WO2007114645A1 - Conductive composite material and method for manufacturing the same - Google Patents

Conductive composite material and method for manufacturing the same Download PDF

Info

Publication number
WO2007114645A1
WO2007114645A1 PCT/KR2007/001643 KR2007001643W WO2007114645A1 WO 2007114645 A1 WO2007114645 A1 WO 2007114645A1 KR 2007001643 W KR2007001643 W KR 2007001643W WO 2007114645 A1 WO2007114645 A1 WO 2007114645A1
Authority
WO
WIPO (PCT)
Prior art keywords
base layer
membrane
conductive fiber
film
conductive
Prior art date
Application number
PCT/KR2007/001643
Other languages
French (fr)
Inventor
Sang-Keun Oh
June-Ki Park
Original Assignee
Topnanosis, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020060030685A external-priority patent/KR100791999B1/en
Priority claimed from KR1020060030684A external-priority patent/KR100791998B1/en
Priority claimed from KR1020060030683A external-priority patent/KR100791997B1/en
Application filed by Topnanosis, Inc. filed Critical Topnanosis, Inc.
Priority to US12/295,859 priority Critical patent/US20090056854A1/en
Publication of WO2007114645A1 publication Critical patent/WO2007114645A1/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24Electrically-conducting paints
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/24Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10Inorganic fibres
    • B32B2262/106Carbon fibres, e.g. graphite fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202Conductive
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/412Transparent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/20Displays, e.g. liquid crystal displays, plasma displays
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2209/00Apparatus and processes for manufacture of discharge tubes
    • H01J2209/02Manufacture of cathodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20Constructional details
    • H01J2211/22Electrodes
    • H01J2211/225Material of electrodes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10Methods of surface bonding and/or assembly therefor

Definitions

  • the present invention relates to a conductive composite material, which is flexible and used in an electronic product such as a flat panel display, and a method for manufacturing the same.
  • Transparent conductive materials have been widely used in a thin-film transistor liquid crystal display (TFT-LCD), a plasma display panel (PDP), an organic light emitting diode (OLED), a touch panel, an electromagnetic-wave shield, an electrostatic-discharge shield, a heat reflector, a surface heater, a photo-electric converter, etc.
  • TFT-LCD thin-film transistor liquid crystal display
  • PDP plasma display panel
  • OLED organic light emitting diode
  • touch panel a touch panel
  • electromagnetic-wave shield an electrostatic-discharge shield
  • heat reflector a surface heater
  • photo-electric converter etc.
  • ITO Indium tin oxide
  • conductive polymers such as polyacetylene, polypyrrole, polyaniline, or polythiophen
  • a conductive polymer electrode is more flexible and less brittle than the ITO electrode such that it is mechanically stable when bent or folded.
  • the conductive polymer absorbs visible light
  • an electrode coated with a thick conductive polymer has a very poor light transmissivity.
  • most of the conductive polymers are insoluble, their thin-film processes are very complicated and their applicable process temperatures are very low.
  • a carbon nanotube has recently been proposed as a conductive material for a transparent electrode.
  • the carbon nanotube has an excellent electrical conductivity, a good adhesiveness to substrates, and a low deformation due to thermal expansion.
  • the carbon nanotube has metallic or semi-conductive characters depending on winding angles of a graphen sheet and diameters of a tube, has a resistivity as low as 10 to 10 ⁇ cm.
  • the carbon nanotube has excellent mechanical characteristic and chemical stability, and a wide surface area. Furthermore, since a low percolation threshold is formed with a small amount of carbon nanotube, a transparent film is obtained in a visible light range.
  • Fig. 1 illustrates a conductive composite material 10 which is disclosed in Korean
  • the conductive composite material 10 includes a substrate 11 and a transparent conductive layer 12.
  • the substrate 11 is made of a transparent material, such as thermoplastic resin, thermosetting resin, or glass.
  • the transparent conductive layer 12 is provided on the substrate 11.
  • the transparent conductive layer 12 includes a carbon nanotube 12a and a binding agent 12b.
  • the binding agent 12b acts to bind the substrate 11 with the carbon nanotube 12a.
  • the binding agent 12b is formed on the substrate 11 and is made of material which exhibits good weathering resistance and corrosion resistance together with high surface strength.
  • the binding agent 12b is normally made of a polymer film.
  • the conductive composite material 10 is prepared by making a coating solution, applying the coating solution on the substrate 11, and drying the coating solution.
  • the coating solution is made by dissolving the binding agent 12b in a volatile solvent and dispersing the carbon nanotube 12a in the volatile solvent.
  • the conductive composite material 10 thus prepared further includes the binding agent 12b to bind the substrate 11 with the carbon nanotube 12a. That is, since the carbon nanotube 12a is dispersed in the binding agent 12b, a relatively large amount of carbon nanotube 12a is needed to obtain an appropriate surface resistance, causing an increased cost and a reduced transparency.
  • the carbon nanotube 12a is formed on the substrate 11 by coating or spray, it is not easy to form patterns on the conductive composite material, such that an additional process is needed to form the patterns.
  • a conductive fiber 22, such as carbon nanotube, is directly formed on the substrate 21 in order to enhance the transparency and conductivity of the conductive composite material.
  • the conductive fiber 22 is not securely fixed to the substrate 21.
  • the conductive fiber 22 is formed on the substrate 21 by coating or spray, it is not easy to form patterns on the conductive composite material, such that an additional process is needed to form the patterns.
  • the present invention provides a conductive composite material, which has stable adhesiveness and high electrical conductivity together with good optical transparency and high transformability, and a method for manufacturing the same.
  • a conductive fiber thin-film is fixed to a base layer by fixing a conductive fiber in a conductive fiber dispersion solution to the base layer and removing the remaining materials through the base layer. Accordingly, the conductive fiber thin-film is reduced in thickness, resulting in enhanced transparency. In addition, the conductive fiber thin- film is formed of the conductive fiber, resulting in enhanced conductivity.
  • the conductive fiber in the conductive fiber dispersion solution is fixed to an initial base layer, the remaining materials are removed through the initial base layer, and the conductive fiber thin-film is moved to a final base layer. Accordingly, the conductive fiber thin-film is reduced in thickness, resulting in high conductivity and enhanced dispersion degree.
  • FIG. 1 is a cross-sectional view of a conventional conductive composite material.
  • FIG. 2 is a cross-sectional view of another conventional conductive composite material.
  • FIG. 3 is a cross-sectional view of a conductive composite material according to an exemplary embodiment of the present invention.
  • Fig. 4 is an enlarged cross-sectional view of the 'A' part of Fig. 3.
  • FIG. 5 is a flow chart of a method for manufacturing a conductive composite material according to an exemplary embodiment of the present invention.
  • FIG. 6 is a flow diagram of a method for manufacturing a conductive composite material according to an exemplary embodiment of the present invention.
  • Fig. 7 illustrates a process of providing a conductive fiber thin-film on a membrane.
  • FIG. 8 illustrates processes of fixing a conductive fiber thin-film to a membrane and making the membrane transparent.
  • Fig. 9 is an enlarged cross-sectional view of the 'B' part of Fig. 6.
  • Fig. 10 is an enlarged cross-sectional view of the 'C part of Fig. 9.
  • FIG. 11 is a flow chart of a method for manufacturing a conductive composite material according to another exemplary embodiment of the invention.
  • Fig. 12 is a cross-sectional view of an initial base layer of Fig. 11.
  • Fig. 13 illustrates a process of providing a conductive fiber thin-film on an initial base layer of Fig. 11.
  • Figs. 14 and 15 illustrate a process of moving a conductive fiber thin-film of Fig. 11 to a final base layer.
  • Fig. 16 illustrates a process of securely fixing a conductive fiber thin-film to a final base layer. Best Mode for Carrying Out the Invention
  • the present invention discloses a conductive composite material including: a base layer; a conductive fiber thin-film made of conductive fiber and formed on the base layer; and a mixture layer in which part of the conductive fiber is inserted into part of the base layer.
  • the present invention also discloses a method for manufacturing a conductive composite material, including: providing a membrane; forming a carbon nano-fiber film on the membrane by removing through pores of the membrane at least part of materials except carbon nano-fiber from a carbon nano-fiber dispersion solution; fixing the carbon nano-fiber film to the membrane; and making the membrane transparent.
  • the present invention also discloses a method for manufacturing a conductive composite material, including: providing an initial base layer; providing a conductive fiber thin-film on the initial base layer; and moving the conductive fiber thin-film provided on the initial base layer to a final base layer.
  • FIG. 3 is a cross-sectional view of a conductive composite material according to an exemplary embodiment of the present invention.
  • Fig. 4 is an enlarged cross-sectional view of the 'A' part of Fig. 3.
  • a conductive composite material 100 includes a base layer 110, a conductive fiber thin-film 130, and a mixture layer 120.
  • the conductive fiber thin-film 130 is provided on the base layer 110, and the mixture layer 120 is provided between the base layer 110 and the conductive fiber thin- film 130 to securely fix the base layer 110 and the conductive fiber thin-film 130 to each other.
  • the base layer 110 may be made of a polymer 111 which is preferably flexible.
  • polymer 111 examples include polycarbonate, polyethylene terephtalate (PET), polyamide, cellulose ester, regenerated cellulose, nylon, polypropylene, polyacry- lonitrile, polysulfone, polyethersulfone, and polyvinylidenfluoride.
  • the polymer 111 may be made of a polymer membrane having pores 113 each having a diameter Dp.
  • all or most of materials, such as a binding agent, except a conductive fiber may be removed, whereby the conductive fiber thin-film 130 is made only of the conductive fiber.
  • the polymer 111 made of the polymer membrane may be made of a material in which the pores 113 are removed when more than a predetermined level of heat and/or pressure is applied to the polymer 111.
  • the polymer 111 may be made of a material in which the pores 113 are removed when more than a predetermined intensity of light is irradiated on the polymer 111.
  • the polymer 111 may be made of a material in which the pores 113 are removed when more than a predetermined level of voltage is applied to the polymer 111.
