems including the above problems, and an object of the present invention is to provide a method for producing a carbon nanotube conductive film having a step of suppressing the remaining of impurities in the manufacturing process.
  • Another object of the present invention is to provide a method for producing a carbon nanotube conductive film having high permeability, high temperature and high humidity stability, chemical resistance and durability, and having excellent conductivity.
  • the carbon nanotube after the coating is further subjected to a process of removing impurities on the substrate, thereby having high transmittance and high conductivity.
  • FIG. 1 is a flowchart illustrating each step of a method of manufacturing a carbon nanotube conductive film according to a preferred embodiment of the present invention.
  • FIG. 2 is a conceptual diagram showing each step of the carbon nanotube conductive film manufacturing method according to a preferred embodiment of the present invention.
  • FIG 3 is a cross-sectional view showing a carbon nanotube conductive film prepared according to the present invention.
  • FIG. 4 is an enlarged cross-sectional view of part A of FIG. 3.
  • Carbon nanotube conductive film manufacturing method the step of preparing a substrate. Coating the carbon nanotubes with a dispersant on the substrate. Removing the contaminants containing the remaining dispersant with a decontamination solution containing pure water. The substrate is washed with water.
  • the dispersant may be a water soluble dispersant.
  • the water-soluble dispersant is preferably at least one selected from SDS (Sodium Dodecyl Sulfate), Triton X-100 (TX-100), NaDDBS (Sodium Dodecylbenzene Sulfonate), dye and Gun Arabic.
  • removing the decontamination may include spraying the decontamination solution on the substrate.
  • the step of spraying the decontamination solution may be achieved by spraying the decontamination solution on the substrate with a nozzle.
  • the spray angle of the nozzle preferably has an angle of 10 ° to 50 ° with the substrate surface.
  • the method may further include injecting air into the air nozzles on the substrate to remove the decontamination solution remaining on the substrate.
  • the method may further include forming a protective layer by coating ceramic on the substrate.
  • the step of coating the carbon nanotubes on the substrate, and removing the contaminants it may have a step of heat-treating the coated substrate at a temperature of 50 °C to 100 °C.
  • Carbon nanotube conductive film production method the step of preparing a substrate.
  • the coated substrate is subjected to a heat treatment at a temperature of 50 °C to 100 °C.
  • the decontamination solution is sprayed onto the substrate to remove contaminants including the remaining dispersant.
  • the substrate is washed with water.
  • the step of spraying the decontamination solution is made by spraying the decontamination solution on the substrate with a nozzle, the spray angle of the nozzle has an angle of 10 to 50 degrees with the substrate surface, the spray The pressure is preferably 1 to 10 kgf / cm 2.
  • the method for preparing a carbon nanotube conductive film includes preparing a substrate (S1), coating a carbon nanotube with a dispersant on the substrate (S2), and the remaining dispersant.
  • the substrate 10 may be made of a transparent polymer such as glass, PET, or PC as a transparent material.
  • the substrate 10 is preferably made of a highly transparent inorganic substrate or a transparent polymer substrate to have flexibility.
  • the substrate 10 may be conveyed along the conveyor while being flatly fixed to the fixing jig in a sheet form as shown in FIG. 2.
  • the carbon nanotube conductive film may be manufactured while the substrate is transferred in a roll to roll manner.
  • the carbon nanotube layer 20 including the dispersant 26 and the carbon nanotubes 21 is formed on the substrate (S2).
  • the carbon nanotubes (CNT) form a tube in which one carbon is combined with another carbon atom and a hexagonal honeycomb pattern to form a tube, and the diameter of the tube is extremely small at the nanometer level, thereby showing specific electrochemical characteristics.
  • the carbon nanotubes 21 are formed of a thin conductive film on a plastic or glass substrate, they can be used as transparent electrodes because they exhibit high transmittance and conductivity in the visible light region.
  • the carbon nanotubes may be single-walled carbon nanotubes or multi-walled carbon nanotubes.
  • the carbon nanotube layer 20 may be formed by spray coating using the spray 120 shown in FIG. 2, a filtering transition method of a dispersion, a roll coating method using a binder mixture, and the like. By coating the carbon nanotubes on the gas phase 10, a carbon nanotube layer is formed on the substrate 10.
  • Carbon nanotubes on the other hand, in the synthesis stage, the physical cohesion of ⁇ m level and the chemical cohesion of several tens of nm occur. Such agglomeration phenomena prevent the formation of three-dimensional network structure in the conductivity implementation and reduce the conductivity efficiency compared to the particles. For example, failure to overcome physical cohesion is very similar to the use of spherical particles at the ⁇ m level rather than nanotubes, and further, theoretical percolation concentrations cannot be achieved without chemical coagulation. Therefore, a dispersant 26 is included to help disperse the carbon nanotubes efficiently.