  • the polymer 111 is not transparent due to the presence of the pores 113. That is, when the pores 113 are removed, the polymer 111 is made transparent. Therefore, when a conductive composite material 100 needs to have an excellent light transmissivity, a transparent polymer is obtained by applying a predetermined condition, such as heat, pressure, light or voltage, to remove the pores 113.
  • the polymer membrane may be changed to be optically transparent at a glass transition temperature Tg, and have a thickness of 10 to 1000mm.
  • the polymer membrane preferably has pores each having a diameter Dp of 0.01 to
  • the polymer membrane may be optically transparent by coating a soluble organic solvent.
  • the soluble organic solvent include benzene, toluene, xylene, chloroform, methylen chloride, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, dioxane, tetrahydrofuran, dimethyl formamide, and dimethylsulfoxide.
  • the conductive fiber thin-film 130 is provided on the base layer 110.
  • the conductive fiber thin-film 130 is made of conductive fibers 131.
  • the conductive fibers 131 may be separated from one another, while at least part of the conductive fibers 131 may be contiguous to one another.
  • the conductive fiber 131 may be a carbon fiber or, preferably, a carbon nanotube.
  • the carbon nanotube is structured in such a manner that a graphene sheet is tubularly wound which is honeycombed with a carbon atom bound with three other carbon atoms.
  • the carbon nanotube has a diameter of 1 to lOOnm.
  • the carbon nanotube is divided into a single-walled carbon nanotube and a multi- walled carbon nanotube according to the number of graphene sheets which form walls of the carbon nanotube.
  • the single- walled carbon nanotube is formed in a bundle of tubes.
  • the carbon nanotube has an excellent conductivity since it has a resistivity as low as 10 to 10 ⁇ cm.
  • the carbon nanotube has excellent mechanical characteristics, is chemically stable and has a large surface area. Since the carbon nanotube shaped like a bar has a large aspect ratio, it is easy to form a low percolation threshold such that its conductivity is excellent.
  • carbon nanotube aqueous dispersion solution or carbon nanotube organic dispersion solution is prepared.
  • the carbon nanotube aqueous dispersion solution is prepared by adding carbon nanotube to an aqueous solution in which a surface active agent, such as Triton X-100, sodium dodecylbenzene sulfonate (Na-DDBS), cetyl trimethyl ammonium bromide (CTAB) or sodium dodecyl sulfate (SDS), is dissolved, and applying ultrasonic waves to the solution for 1 to 120 minutes.
  • a surface active agent such as Triton X-100, sodium dodecylbenzene sulfonate (Na-DDBS), cetyl trimethyl ammonium bromide (CTAB) or sodium dodecyl sulfate (SDS)
  • the carbon nanotube organic dispersion solution is prepared by adding carbon nanotube to an organic solution, such as N-methylpyrrolidone (NMP), o-dichlorobenzene, dichloroethane, dimethyl formamide (DMF) or chloroform, and applying ultrasonic waves to the solution for 1 to 120 minutes.
  • NMP N-methylpyrrolidone
  • o-dichlorobenzene o-dichlorobenzene
  • dichloroethane dichloroethane
  • DMF dimethyl formamide
  • chloroform chloroform
  • the carbon nanotube aqueous dispersion solution or carbon nanotube organic dispersion solution thus prepared is filtered by a large-sized vacuum filter equipped with the base layer 110, at lease part of or, preferably, all of materials, except the carbon nanotube, are removed through the pores 113 of the polymer membrane, such that a uniform carbon nanotube film is formed on the base layer 110.
  • the thickness of the carbon nanotube film thus formed i.e., the thickness H of the sum of the mixture layer 120 and the conductive fiber thin-film 130 in Fig. 3, can be easily controlled by adjusting the amount of the carbon nanotube dispersion solution to be filtered.
  • the carbon nanotube film formed on the polymer membrane can be additionally cleaned using water to remove the surface active agent remaining on the carbon nanotube film after filtering the carbon nanotube aqueous dispersion solution.
  • the carbon nanotube film preferably has a thickness of 1 to 500nm. When the thickness H is smaller than lnm, it is not possible to obtain a satisfactory conductivity. When the thickness is larger than 50nm, the light transmissivity of the electrode may decrease.
  • the conductive fiber 131 such as carbon nanotube
  • the base layer it is possible to manufacture a transparent electrode with a good conductivity using a small amount of the conductive fiber, compared to the existing conductive composite material in which the carbon nanotube exists inside the polymer membrane.
  • At least part of materials except the conductive fiber 131 is removed through the polymer membrane while the conductive fiber 131 is uniformly dispersed in the solvent, such that the conductive fiber 131 is uniformly dispersed on the polymer 111.
  • the conductive composite material 100 has an excellent conductivity.
  • the conductive fiber thin-film 130 has a reduced thickness and has more than a predetermined conductivity, the conductive composite material 100 has an excellent transparency.
  • the mixture layer 120 is provided between the base layer 110 and the conductive fiber thin-film 130.
  • the mixture layer 120 is formed by inserting part 131a of the conductive fiber 131 into part 11 Ia of the base layer 110.
  • the mixture layer 120 may be formed by pressing the base layer 110 and the conductive fiber thin-film 130. Prior to pressing, the base layer 110 is subjected to heat treatment so that the conductive fiber of the conductive fiber thin-film 130 can be satisfactorily dispersed in the base layer 110 upon pressing.
  • the mixture layer 120 is formed by inserting the part 131a of the conductive fiber into the base layer 110.
  • the density of the conductive fiber 131 per the unit volume of the mixture layer 120 is less than the density of the conductive fiber 131 per the unit volume of the conductive fiber thin-film 130. Therefore, the conductive fiber thin-film 130 has an excellent conductivity.
  • the conductive fiber thin-film 130 may have a resistivity of 10 to 10 ⁇ /sq.
  • the mixture layer 120 may be formed by inserting part of the conductive fiber 131 of the conductive fiber thin-film 130 into at least part of the pores 113 of the polymer membrane which is provided in the base layer 110. That is, the conductive fiber and t he polymer membrane are more securely bound with each other by directly binding the conductive fiber thin-film 130 with the base layer 110.
  • the conductive fiber and the polymer membrane are physicochemically bound with each other due to interdigitation on an interface therebetween, such that the conductive fiber thin-film is bounded much more securely. According to the present embodiment of the invention, it is possible to save the amount of conductive fiber, and to prevent the conductivity from decreasing when the conductive fiber, particularly carbon nanotube, is dispersed in the polymer. Therefore, it is possible to obtain an excellent conductivity without the need to coat an additional conductive polymer film.
  • a carbon nanotube film is not uniform and is not securely fixed, such that it is very difficult or not possible to manufacture a conductive composite film which is large and uniform.
  • it is possible to very securely fix a conductive fiber thin-film to a polymer by positioning a uniform conductive fiber (carbon nanotube) thin-film on a non-transparent polymer (polymer film), and fixing the conductive fiber thin-film to the polymer simultaneously with or following making the polymer transparent by heat, pressure, or solvent-coating.
  • the conductive fiber such as carbon nanotube is provided on the transparent polymer, it is possible to manufacture a soft and transparent conductive composite material 100 having an excellent conductivity using an extremely small amount of conductive fiber, compared to the conventional composite film in which the carbon nanotube is uniformly dispersed in the polymer matrix.
  • the transparent conductive composite material 100 may be used in a thin-film transistor liquid crystal display (TFT-LCD), a plasma display panel (PDP), an organic light emitting diode (OLED), a touch panel, an electromagnetic-wave shield, an electrostatic-discharge shield, a heat reflector, a surface heater, a photo-electric converter, etc.
  • TFT-LCD thin-film transistor liquid crystal display
  • PDP plasma display panel
  • OLED organic light emitting diode
  • touch panel a touch panel
  • an electromagnetic-wave shield an electrostatic-discharge shield
  • a heat reflector a surface heater
  • a photo-electric converter etc.
  • the transparent conductive composite material 100 is flexible, light and mechanically stable, such that it may be used as a transparent electrode of a large- sized flexible display.
  • FIG. 5 is a flow chart of a method for manufacturing a conductive composite material according to an exemplary embodiment of the present invention.
  • the method according to the present embodiment of the invention includes providing a membrane (Sl 10), and fixing a conductive fiber thin-film to the membrane (S 120). The method may further include making the membrane transparent (S 130).
  • FIG. 6 is a flow diagram of a method for manufacturing a conductive composite material according to an exemplary embodiment of the present invention.
  • Figs. 7 to 9 illustrate individual processes shown in Fig. 6.
  • a membrane is provided.
  • the membrane is made of the polymer 111 and has a plurality of pores 113 as shown in Fig. 4.
  • the membrane acts so that all or most of materials, such as a solvent normally including dispersion agent and binding agent, except the conductive fiber can be removed through the pores 113 of the membrane while the conductive fiber thin-film is formed.
  • the polymer membrane examples include polycarbonate, polyethylene terephtalate (PET), polyamides, cellulose ester, regenerated cellulose, nylon, polypropylene, polyacrylonitrile, polysulfone, polyethersulfone, and polyvinyli- denfluoride.
  • the membrane may be a polymer membrane with pores each having a diameter Dp of 0.01 to 10mm and a thickness of 10 to 1000mm.
  • the conductive fiber thin-film 130 is fixed to the membrane.
  • the conductive fiber thin-film 130 is made only or mostly of a conductive fiber formed in a thin-film layer.
  • the conductive fiber 131 may be carbon fiber.
  • the carbon fiber include a single- walled carbon nanotube, a double-walled carbon nanotube, a multi- walled carbon nanotube, a carbon nano-fiber, and graphite.
  • the conductive fiber 131 may preferably be a carbon nanotube.
  • the carbon nanotube is structured in such a manner that a graphene sheet is tubularly wound which is honeycombed with a carbon atom bound with three other carbon atoms.
  • the carbon nanotube has a diameter of 1 to 100 nm.
  • the carbon nanotube is divided into a single- walled carbon nanotube and a multi- walled carbon nanotube according to the number of graphene sheets which form walls of the carbon nanotube.