  • One method of dispersing carbon nanotubes is to disperse the carbon nanotubes in an organic solvent such as amide-based DMF (NN-dimethylformamide) or NMP (1,2-dichlorobenzene, N-methylpyrrolidone).
  • organic solvent such as amide-based DMF (NN-dimethylformamide) or NMP (1,2-dichlorobenzene, N-methylpyrrolidone).
  • This dispersion method has a problem of poor stability because it is dispersion by simple dissolution, and also has a very low solubility of carbon nanotubes.
  • a water-soluble dispersant 26 may be applied as another method of dispersing carbon nanotubes.
  • the water-soluble dispersant includes sodium dodecyl sulfate (SDS), triton x-100 (tx-100), sodium dodecylbenzene sulfonate (NaDDBS), gum arabic, dyes, and the like.
  • SDS sodium dodecyl sulfate
  • tx-100 triton x-100
  • NaDDBS sodium dodecylbenzene sulfonate
  • gum arabic dyes, and the like.
  • the water-soluble dispersant has advantages such as the most stable solution and maximum solubility, and thus has the advantage of effectively dispersing carbon nanotubes.
  • the substrate 10 may be raised to a temperature of 50 ° C. to 100 ° C. to facilitate the coating by a heating device such as a heating block 122.
  • the step of preparing the substrate (S1) and the step of forming the carbon nanotube layer (S2) may be subjected to the step (S1_5) to remove the delimiter and particles on the substrate.
  • the surface modification step may be performed to maximize the coating ability of the substrate.
  • step (S1) may have a step (S1_8) of heat-treating the substrate at a temperature of 50 °C to 100 °C. This is to improve the coating power on the substrate during the coating of carbon nanotubes.
  • the contaminants including the remaining dispersant 26 are removed by the decontamination solution 140 including ultrapure water (S3).
  • dispersants 26 serve as impurities that degrade the conductivity of the film after the carbon nanotube layer 21 is formed. Therefore, it is preferable to increase the conductivity of the electrode by removing the dispersant 26 after the carbon nanotube layer 21 is formed.
  • the dispersant 26 may be mixed with the carbon nanotubes 21 in a solvent and coated on a substrate with a mixed solution, and the solvent is usually removed by evaporation. However, at least some of the dispersant 26 remains with the carbon nanotubes 21 without being completely removed by evaporation. Therefore, after the step of removing the dispersant (S3) after the carbon nanotube layer forming step (S2), the conductivity and transparency is improved.
  • washing with distilled water can remove internal residual dispersant along with surface washing.
  • adding a reagent for changing the dispersant may split the dispersant into unit molecules together with surface cleaning, so that the dispersant may be better washed with water.
  • the decontamination solution 140 preferably includes pure water. That is, when the substrate 10 on which the carbon nanotube layer 21 is formed is in contact with or impregnated with pure water, the water-soluble dispersant is separated from the carbon nanotubes and removed.
  • Pure water refers to water in which ions (mainly alkalis and metal ions) are removed from ordinary water. Pure water is more preferably ultrapure water that has removed other impurities (such as organic) that are not ionized.
  • the decontamination solution may be sprayed by inclining at a predetermined angle on the substrate with the nozzle 142.
  • the spray angle of the nozzle is preferably to have an angle ⁇ of 10 to 50 degrees with the substrate surface.
  • the injection pressure has 1 to 10 kgf / cm 2.
  • the carbon nanotubes 21 should be strongly bonded to the substrate 142. That is, if the carbon nanotubes 21 are not strongly bonded to the substrate 10 after the carbon nanotube layer forming process S2, the carbon nanotubes 21 are also separated from the substrate 10 in the process of removing contaminants. This is because it is removed together with the contaminants.
  • the step of heat-treating the coated substrate at a temperature of 50 °C to 100 °C (S2_1 It is preferable to have). This is because, when the coated substrate is heat-treated after the coating process, the bonding force between the substrate and the carbon nanotubes becomes more excellent, and the carbon nanotubes may be bonded to the carbon nanotubes even under high pressure injection pressure. .
  • the step S1_8 and the step S2_1 may be performed by allowing the heat block 122 to rise to be adjacent to the rear surface of the substrate 10.
  • the substrate is washed with the step (S4).
  • the said water washing can be obtained by performing atomization spray by a nozzle.
  • the washing water for washing may be removed by air blowing. In this case, a compressed air of 1 to 10 Kg / cm 2 may be applied.
  • step of washing the substrate (S4) it may be further subjected to the step (S5) of forming a protective layer by coating a ceramic on the substrate.
  • the protective layer 30 is formed on the carbon nanotube layer 20 and includes a ceramic binder.
  • the protective layer 30 functions to protect the carbon nanotube layer 20 from the outside, and in this case, the transparency and electrical conductivity of the substrate coated with carbon nanotubes should not be reduced.
  • the protective layer 30 may be made of a binder material of ceramic material.