  • the single- walled carbon nanotube is formed in a bundle of tubes.
  • the carbon nanotube has an excellent conductivity since it has a resistivity as low as 10 to 10 ⁇ cm.
  • the carbon nanotube has excellent mechanical characteristics, is chemically stable and has a large surface area. Since the carbon nanotube shaped like a bar has a large aspect ratio, it is easy to form a low percolation threshold such that an excellent conductivity is obtained.
  • the carbon nanotube film preferably has a thickness H of 1 to 500nm.
  • the thickness is smaller than lnm, it is not possible to obtain a satisfactory conductivity.
  • the thickness is larger than 500nm, the light transmissivity of the electrode may decrease.
  • the step of fixing the conductive fiber thin-film 131 to the membrane may include placing a conductive fiber dispersion solution 140 on the membrane, and removing at least part of materials except the conductive fiber 131 from the conductive fiber dispersion solution 140 through the pores 113 of the membrane.
  • the materials 141 such as a solvent normally including a binding agent and a dispersion agent, except the conductive fiber 131 is removed through the membrane from the solvent in which the conductive fiber 131 is dispersed, whereby the conductive fiber thin-film 130 can be uniformly dispersed on the membrane. Furthermore, since the whole or most of the conductive fiber thin-film 130 is made only of the conductive fiber 131, its conductivity is enhanced. Accordingly, the thickness of the conductive fiber thin-film 130 can be reduced, such that the conductive composite material has an enhanced transparency. In addition, the solvent can be removed when the conductive fiber 131 is uniformly dispersed in the solvent, whereby the conductive fiber 131 has an excellent dispersion degree on the membrane, and has a more improved conductivity.
  • the materials 141 such as a solvent normally including a binding agent and a dispersion agent
  • the conductive fiber dispersion solution may be formed on the membrane by vacuum filtering, self-assembly technique, Langmuir-Blodgett technique, solution casting, bar coating, dip coating, spin coating, jet coating, etc.
  • the conductive fiber thin-film 130 may be uniformly dispersed on the membrane by vacuum filtering.
  • the conductive fiber aqueous dispersion solution 140 is prepared by adding the conductive fiber 131 to the solvent 141 in which a surface active agent is dissolved.
  • the surface active agent include Triton X-100, sodium dodecylbenzene sulfonate (Na-DDBS), cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS).
  • the conductive fiber aqueous dispersion solution is prepared by adding the conductive fiber to the aqueous solution and applying ultrasonic waves to the solution, for example, for 1 to 120 minutes.
  • the conductive fiber aqueous dispersion solution 140 may be prepared by other methods.
  • the conductive fiber aqueous dispersion solution 140 may be prepared by adding the conductive fiber 131 to an organic solvent, such as N- methylpyrrolidone (NMP), o-dichlorobenzene, dichloroethane, dimethylformamide (DMF), and chloroform.
  • NMP N- methylpyrrolidone
  • o-dichlorobenzene o-dichlorobenzene
  • dichloroethane dichloroethane
  • DMF dimethylformamide
  • the conductive fiber aqueous dispersion solution 140 stored in a solution container 150 is filtered through a vacuum filter 160.
  • the membrane is provided facing the solution container 150 of the vacuum filter 160.
  • the solvent 141 except the conductive fiber 131 is filtered through the pores 113 of the membrane, such that the conductive fiber thin-film 130 is uniformly formed on the membrane.
  • the carbon nanotube film 130 thus formed is cleaned with water.
  • the conductive fiber 131 can be inserted into part of the membrane.
  • the conductive fiber 131 may be inserted into the pores 113 of the membrane.
  • the method according to the present embodiment of the invention may further include inserting at least part of the conductive fiber thin-film 130 into at least part of the membrane to securely fix the conductive fiber thin-film 130 to the membrane.
  • the conductive composite material 100 may include the base layer 110 formed only of the membrane, the mixture layer 120 having the membrane mixed with the conductive fiber, and the conductive fiber thin-film 130 formed only of the conductive fiber.
  • a predetermined level of heat is applied to the membrane, and the membrane and the conductive fiber thin-film 130 are pressed by a pressing unit 170, such as a roller.
  • the polymer membrane is softened at a predetermined high temperature, and the membrane and the conductive fiber thin-film 130 are pressed with the pressing unit 170, such that part of the conductive fiber 131 is inserted into part of the membrane.
  • the membrane with part of the conductive fiber 131 inserted is hardened. Accordingly, the conductive fiber thin-film 130 is securely fixed to the membrane.
  • the conductive composite material may neither be transparent nor have a satisfactory transparency. Accordingly, the method according to the present embodiment of the invention may further include making the membrane transparent.
  • the membrane may be made transparent by removing the pores 113.
  • the membrane may be made of a material in which the pores 113 are removed upon applying more than a predetermined level of heat and/or pressure to the membrane, a material in which the pores 113 are removed upon irradiating more than a predetermined intensity of light on the membrane, or a material in which the pores 113 are removed upon applying more than a predetermined level of voltage to the membrane.
  • the membrane is made of a material which changes to be optically transparent at a glass transition temperature Tg
  • the pores 113 of the membrane are removed by applying heat to the membrane at more than the glass transition temperature Tg.
  • the membrane may be changed to be optically transparent by coating a soluble organic solvent on the membrane.
  • the soluble organic solvent include benzene, toluene, xylene, chloroform, methylen chloride, acetone, methyl ethyl ketone, cyclohexane, etyle acetate, dioxane, tetrahydrofuran, dimethylformamide, and dimethylsulfoxide.
  • the membrane having the conductive fiber thin-film 130 formed thereon may be made transparent either in a consecutive manner using a hot-pressing roller which has preheating, heating and cooling roller units, or in a discontinuous manner using a plane -pressing unit.
  • the heating roller unit of the hot-pressing roller preferably has a surface with an average roughness less than 0.2a, and is made of stainless steel (SUS) which will not stick to the heated polymer.
  • an optically transparent plastic film may be formed on an upper surface of the conductive fiber thin-film and/or a lower surface of the membrane.
  • the step of making the membrane transparent may be carried out simultaneously with the step of securely fixing the conductive fiber thin-film to the membrane. That is, when part of the conductive fiber 131 is inserted into the membrane, a high-temperature heat may be applied to the membrane so that the pores 113 of the membrane can be removed.
  • the membrane made of polymer is made transparent when the membrane holds the conductive fiber thin-film, such as carbon nanotube. Accordingly, interdigitation occurs in an interface between the membrane and the conductive fiber thin-film, whereby the carbon nanotube film is securely fixed to the membrane. Therefore, it is possible to substantially reduce an amount of conductive fiber, such as carbon nanotube, and to securely fix the conductive fiber thin-film to the membrane. In addition, since the conductivity is not lowered even though the carbon nanotube is dispersed in the polymer, it is possible to obtain a conductive composite material having an excellent conductivity without coating an additional conductive polymer film.
  • a uniform conductive fiber thin-film is formed on a non- transparent membrane, and the membrane is made transparent and is fixed to the conductive fiber thin-film by heating, pressing, or solvent-coating, whereby it is possible to very securely fix the conductive fiber thin-film to the membrane.
  • the conductive fiber is formed only on the surface of the transparent membrane, it is possible to prepare a soft, transparent conductive composite material having an excellent conductivity using a small amount of conductive fiber, compared to the conventional composite film in which a carbon nanotube is uniformly dispersed in a polymer material.
  • Fig. 9 illustrates the conductive composite material 100 which is prepared by the above-mentioned method.
  • Fig. 10 illustrates an enlarged cross-sectional view of the 'C part of Fig. 9.
  • the mixture layer 120 is provided between the base layer 110 and the conductive fiber thin-film 130.
  • the mixture layer 120 is formed by inserting part of the conductive fiber 131 of the conductive fiber thin-film 130 into at least part of the pores 113 of the membrane. Accordingly, it is possible to very securely fix the conductive fiber thin- film 130 to the base layer 110.
  • the conductive composite material has an excellent conductivity.
  • the conductive composite material may have a resistivity of 10 to l0 8 ⁇ /sq.
  • a carbon nanotube was used as the conductive fiber 130, and a polyethersulfone membrane with pores 113 each having a diameter of 0.2mm was used.
  • 0.0015 wt% carbon nanotube aqueous dispersion solution 140 was prepared by adding 15mg of a single- walled carbon nanotube 131 (mfg. by ILJIN Nanotech) to 11 of aqueous solution 141 in which 1Og of SDS as a surface active agent was dissolved, and applying 4OkHz ultrasonic waves of 45W for 30 minutes.
  • the base layer 110 made of a polyethersulfone membrane with pores each having a diameter of 0.2mm is provided in the large-sized vacuum filter 160.
  • a solvent except the carbon nanotube was filtered through the pores 113, such that a carbon nanotube film was uniformly formed on the polymer membrane.
  • the carbon nanotube film thus formed was cleaned with water.
  • the polymer membrane was made transparent using the hot-pressing roller, such that a transparent conductive composite material 100 was obtained in which the carbon nanotube film 130 is formed on the transparent base layer 110.
  • the conductive fiber 130 and the membrane was preheated to a temperature of 11O 0 C using a preheating roller, and the polymer membrane was made transparent through a heating roller with a temperature of 22O 0 C.
  • the carbon nanotube forming the conductive fiber thin-film 130 is inserted into the membrane to form the mixture layer 120.
  • the light transmissivity of the transparent electrode thus manufactured was measured to be about 90% at 550nm by an ultraviolet- visible spectroscope.
  • the surface resistance of the transparent electrode was measured to be less than 200 ⁇ /sq by a surface resistance meter.
  • the uniformity of surface resistance i.e., the standard- deviation/average of surface resistance, was less than 7%.
  • the transparent electrode manufactured according to the present embodiment of the invention was proved to be excellent in transparency, conductivity, uniformity of conductivity, flexibility, and adhesion stability of the carbon nanotube film.
  • the transparent conductive composite material 100 was prepared in the same method as that of Embodiment 1, except that a carbon nanotube/membrane composite material with a small amount of dimethylformamide (DMF) coated passed through a heating roller with a temperature of 8O 0 C to make the membrane film transparent.
  • DMF dimethylformamide
  • the transparent conductive composite material 100 was prepared in the same manner as that of Embodiment 1, except that during the process of making transplant the membrane having the carbon nanotube film formed thereon, an optically transparent polyethylene terephtalate film was stacked on a lower surface of a polymer film, and a carbon nanotube/membrane composite material with a small amount of dimethylformamide (DMF) coated passed through a heating roller with a temperature of 8O 0 C to make the membrane film transparent.
  • DMF dimethylformamide
  • the transparent conductive composite material 100 was prepared in the same method as that of Embodiment 1, except that the carbon nanotube/membrane composite material was made transparent using a plane-pressing unit rather than a hot- pressing roller.
  • FIG. 11 is a flow chart of a method for manufacturing a conductive composite material according to another exemplary embodiment of the invention.
  • the method according to the present embodiment of the invention includes providing an initial base layer (S210), placing a conductive fiber thin-film on the initial base layer (S220), and moving the conductive fiber thin-film onto a final base layer (S230).
  • Figs. 12 to 16 are views for explaining a method for manufacturing a conductive composite material according to an exemplary embodiment of the present invention.
  • an initial base layer 210 is provided.
  • the initial base layer 210 may be formed of a polymer membrane 211 having a plurality of pores 213.
  • the membrane is provided such that all or most of materials except a conductive fiber are removed through the pores 213 of the membrane during the process of manufacturing the conductive fiber thin-film.
  • the polymer membrane 211 may be made of polycarbonate, polyethylene terephtalate (PET), polyamides, cellulose ester, regenerated cellulose, nylon, polypropylene, polyacrylonitrile, polysulfone, polyethersulfone, or polyvinyli- denfluoride.
  • PET polyethylene terephtalate
  • polyamides polyamides
  • cellulose ester regenerated cellulose
  • nylon polypropylene
  • polyacrylonitrile polysulfone
  • polyethersulfone polyethersulfone
  • polyvinyli- denfluoride polyvinyli- denfluoride
  • the polymer membrane may have pores each having a diameter Dp of
  • the conductive fiber thin-film 130 is placed on the initial base layer 210.
  • the conductive fiber thin-film 130 is made only or mostly of the conductive fiber 131.
  • the conductive fiber thin-film 130 may be formed and dispersed on the initial base layer 210, or may be formed on the initial base layer 210.
  • the conductive fiber 131 may be a carbon fiber.
  • the carbon fiber include a single-walled carbon nanotube, a double-walled carbon nanotube, a multi- walled carbon nanotube, a carbon nano-fiber, and graphite.
  • the conductive fiber 131 may preferably be a carbon nanotube.
  • the carbon nanotube is structured in such a manner that a graphene sheet is tubularly wound which is honeycombed with a carbon atom bound with three other carbon atoms.
  • the carbon nanotube has a diameter Dc of 1 to lOOnm.
  • the carbon nanotube is divided into a single- walled carbon nanotube and a multi- walled carbon nanotube according to the number of graphene sheets which form walls of the carbon nanotube.
  • the single- walled carbon nanotube is formed in a bundle of tubes.
  • the carbon nanotube has an excellent conductivity since it has a resistivity as low as 10 to 10 ⁇ cm.
  • the carbon nanotube has excellent mechanical characteristics, is chemically stable and has a large surface area. Since the carbon nanotube shaped like a bar has a large aspect ratio, it is easy to form a low percolation threshold such that its conductivity is excellent.
  • the carbon nanotube preferably has a thickness H of 1 to 500nm.
  • the carbon nanotube with a thickness smaller than lnm does not exhibit a satisfactory conductivity.
  • the carbon nanotube with a thickness larger than 500nm may show a reduced light transmissivity of the electrode.
  • the step of placing the conductive fiber thin-film 130 on the initial base layer 210 may include placing the conductive fiber dispersion solution 140 on the initial base layer 210, and removing at least part of materials except the conductive fiber 131 from the conductive fiber dispersion solution 140.
  • the conductive fiber dispersion solution 140 may be placed on the initial base layer 210 by vacuum filtering, self-assembly technique, Langmuir-Blodgett technique, solution casting, bar coating, dip coating, spin coating, spray coating, etc.
  • the step of placing the conductive fiber thin-film 130 on the initial base layer 210 may include placing the conductive fiber dispersion solution 140 on the membrane, and removing at least part of materials except the conductive fiber 131 from the conductive fiber dispersion solution 140 through the pores 213 of the membrane.
  • the conductive fiber thin-film 130 can be uniformly dispersed on the initial base layer 210 by removing through the membrane at least part of the materials 141, such as solvent normally including a dispersion agent or a binding agent, except the conductive fiber 131. Furthermore, since the whole or most of the conductive fiber thin-film 130 is made only of the conductive fiber 131, the conductive fiber thin-film 130 has an excellent conductivity even though the conductive fiber thin-film 130 is reduced in thickness. As a result, the conductive fiber thin-film 130 has an excellent transparency. In addition, when at least part of or, preferably, the whole of the materials 141 except the conductive fiber 131 is removed, the conductive fiber 131 can be uniformly dispersed on the initial base layer 210 and thus have an excellent conductivity.
  • the materials 141 such as solvent normally including a dispersion agent or a binding agent
  • the conductive fiber thin-film 130 is uniformly dispersed on the initial base layer
  • the conductive fiber aqueous dispersion solution 140 is prepared by adding the conductive fiber 131 to the solvent 141 in which the surface active agent is dissolved.
  • the surface active agent include Triton X-100, sodium dodecylbenzene sulfonate (Na-DDBS), cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS).
  • the conductive fiber aqueous dispersion solution is prepared by adding the conductive fiber to the aqueous solution and applying ultrasonic waves to the solution, for example, for 1 to 120 minutes.
  • the conductive fiber dispersion solution 140 may be prepared by other methods.
  • the conductive fiber dispersion solution 140 may be prepared by adding the conductive fiber 131 to an organic solvent, such as N-methylpyrrolidone (NMP), o-dichlorobenzene, dichloroethane, dimethylformamide (DMF) and chloroform.
  • NMP N-methylpyrrolidone
  • o-dichlorobenzene o-dichlorobenzene
  • dichloroethane dichloroethane
  • dimethylformamide (DMF) dimethylformamide
  • the conductive fiber dispersion solution 140 stored in the solution container 150 is filtered by the vacuum filter 160.
  • the initial base layer 210 is mounted on a part of the vacuum filter 160, which faces the solution container 150, and the conductive fiber dispersion solution 140 is provided on the initial base layer 210.
  • a negative pressure is applied from the vacuum filter 160 to the initial base layer 210.
  • the conductive fiber thin-film 130 is uniformly formed on the initial base layer 210. Subsequently, the conductive fiber thin-film 130 thus formed is cleaned with water.
  • the conductive fiber thin-film may be prepared by other methods.
  • the conductive fiber thin-film 130 formed on the initial base layer 210 is moved to a final base layer 110. That is, the conductive fiber thin-film 130 is uniformly dispersed on the initial base layer 210 by vacuum filtering, and the conductive fiber thin-film 130 is moved to the final base layer 110, whereby the conductive composite material 100 is formed of the final base layer 110 and the conductive fiber thin-film 130 formed on the final base layer 110.
  • the initial base layer 210 and the final base layer 110 are tightly joined and then separated with more than a predetermined level of heat applied or with a binding member provided on a portion in which a pattern of the final base layer 110 is to be formed.
  • the conductive fiber having the pattern is formed on the final base layer 110. Accordingly, it is easy to form the pattern compared to the conventional method for manufacturing the conductive composite material in which the transparent conductive thin-film is formed on the substrate by coating, spraying, etc.
  • the conductive composite material is prepared by moving the conductive fiber thin-film 130, which is placed on the initial base layer 210 using the organic solvent, to the final base layer 110 without contacting with the organic solvent, whereby the conductive composite material has an enhanced evenness and conductivity. After the conductive fiber thin-film 130 is moved, the initial base layer 210 can be reused to manufacture another conductive fiber thin-film.
  • the conductive fiber thin-film 130 is thin in thickness and has a high conductivity, whereby the conductive composite material has an enhanced transparency.
  • the final base layer 110 may be made of a transparent polymer, which increases the transparency of the conductive composite material.
  • the final base layer 110 may be made of polyethylene terephtalate.
  • the final base layer 110 is made of a material which is lower in softening point than the first base layer 210.
  • the step of moving the conductive fiber thin-film 130 to the final base layer 110 is performed, as shown in Figs. 14 and 16, by pressing the final base layer 110 to the conductive fiber thin-film 130 and separating the first base layer 210 and the final base layer 110 from each other at a certain temperature between a softening point of the first base layer 210 and a softening point of the final base layer 110. That is, at a temperature higher than the softening point of the final base layer 110, the final base layer 110 is softened such that a different material tends to be inserted.
  • the conductive fiber thin-film 130 is not fixed to the initial base layer 210 very securely. Accordingly, when the conductive fiber thin-film 130 placed on the initial base layer 210 is made contact with or pressed to the final base layer 110 at the temperature, the conductive fiber thin-film 130 is moved to the final base layer 110 with a high level of adhesion.
  • an additional adhesion layer having a higher level of adhesion than that of the initial base layer 210 to the conductive fiber thin-film 130 is formed on the surface of the final base layer 110, and the conductive fiber thin-film 130 placed on the initial base layer 210 is made contact with or pressed to the final base layer 110.
  • the initial base layer having the conductive fiber thin-film formed thereon may be made contact with an additional final base layer having a higher surface energy than that of the initial base layer to move the conductive fiber thin-film.
  • the conductive fiber thin-film placed on the initial base layer is moved onto the final base layer by heat-transfer printing to obtain a patterned conductive fiber thin-film.
  • the method according to the present embodiment of the invention may further include inserting at least part of the conductive fiber 131 of the conductive fiber thin-film 130 into at least part of the final base layer 110.