  • the ceramic binder is capable of producing a coating film having a high light transmittance, and has excellent adhesive strength, which is advantageous for reinforcing microcracking, having excellent heat and fire resistance, and coating application.
  • the ceramic binder may be of various types, for example, tin oxide (SnO 2 ) of a conductive material, yttrium oxide (Y 2 O 3 ) having strong water repellency, magnesium oxide (MgO) used as an electronic filter, and used as an adhesive Silicon oxide (SiO 2 ), zinc oxide of a sunscreen (ZnO), silicon and the like.
  • tin oxide (SnO 2 ) of a conductive material yttrium oxide (Y 2 O 3 ) having strong water repellency, magnesium oxide (MgO) used as an electronic filter, and used as an adhesive Silicon oxide (SiO 2 ), zinc oxide of a sunscreen (ZnO), silicon and the like.
  • a silicone binder exhibits various physical properties according to a functional group substituted with a silicon element. These functional groups may be converted to other functional groups by various chemical reactions, and in addition to the methyl group, organic groups such as phenyl group, vinyl group, propyl trifluoride group, alkyl group, etc. are substituted and are widely used commercially.
  • the silicon binder according to the embodiment of the present invention may have a structure having a skeleton of [Si (R1R2) -O-] n type in which two alkyl groups are substituted on silicon.
  • the alkyl group exhibits hydrophobic properties so that when coated on the surface of the carbon nanotube electrode layer, the alkyl group is arranged outwardly opposite to the surface of the carbon nanotube electrode layer, thereby improving durability of the electrode at high temperature and high humidity.
  • two alkyl-substituted [Si (R1R2) -O-] moieties and two bonding moieties of silicon and oxygen in the structure of silicon face in the opposite direction [O-SiR1R2-O-] structurally. It can also be effectively directed to the outside surface.
  • the protective layer 30 made of the silicone polymer has excellent oxidation stability, excellent weather resistance, low surface tension, stain resistance, and excellent gas permeability.
  • the organic group of the ceramic constituting the protective layer 30 is easily mixed with carbon nanotubes and maintains stability. Accordingly, the protective layer 30 has contact stability with the surface of the carbon nanotube layer.
  • the protective layer 30 preferably has a thickness of several to several hundred nanometers, in order to maintain the conductivity of the carbon nanotube layer 20.
  • a thin ceramic coating film of nano units is formed on the carbon nanotubes. This is to avoid degrading the electrode characteristics of carbon nanotubes as much as possible.
  • the protective layer thickness / carbon nanotube thickness ratio should be adjusted in a range of 2 or less.
  • the protective layer 30 may be formed of a mixture of the ceramic binder 33 and the carbon nanotubes 31. That is, by making a coating solution in which the ceramic binder 33 and the carbon nanotubes 31 are mixed at a constant ratio, by coating the carbon nanotubes on the carbon nanotube layer 20 of the substrate 10 coated with the carbon nanotubes, Overcoming the disadvantages of increased sheet resistance due to the coating of the protective layer can maintain the electrode characteristics of carbon nanotubes.
  • the forming of the protective layer (S5) comprises the steps of preparing a carbon nanotube dispersion solution having the carbon nanotube concentration of 0.01 to 0.1 wt%, and ceramics in the carbon nanotube dispersion solution in a weight ratio of 1 to 1. It may include the step of preparing a mixed coating solution by adding 20 wt%.
  • the protective layer (S5) after forming the protective layer (S5) it may be further subjected to the step (S6) of washing the completed carbon nanotube conductive film.
  • the protective layer (S5) may further comprise the step of heat-treating the substrate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un film conducteur à nanotubes de carbone. Selon un mode de réalisation préféré de l'invention, ce procédé de fabrication comprend les étapes suivantes: la préparation d'une base; le revêtement de la surface supérieure de la base avec un nanotube de carbone et un agent de dispersion; l'élimination de contaminants contenant l'agent de dispersion résiduel au moyen d'une solution de décontamination contenant de l'eau pure, et le lavage de la base.
PCT/KR2010/007153 2009-10-22 2010-10-19 Procédé de fabrication d'un film conducteur à nanotubes de carbone WO2011049347A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020090100576A KR101162354B1 (ko) 2009-10-22 2009-10-22 탄소나노튜브 도전막 제조방법
KR10-2009-0100576 2009-10-22

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WO2011049347A2 true WO2011049347A2 (fr) 2011-04-28
WO2011049347A3 WO2011049347A3 (fr) 2011-07-14

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KR101321097B1 (ko) * 2012-02-27 2013-10-23 경북대학교 산학협력단 탄소나노튜브 투명전극, 이의 제조 방법, 및 탄소나노튜브 투명전극용 코팅용액

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KR100863273B1 (ko) * 2006-08-01 2008-10-15 세종대학교산학협력단 수직 정렬되는 탄소나노튜브 필름 제조 방법
KR100924766B1 (ko) * 2007-06-22 2009-11-05 삼성전자주식회사 금속 나노입자를 포함하는 탄소 나노튜브(ｃｎｔ) 박막 및그 제조방법
KR100929433B1 (ko) * 2007-08-22 2009-12-03 (주)탑나노시스 탄소나노튜브 도전막의 제조방법

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KR101162354B1 (ko) 2012-07-04
WO2011049347A3 (fr) 2011-07-14
KR20110043862A (ko) 2011-04-28

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