  • the conductive composite material 100 includes the final base layer
  • the final base layer 110 and the conductive fiber thin-film 130 are pressed with a pressing unit, such as a roller. That is, when the final base layer 110 is softened at a predetermined high temperature, the final base layer 110 and the conductive fiber thin-film 130 are pressed with a pressing unit, whereby part of the conductive fiber 131 impregnates part of the final base layer 110.
  • a pressing unit such as a roller. That is, when the final base layer 110 is softened at a predetermined high temperature, the final base layer 110 and the conductive fiber thin-film 130 are pressed with a pressing unit, whereby part of the conductive fiber 131 impregnates part of the final base layer 110.
  • the conductive composite fiber 100 is cooled down during a predetermined time, the final base layer 110 is hardened with the part of the conductive fiber 131 inserted therein. Therefore, the conductive fiber thin-film 130 is securely fixed to the final base layer 110.
  • a carbon nanotube was used as the conductive fiber 130, and a polyethersulfone membrane with pores 213 each having a diameter of 0.2mm was used as the initial base layer 210.
  • the step of fixing the conductive fiber thin-film 130 to the initial base layer 210 was performed using the vacuum filter shown in Fig. 13.
  • 0.0015 wt% carbon nanotube aqueous dispersion solution 140 was prepared by adding 15mg of a single- walled carbon nanotube 131 (mfg. by ILJIN Nanotech) to 11 of the aqueous solution 141 in which 1Og of SDS as a surface active agent was dissolved, and applying 4OkHz ultrasonic waves of 45W for 30 minutes.
  • the initial base layer 210 made of a polyethersulfone membrane with pores each having a diameter of 0.2mm is provided in the large-sized vacuum filter 160.
  • a solvent except the carbon nanotube was filtered through the pores 213, such that a carbon nanotube film was uniformly formed on the initial base layer 210.
  • the carbon nanotube film thus formed was cleaned with water.
  • the light transmissivity of the transparent conductive composite material thus manufactured was measured to be about 90% at 550nm by an ultraviolet- visible spectroscope.
  • the surface resistance of the transparent electrode was measured to be less than 200 ⁇ /sq by a surface resistance meter.
  • the uniformity of surface resistance i.e., the standard-deviation/average of surface resistance, was less than 7%.
  • the transparent electrode manufactured according to the present embodiment of the invention was proved to be excellent in transparency, conductivity, uniformity of conductivity, flexibility, and adhesion stability of the carbon nanotube film.
  • the present invention can effectively be applied to a conductive composite material, which is flexible and used in an electronic product such as a flat panel display, and a method for manufacturing the same.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

A conductive composite material is provided, including: a base layer; a conductive fiber thin-film made of conductive fiber and formed on the base layer; and a mixture layer in which part of the conductive fiber is inserted into part of the base layer.

Description

Description
CONDUCTIVE COMPOSITE MATERIAL AND METHOD FOR
MANUFACTURING THE SAME
Technical Field
[1] The present invention relates to a conductive composite material, which is flexible and used in an electronic product such as a flat panel display, and a method for manufacturing the same. Background Art
[2] Transparent conductive materials have been widely used in a thin-film transistor liquid crystal display (TFT-LCD), a plasma display panel (PDP), an organic light emitting diode (OLED), a touch panel, an electromagnetic-wave shield, an electrostatic-discharge shield, a heat reflector, a surface heater, a photo-electric converter, etc.
[3] Indium tin oxide (ITO) has been widely used as a transparent conductive material because of its good electrical characteristics and high light transmissivity. However, ITO is brittle such that it is mechanically unstable when folded or bent. Furthermore, ITO tends to be deformed when thermally expanded.
[4] As an electrode material, researches have recently been focused on conductive polymers, such as polyacetylene, polypyrrole, polyaniline, or polythiophen, as substitutes for ITO. A conductive polymer electrode is more flexible and less brittle than the ITO electrode such that it is mechanically stable when bent or folded. However, since the conductive polymer absorbs visible light, an electrode coated with a thick conductive polymer has a very poor light transmissivity. In addition, since most of the conductive polymers are insoluble, their thin-film processes are very complicated and their applicable process temperatures are very low.
[5] A carbon nanotube (CNT) has recently been proposed as a conductive material for a transparent electrode. The carbon nanotube has an excellent electrical conductivity, a good adhesiveness to substrates, and a low deformation due to thermal expansion. The carbon nanotube has metallic or semi-conductive characters depending on winding angles of a graphen sheet and diameters of a tube, has a resistivity as low as 10 to 10 Ωcm. In addition, the carbon nanotube has excellent mechanical characteristic and chemical stability, and a wide surface area. Furthermore, since a low percolation threshold is formed with a small amount of carbon nanotube, a transparent film is obtained in a visible light range.
[6] Fig. 1 illustrates a conductive composite material 10 which is disclosed in Korean
Laid-Open Patent Application No. 2005-115230. The conductive composite material 10 includes a substrate 11 and a transparent conductive layer 12. The substrate 11 is made of a transparent material, such as thermoplastic resin, thermosetting resin, or glass.
[7] The transparent conductive layer 12 is provided on the substrate 11. The transparent conductive layer 12 includes a carbon nanotube 12a and a binding agent 12b. The binding agent 12b acts to bind the substrate 11 with the carbon nanotube 12a. The binding agent 12b is formed on the substrate 11 and is made of material which exhibits good weathering resistance and corrosion resistance together with high surface strength. The binding agent 12b is normally made of a polymer film.
[8] The conductive composite material 10 is prepared by making a coating solution, applying the coating solution on the substrate 11, and drying the coating solution. The coating solution is made by dissolving the binding agent 12b in a volatile solvent and dispersing the carbon nanotube 12a in the volatile solvent.
[9] The conductive composite material 10 thus prepared further includes the binding agent 12b to bind the substrate 11 with the carbon nanotube 12a. That is, since the carbon nanotube 12a is dispersed in the binding agent 12b, a relatively large amount of carbon nanotube 12a is needed to obtain an appropriate surface resistance, causing an increased cost and a reduced transparency.
[10] Furthermore, since the carbon nanotube 12a is formed on the substrate 11 by coating or spray, it is not easy to form patterns on the conductive composite material, such that an additional process is needed to form the patterns.
[11] As shown in Fig. 2, a conductive fiber 22, such as carbon nanotube, is directly formed on the substrate 21 in order to enhance the transparency and conductivity of the conductive composite material. In this case, however, since a binding part binding the substrate 21 with the conductive fiber 22 is thin, and the conductive fiber 22 has a poor dispersion degree and a poor adhesiveness to the substrate 21, the conductive fiber 22 is not securely fixed to the substrate 21. In addition, since the conductive fiber 22 is formed on the substrate 21 by coating or spray, it is not easy to form patterns on the conductive composite material, such that an additional process is needed to form the patterns.
Disclosure of Invention Technical Solution
[12] The present invention provides a conductive composite material, which has stable adhesiveness and high electrical conductivity together with good optical transparency and high transformability, and a method for manufacturing the same.
[13] Additional features of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention.
Advantageous Effects
[14] A conductive fiber thin-film is fixed to a base layer by fixing a conductive fiber in a conductive fiber dispersion solution to the base layer and removing the remaining materials through the base layer. Accordingly, the conductive fiber thin-film is reduced in thickness, resulting in enhanced transparency. In addition, the conductive fiber thin- film is formed of the conductive fiber, resulting in enhanced conductivity.
[15] In addition, since part of the conductive fiber thin-film is dispersed and inserted into part of the base layer, it is not necessary to have an additional element to fix the conductive fiber thin-film to the base layer, resulting in stable adhesiveness and high conductivity.
[16] Furthermore, the conductive fiber in the conductive fiber dispersion solution is fixed to an initial base layer, the remaining materials are removed through the initial base layer, and the conductive fiber thin-film is moved to a final base layer. Accordingly, the conductive fiber thin-film is reduced in thickness, resulting in high conductivity and enhanced dispersion degree. Brief Description of the Drawings
[17] The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention, and together with the description serve to explain the principles of the invention.
[18] Fig. 1 is a cross-sectional view of a conventional conductive composite material.
[19] Fig. 2 is a cross-sectional view of another conventional conductive composite material.
[20] Fig. 3 is a cross-sectional view of a conductive composite material according to an exemplary embodiment of the present invention.
[21] Fig. 4 is an enlarged cross-sectional view of the 'A' part of Fig. 3.
[22] Fig. 5 is a flow chart of a method for manufacturing a conductive composite material according to an exemplary embodiment of the present invention.
[23] Fig. 6 is a flow diagram of a method for manufacturing a conductive composite material according to an exemplary embodiment of the present invention.
[24] Fig. 7 illustrates a process of providing a conductive fiber thin-film on a membrane.
[25] Fig. 8 illustrates processes of fixing a conductive fiber thin-film to a membrane and making the membrane transparent.
[26] Fig. 9 is an enlarged cross-sectional view of the 'B' part of Fig. 6.
[27] Fig. 10 is an enlarged cross-sectional view of the 'C part of Fig. 9.
[28] Fig. 11 is a flow chart of a method for manufacturing a conductive composite material according to another exemplary embodiment of the invention.
[29] Fig. 12 is a cross-sectional view of an initial base layer of Fig. 11.
[30] Fig. 13 illustrates a process of providing a conductive fiber thin-film on an initial base layer of Fig. 11.
[31] Figs. 14 and 15 illustrate a process of moving a conductive fiber thin-film of Fig. 11 to a final base layer.
[32] Fig. 16 illustrates a process of securely fixing a conductive fiber thin-film to a final base layer. Best Mode for Carrying Out the Invention
[33] The present invention discloses a conductive composite material including: a base layer; a conductive fiber thin-film made of conductive fiber and formed on the base layer; and a mixture layer in which part of the conductive fiber is inserted into part of the base layer.
[34] The present invention also discloses a method for manufacturing a conductive composite material, including: providing a membrane; forming a carbon nano-fiber film on the membrane by removing through pores of the membrane at least part of materials except carbon nano-fiber from a carbon nano-fiber dispersion solution; fixing the carbon nano-fiber film to the membrane; and making the membrane transparent.
[35] The present invention also discloses a method for manufacturing a conductive composite material, including: providing an initial base layer; providing a conductive fiber thin-film on the initial base layer; and moving the conductive fiber thin-film provided on the initial base layer to a final base layer.
[36] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. Mode for the Invention
[37] The invention is described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure is thorough, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the size and relative sizes of layers and regions may be exaggerated for clarity. Like reference numerals in the drawings denote like elements.
[38] It will be understood that when an element or layer is referred to as being "on" or
"connected to" another element or layer, it can be directly on or directly connected to the other element or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being "directly on" or "directly connected to" another element or layer, there are no intervening elements or layers present.
[39] Fig. 3 is a cross-sectional view of a conductive composite material according to an exemplary embodiment of the present invention. Fig. 4 is an enlarged cross-sectional view of the 'A' part of Fig. 3.
[40] A conductive composite material 100 includes a base layer 110, a conductive fiber thin-film 130, and a mixture layer 120.
[41] The conductive fiber thin-film 130 is provided on the base layer 110, and the mixture layer 120 is provided between the base layer 110 and the conductive fiber thin- film 130 to securely fix the base layer 110 and the conductive fiber thin-film 130 to each other.
[42] The base layer 110 may be made of a polymer 111 which is preferably flexible.
Examples of the polymer 111 include polycarbonate, polyethylene terephtalate (PET), polyamide, cellulose ester, regenerated cellulose, nylon, polypropylene, polyacry- lonitrile, polysulfone, polyethersulfone, and polyvinylidenfluoride.
[43] As shown in Fig. 4, the polymer 111 may be made of a polymer membrane having pores 113 each having a diameter Dp. In a process of forming the conductive fiber thin-film 130, all or most of materials, such as a binding agent, except a conductive fiber, may be removed, whereby the conductive fiber thin-film 130 is made only of the conductive fiber.
[44] In this case, the polymer 111 made of the polymer membrane may be made of a material in which the pores 113 are removed when more than a predetermined level of heat and/or pressure is applied to the polymer 111. The polymer 111 may be made of a material in which the pores 113 are removed when more than a predetermined intensity of light is irradiated on the polymer 111. The polymer 111 may be made of a material in which the pores 113 are removed when more than a predetermined level of voltage is applied to the polymer 111. The polymer 111 is not transparent due to the presence of the pores 113. That is, when the pores 113 are removed, the polymer 111 is made transparent. Therefore, when a conductive composite material 100 needs to have an excellent light transmissivity, a transparent polymer is obtained by applying a predetermined condition, such as heat, pressure, light or voltage, to remove the pores 113.
[45] In this case, the polymer membrane may be changed to be optically transparent at a glass transition temperature Tg, and have a thickness of 10 to 1000mm.
[46] The polymer membrane preferably has pores each having a diameter Dp of 0.01 to
10mm. When the diameter Dp is larger than 10mm, the conductive fiber is removed through the pores. When the diameter Dp is smaller than 0.01mm, the permeability of solution is very low.
[47] The polymer membrane may be optically transparent by coating a soluble organic solvent. Examples of the soluble organic solvent include benzene, toluene, xylene, chloroform, methylen chloride, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, dioxane, tetrahydrofuran, dimethyl formamide, and dimethylsulfoxide.
[48] The conductive fiber thin-film 130 is provided on the base layer 110. The conductive fiber thin-film 130 is made of conductive fibers 131. The conductive fibers 131 may be separated from one another, while at least part of the conductive fibers 131 may be contiguous to one another.
[49] The conductive fiber 131 may be a carbon fiber or, preferably, a carbon nanotube.
The carbon nanotube is structured in such a manner that a graphene sheet is tubularly wound which is honeycombed with a carbon atom bound with three other carbon atoms. The carbon nanotube has a diameter of 1 to lOOnm. The carbon nanotube is divided into a single-walled carbon nanotube and a multi- walled carbon nanotube according to the number of graphene sheets which form walls of the carbon nanotube. The single- walled carbon nanotube is formed in a bundle of tubes.
[50] The carbon nanotube has an excellent conductivity since it has a resistivity as low as 10 to 10 Ωcm. The carbon nanotube has excellent mechanical characteristics, is chemically stable and has a large surface area. Since the carbon nanotube shaped like a bar has a large aspect ratio, it is easy to form a low percolation threshold such that its conductivity is excellent.
[51] A method for manufacturing the conductive fiber thin-film 130 from the carbon nanotube as the conductive fiber will be described.
[52] First, carbon nanotube aqueous dispersion solution or carbon nanotube organic dispersion solution is prepared. The carbon nanotube aqueous dispersion solution is prepared by adding carbon nanotube to an aqueous solution in which a surface active agent, such as Triton X-100, sodium dodecylbenzene sulfonate (Na-DDBS), cetyl trimethyl ammonium bromide (CTAB) or sodium dodecyl sulfate (SDS), is dissolved, and applying ultrasonic waves to the solution for 1 to 120 minutes. The carbon nanotube organic dispersion solution is prepared by adding carbon nanotube to an organic solution, such as N-methylpyrrolidone (NMP), o-dichlorobenzene, dichloroethane, dimethyl formamide (DMF) or chloroform, and applying ultrasonic waves to the solution for 1 to 120 minutes. However, the carbon nanotube aqueous dispersion solution or carbon nanotube organic dispersion solution may be prepared by other methods.
[53] When the carbon nanotube aqueous dispersion solution or carbon nanotube organic dispersion solution thus prepared is filtered by a large-sized vacuum filter equipped with the base layer 110, at lease part of or, preferably, all of materials, except the carbon nanotube, are removed through the pores 113 of the polymer membrane, such that a uniform carbon nanotube film is formed on the base layer 110. [54] The thickness of the carbon nanotube film thus formed, i.e., the thickness H of the sum of the mixture layer 120 and the conductive fiber thin-film 130 in Fig. 3, can be easily controlled by adjusting the amount of the carbon nanotube dispersion solution to be filtered. When the carbon nanotube aqueous dispersion solution is used, the carbon nanotube film formed on the polymer membrane can be additionally cleaned using water to remove the surface active agent remaining on the carbon nanotube film after filtering the carbon nanotube aqueous dispersion solution. In this case, the carbon nanotube film preferably has a thickness of 1 to 500nm. When the thickness H is smaller than lnm, it is not possible to obtain a satisfactory conductivity. When the thickness is larger than 50nm, the light transmissivity of the electrode may decrease.
[55] Since the conductive fiber 131, such as carbon nanotube, is formed of a nano-sized film on the base layer, it is possible to manufacture a transparent electrode with a good conductivity using a small amount of the conductive fiber, compared to the existing conductive composite material in which the carbon nanotube exists inside the polymer membrane.
[56] At least part of materials except the conductive fiber 131 is removed through the polymer membrane while the conductive fiber 131 is uniformly dispersed in the solvent, such that the conductive fiber 131 is uniformly dispersed on the polymer 111. In addition, when the whole or most of the conductive fiber thin-film 130 is made only of the conductive fiber 131, the conductive composite material 100 has an excellent conductivity. Furthermore, since the conductive fiber thin-film 130 has a reduced thickness and has more than a predetermined conductivity, the conductive composite material 100 has an excellent transparency.
[57] The mixture layer 120 is provided between the base layer 110 and the conductive fiber thin-film 130. The mixture layer 120 is formed by inserting part 131a of the conductive fiber 131 into part 11 Ia of the base layer 110. The mixture layer 120 may be formed by pressing the base layer 110 and the conductive fiber thin-film 130. Prior to pressing, the base layer 110 is subjected to heat treatment so that the conductive fiber of the conductive fiber thin-film 130 can be satisfactorily dispersed in the base layer 110 upon pressing.
[58] The mixture layer 120 is formed by inserting the part 131a of the conductive fiber into the base layer 110. The density of the conductive fiber 131 per the unit volume of the mixture layer 120 is less than the density of the conductive fiber 131 per the unit volume of the conductive fiber thin-film 130. Therefore, the conductive fiber thin-film 130 has an excellent conductivity. In the present embodiment of the invention, the conductive fiber thin-film 130 may have a resistivity of 10 to 10 Ω/sq.
[59] The mixture layer 120 may be formed by inserting part of the conductive fiber 131 of the conductive fiber thin-film 130 into at least part of the pores 113 of the polymer membrane which is provided in the base layer 110. That is, the conductive fiber and t he polymer membrane are more securely bound with each other by directly binding the conductive fiber thin-film 130 with the base layer 110.
[60] The conductive fiber and the polymer membrane are physicochemically bound with each other due to interdigitation on an interface therebetween, such that the conductive fiber thin-film is bounded much more securely. According to the present embodiment of the invention, it is possible to save the amount of conductive fiber, and to prevent the conductivity from decreasing when the conductive fiber, particularly carbon nanotube, is dispersed in the polymer. Therefore, it is possible to obtain an excellent conductivity without the need to coat an additional conductive polymer film.
[61] According to a conventional method for coating a carbon nanotube dispersion solution on a transparent polymer film, a carbon nanotube film is not uniform and is not securely fixed, such that it is very difficult or not possible to manufacture a conductive composite film which is large and uniform. However, according to the present embodiment of the invention, it is possible to very securely fix a conductive fiber thin-film to a polymer by positioning a uniform conductive fiber (carbon nanotube) thin-film on a non-transparent polymer (polymer film), and fixing the conductive fiber thin-film to the polymer simultaneously with or following making the polymer transparent by heat, pressure, or solvent-coating. In addition, since the conductive fiber such as carbon nanotube is provided on the transparent polymer, it is possible to manufacture a soft and transparent conductive composite material 100 having an excellent conductivity using an extremely small amount of conductive fiber, compared to the conventional composite film in which the carbon nanotube is uniformly dispersed in the polymer matrix.
[62] The transparent conductive composite material 100 may be used in a thin-film transistor liquid crystal display (TFT-LCD), a plasma display panel (PDP), an organic light emitting diode (OLED), a touch panel, an electromagnetic-wave shield, an electrostatic-discharge shield, a heat reflector, a surface heater, a photo-electric converter, etc. In particular, the transparent conductive composite material 100 is flexible, light and mechanically stable, such that it may be used as a transparent electrode of a large- sized flexible display.
[63] Fig. 5 is a flow chart of a method for manufacturing a conductive composite material according to an exemplary embodiment of the present invention.
[64] The method according to the present embodiment of the invention includes providing a membrane (Sl 10), and fixing a conductive fiber thin-film to the membrane (S 120). The method may further include making the membrane transparent (S 130).
[65] Fig. 6 is a flow diagram of a method for manufacturing a conductive composite material according to an exemplary embodiment of the present invention. Figs. 7 to 9 illustrate individual processes shown in Fig. 6.
[66] First, a membrane is provided. The membrane is made of the polymer 111 and has a plurality of pores 113 as shown in Fig. 4. The membrane acts so that all or most of materials, such as a solvent normally including dispersion agent and binding agent, except the conductive fiber can be removed through the pores 113 of the membrane while the conductive fiber thin-film is formed.
[67] Examples of the polymer membrane include polycarbonate, polyethylene terephtalate (PET), polyamides, cellulose ester, regenerated cellulose, nylon, polypropylene, polyacrylonitrile, polysulfone, polyethersulfone, and polyvinyli- denfluoride. In this case, the membrane may be a polymer membrane with pores each having a diameter Dp of 0.01 to 10mm and a thickness of 10 to 1000mm.
[68] Subsequently, as shown in Fig. 7, the conductive fiber thin-film 130 is fixed to the membrane. The conductive fiber thin-film 130 is made only or mostly of a conductive fiber formed in a thin-film layer.
[69] The conductive fiber 131 may be carbon fiber. Examples of the carbon fiber include a single- walled carbon nanotube, a double-walled carbon nanotube, a multi- walled carbon nanotube, a carbon nano-fiber, and graphite.
[70] The conductive fiber 131 may preferably be a carbon nanotube. The carbon nanotube is structured in such a manner that a graphene sheet is tubularly wound which is honeycombed with a carbon atom bound with three other carbon atoms. The carbon nanotube has a diameter of 1 to 100 nm. The carbon nanotube is divided into a single- walled carbon nanotube and a multi- walled carbon nanotube according to the number of graphene sheets which form walls of the carbon nanotube. The single- walled carbon nanotube is formed in a bundle of tubes.
[71] The carbon nanotube has an excellent conductivity since it has a resistivity as low as 10 to 10 Ωcm. The carbon nanotube has excellent mechanical characteristics, is chemically stable and has a large surface area. Since the carbon nanotube shaped like a bar has a large aspect ratio, it is easy to form a low percolation threshold such that an excellent conductivity is obtained.
[72] In this case, the carbon nanotube film preferably has a thickness H of 1 to 500nm.
When the thickness is smaller than lnm, it is not possible to obtain a satisfactory conductivity. When the thickness is larger than 500nm, the light transmissivity of the electrode may decrease.
[73] The step of fixing the conductive fiber thin-film 131 to the membrane may include placing a conductive fiber dispersion solution 140 on the membrane, and removing at least part of materials except the conductive fiber 131 from the conductive fiber dispersion solution 140 through the pores 113 of the membrane.
[74] During the above-mentioned process, at least part of the materials 141, such as a solvent normally including a binding agent and a dispersion agent, except the conductive fiber 131 is removed through the membrane from the solvent in which the conductive fiber 131 is dispersed, whereby the conductive fiber thin-film 130 can be uniformly dispersed on the membrane. Furthermore, since the whole or most of the conductive fiber thin-film 130 is made only of the conductive fiber 131, its conductivity is enhanced. Accordingly, the thickness of the conductive fiber thin-film 130 can be reduced, such that the conductive composite material has an enhanced transparency. In addition, the solvent can be removed when the conductive fiber 131 is uniformly dispersed in the solvent, whereby the conductive fiber 131 has an excellent dispersion degree on the membrane, and has a more improved conductivity.
[75] The conductive fiber dispersion solution may be formed on the membrane by vacuum filtering, self-assembly technique, Langmuir-Blodgett technique, solution casting, bar coating, dip coating, spin coating, jet coating, etc.
[76] The conductive fiber thin-film 130 may be uniformly dispersed on the membrane by vacuum filtering. For example, as shown in Fig. 7, the conductive fiber aqueous dispersion solution 140 is prepared by adding the conductive fiber 131 to the solvent 141 in which a surface active agent is dissolved. Examples of the surface active agent include Triton X-100, sodium dodecylbenzene sulfonate (Na-DDBS), cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS). For another example, the conductive fiber aqueous dispersion solution is prepared by adding the conductive fiber to the aqueous solution and applying ultrasonic waves to the solution, for example, for 1 to 120 minutes.
[77] The conductive fiber aqueous dispersion solution 140 may be prepared by other methods. For example, the conductive fiber aqueous dispersion solution 140 may be prepared by adding the conductive fiber 131 to an organic solvent, such as N- methylpyrrolidone (NMP), o-dichlorobenzene, dichloroethane, dimethylformamide (DMF), and chloroform.
[78] Subsequently, the conductive fiber aqueous dispersion solution 140 stored in a solution container 150 is filtered through a vacuum filter 160. The membrane is provided facing the solution container 150 of the vacuum filter 160. The solvent 141 except the conductive fiber 131 is filtered through the pores 113 of the membrane, such that the conductive fiber thin-film 130 is uniformly formed on the membrane. Subsequently, the carbon nanotube film 130 thus formed is cleaned with water.
[79] Through the above-mentioned process, at least part of the conductive fiber 131 can be inserted into part of the membrane. For example, the conductive fiber 131 may be inserted into the pores 113 of the membrane.
[80] As shown in Fig. 8, the method according to the present embodiment of the invention may further include inserting at least part of the conductive fiber thin-film 130 into at least part of the membrane to securely fix the conductive fiber thin-film 130 to the membrane. The conductive composite material 100 may include the base layer 110 formed only of the membrane, the mixture layer 120 having the membrane mixed with the conductive fiber, and the conductive fiber thin-film 130 formed only of the conductive fiber. For an example of the above-mentioned process, as shown in Fig. 8, a predetermined level of heat is applied to the membrane, and the membrane and the conductive fiber thin-film 130 are pressed by a pressing unit 170, such as a roller. That is, the polymer membrane is softened at a predetermined high temperature, and the membrane and the conductive fiber thin-film 130 are pressed with the pressing unit 170, such that part of the conductive fiber 131 is inserted into part of the membrane. Next, after cooling down the conductive composite fiber during a predetermined time, the membrane with part of the conductive fiber 131 inserted is hardened. Accordingly, the conductive fiber thin-film 130 is securely fixed to the membrane.
[81] However, since the membrane has the pores 113 therein, the conductive composite material may neither be transparent nor have a satisfactory transparency. Accordingly, the method according to the present embodiment of the invention may further include making the membrane transparent.
[82] The membrane may be made transparent by removing the pores 113. The membrane may be made of a material in which the pores 113 are removed upon applying more than a predetermined level of heat and/or pressure to the membrane, a material in which the pores 113 are removed upon irradiating more than a predetermined intensity of light on the membrane, or a material in which the pores 113 are removed upon applying more than a predetermined level of voltage to the membrane. For example, when the membrane is made of a material which changes to be optically transparent at a glass transition temperature Tg, the pores 113 of the membrane are removed by applying heat to the membrane at more than the glass transition temperature Tg.
[83] The membrane may be changed to be optically transparent by coating a soluble organic solvent on the membrane. Examples of the soluble organic solvent include benzene, toluene, xylene, chloroform, methylen chloride, acetone, methyl ethyl ketone, cyclohexane, etyle acetate, dioxane, tetrahydrofuran, dimethylformamide, and dimethylsulfoxide.
[84] The membrane having the conductive fiber thin-film 130 formed thereon may be made transparent either in a consecutive manner using a hot-pressing roller which has preheating, heating and cooling roller units, or in a discontinuous manner using a plane -pressing unit.
[85] In the above-mentioned process of preparing the transparent conductive composite material, all equipment contacting with the surface of the membrane are hard-faced so that the heated membrane cannot stick to the equipment. In particular, the heating roller unit of the hot-pressing roller preferably has a surface with an average roughness less than 0.2a, and is made of stainless steel (SUS) which will not stick to the heated polymer.
[86] Before, after or during making transparent the membrane having the conductive fiber formed thereon, an optically transparent plastic film may be formed on an upper surface of the conductive fiber thin-film and/or a lower surface of the membrane.
[87] As shown in Fig. 8, the step of making the membrane transparent may be carried out simultaneously with the step of securely fixing the conductive fiber thin-film to the membrane. That is, when part of the conductive fiber 131 is inserted into the membrane, a high-temperature heat may be applied to the membrane so that the pores 113 of the membrane can be removed.
[88] According to the present embodiment of the invention, the membrane made of polymer is made transparent when the membrane holds the conductive fiber thin-film, such as carbon nanotube. Accordingly, interdigitation occurs in an interface between the membrane and the conductive fiber thin-film, whereby the carbon nanotube film is securely fixed to the membrane. Therefore, it is possible to substantially reduce an amount of conductive fiber, such as carbon nanotube, and to securely fix the conductive fiber thin-film to the membrane. In addition, since the conductivity is not lowered even though the carbon nanotube is dispersed in the polymer, it is possible to obtain a conductive composite material having an excellent conductivity without coating an additional conductive polymer film.
[89] According to the conventional method for coating a carbon nanotube dispersion solution on a transparent polymer film, it is difficult or not possible to manufacture a large-sized, uniform conductive composite film since a carbon nanotube film is not uniformly formed and is securely fixed. However, according to the present embodiment of the invention, a uniform conductive fiber thin-film is formed on a non- transparent membrane, and the membrane is made transparent and is fixed to the conductive fiber thin-film by heating, pressing, or solvent-coating, whereby it is possible to very securely fix the conductive fiber thin-film to the membrane. In addition, since the conductive fiber is formed only on the surface of the transparent membrane, it is possible to prepare a soft, transparent conductive composite material having an excellent conductivity using a small amount of conductive fiber, compared to the conventional composite film in which a carbon nanotube is uniformly dispersed in a polymer material.
[90] Fig. 9 illustrates the conductive composite material 100 which is prepared by the above-mentioned method. Fig. 10 illustrates an enlarged cross-sectional view of the 'C part of Fig. 9. [91] The mixture layer 120 is provided between the base layer 110 and the conductive fiber thin-film 130. The mixture layer 120 is formed by inserting part of the conductive fiber 131 of the conductive fiber thin-film 130 into at least part of the pores 113 of the membrane. Accordingly, it is possible to very securely fix the conductive fiber thin- film 130 to the base layer 110.
[92] In addition, since the part 131a of the conductive fiber 131 is inserted into the base layer 110 to form the mixture layer 120, the density of the conductive fiber 131 per the unit volume of the mixture layer 120 is less than the density of the conductive fiber 131 per the unit volume of the conductive fiber thin-film 130. Therefore, the conductive composite material has an excellent conductivity. In the present embodiment of the invention, the conductive composite material may have a resistivity of 10 to l08 Ω/sq.
[93]
[94] <Embodiment 1>
[95] A carbon nanotube was used as the conductive fiber 130, and a polyethersulfone membrane with pores 113 each having a diameter of 0.2mm was used.
[96] The conductive fiber thin-film 130 was fixed to the membrane using the vacuum filter shown in Fig. 6. Referring to Fig. 6, 0.0015 wt% carbon nanotube aqueous dispersion solution 140 was prepared by adding 15mg of a single- walled carbon nanotube 131 (mfg. by ILJIN Nanotech) to 11 of aqueous solution 141 in which 1Og of SDS as a surface active agent was dissolved, and applying 4OkHz ultrasonic waves of 45W for 30 minutes.
[97] Next, 80ml of the carbon nanotube aqueous dispersion solution 140 from the container 150 was filtered by the large-sized vacuum filter 160 with a filtering area of 500cm2.
[98] In this case, the base layer 110 made of a polyethersulfone membrane with pores each having a diameter of 0.2mm is provided in the large-sized vacuum filter 160. A solvent except the carbon nanotube was filtered through the pores 113, such that a carbon nanotube film was uniformly formed on the polymer membrane. Next, the carbon nanotube film thus formed was cleaned with water.
[99] Subsequently, as shown in Fig. 8, the polymer membrane was made transparent using the hot-pressing roller, such that a transparent conductive composite material 100 was obtained in which the carbon nanotube film 130 is formed on the transparent base layer 110. In more detail, the conductive fiber 130 and the membrane was preheated to a temperature of 11O0C using a preheating roller, and the polymer membrane was made transparent through a heating roller with a temperature of 22O0C. In this case, at least part of the carbon nanotube forming the conductive fiber thin-film 130 is inserted into the membrane to form the mixture layer 120. Subsequently, it passed through a cooling roller to prevent wrinkles of the polymer membrane and improve the optical characteristic of the transparent polymer membrane.
[100] About 2.4mg/cm of the carbon nanotube was obtained per the unit area of the transparent carbon nanotube film.
[101] The light transmissivity of the transparent electrode thus manufactured was measured to be about 90% at 550nm by an ultraviolet- visible spectroscope. The surface resistance of the transparent electrode was measured to be less than 200Ω/sq by a surface resistance meter. The uniformity of surface resistance, i.e., the standard- deviation/average of surface resistance, was less than 7%.
[102] The adhesion stability of the carbon nanotube film was estimated at 5B (indicating that there is no carbon nanotube to be removed) by the tape test (ASTM D 3359-02).
[103] As described above, the transparent electrode manufactured according to the present embodiment of the invention was proved to be excellent in transparency, conductivity, uniformity of conductivity, flexibility, and adhesion stability of the carbon nanotube film.
[104]
[105] <Embodiment 2>
[106] The transparent conductive composite material 100 was prepared in the same method as that of Embodiment 1, except that a carbon nanotube/membrane composite material with a small amount of dimethylformamide (DMF) coated passed through a heating roller with a temperature of 8O0C to make the membrane film transparent.
[107] The transparency, conductivity, uniformity of conductivity, and adhesion stability of the transparent film thus manufactured were examined in the same method as that of Embodiment 1. As a result, the transparent film was proved to have excellent transparency, conductivity, uniformity of conductivity, and adhesion stability, similarly to that of Embodiment 1.
[108]
[109] Embodiment 3>
[110] The transparent conductive composite material 100 was prepared in the same manner as that of Embodiment 1, except that during the process of making transplant the membrane having the carbon nanotube film formed thereon, an optically transparent polyethylene terephtalate film was stacked on a lower surface of a polymer film, and a carbon nanotube/membrane composite material with a small amount of dimethylformamide (DMF) coated passed through a heating roller with a temperature of 8O0C to make the membrane film transparent.
[I l l] The transparency, conductivity, uniformity of conductivity, and adhesion stability of the conductive composite material thus manufactured were examined in the same method as that of Embodiment 1. As a result, the transparent film was proved to have excellent transparency, conductivity, uniformity of conductivity, and adhesion stability, similarly to that of Embodiment 1.
[112]
[113] <Embodiment 4>
[114] The transparent conductive composite material 100 was prepared in the same method as that of Embodiment 1, except that the carbon nanotube/membrane composite material was made transparent using a plane-pressing unit rather than a hot- pressing roller.
[115] The transparency, conductivity, uniformity of conductivity, and adhesion stability of the conductive composite material thus manufactured were examined in the same method as that of Embodiment 1. As a result, the transparent film was proved to have excellent transparency, conductivity, uniformity of conductivity, and adhesion stability, similarly to that of Embodiment 1.
[116] Fig. 11 is a flow chart of a method for manufacturing a conductive composite material according to another exemplary embodiment of the invention.
[117] The method according to the present embodiment of the invention includes providing an initial base layer (S210), placing a conductive fiber thin-film on the initial base layer (S220), and moving the conductive fiber thin-film onto a final base layer (S230).
[118] Figs. 12 to 16 are views for explaining a method for manufacturing a conductive composite material according to an exemplary embodiment of the present invention.
[119] As shown in Fig. 12, an initial base layer 210 is provided. The initial base layer 210 may be formed of a polymer membrane 211 having a plurality of pores 213. The membrane is provided such that all or most of materials except a conductive fiber are removed through the pores 213 of the membrane during the process of manufacturing the conductive fiber thin-film.
[120] The polymer membrane 211 may be made of polycarbonate, polyethylene terephtalate (PET), polyamides, cellulose ester, regenerated cellulose, nylon, polypropylene, polyacrylonitrile, polysulfone, polyethersulfone, or polyvinyli- denfluoride. In particular, polyethersulfone exhibits a more improved filtering performance of conductive fiber such that it is easy to separate the conductive fiber thin-film.
[121] In this case, the polymer membrane may have pores each having a diameter Dp of
0.01 to 10mm, and a thickness K of 10 to 1000mm.
[122] Subsequently, as shown in Fig. 13, the conductive fiber thin-film 130 is placed on the initial base layer 210. The conductive fiber thin-film 130 is made only or mostly of the conductive fiber 131. In this case, the conductive fiber thin-film 130 may be formed and dispersed on the initial base layer 210, or may be formed on the initial base layer 210.
[123] The conductive fiber 131 may be a carbon fiber. Examples of the carbon fiber include a single-walled carbon nanotube, a double-walled carbon nanotube, a multi- walled carbon nanotube, a carbon nano-fiber, and graphite.
[124] The conductive fiber 131 may preferably be a carbon nanotube. The carbon nanotube is structured in such a manner that a graphene sheet is tubularly wound which is honeycombed with a carbon atom bound with three other carbon atoms. The carbon nanotube has a diameter Dc of 1 to lOOnm. The carbon nanotube is divided into a single- walled carbon nanotube and a multi- walled carbon nanotube according to the number of graphene sheets which form walls of the carbon nanotube. The single- walled carbon nanotube is formed in a bundle of tubes.
[125] The carbon nanotube has an excellent conductivity since it has a resistivity as low as 10 to 10 Ωcm. The carbon nanotube has excellent mechanical characteristics, is chemically stable and has a large surface area. Since the carbon nanotube shaped like a bar has a large aspect ratio, it is easy to form a low percolation threshold such that its conductivity is excellent.
[126] In this case, the carbon nanotube preferably has a thickness H of 1 to 500nm. The carbon nanotube with a thickness smaller than lnm does not exhibit a satisfactory conductivity. The carbon nanotube with a thickness larger than 500nm may show a reduced light transmissivity of the electrode.
[127] The step of placing the conductive fiber thin-film 130 on the initial base layer 210 may include placing the conductive fiber dispersion solution 140 on the initial base layer 210, and removing at least part of materials except the conductive fiber 131 from the conductive fiber dispersion solution 140. The conductive fiber dispersion solution 140 may be placed on the initial base layer 210 by vacuum filtering, self-assembly technique, Langmuir-Blodgett technique, solution casting, bar coating, dip coating, spin coating, spray coating, etc.
[128] When the initial base layer 210 is made of a membrane material, the step of placing the conductive fiber thin-film 130 on the initial base layer 210 may include placing the conductive fiber dispersion solution 140 on the membrane, and removing at least part of materials except the conductive fiber 131 from the conductive fiber dispersion solution 140 through the pores 213 of the membrane.
[129] When the conductive fiber 131 is dispersed in the solvent in the above-mentioned process, the conductive fiber thin-film 130 can be uniformly dispersed on the initial base layer 210 by removing through the membrane at least part of the materials 141, such as solvent normally including a dispersion agent or a binding agent, except the conductive fiber 131. Furthermore, since the whole or most of the conductive fiber thin-film 130 is made only of the conductive fiber 131, the conductive fiber thin-film 130 has an excellent conductivity even though the conductive fiber thin-film 130 is reduced in thickness. As a result, the conductive fiber thin-film 130 has an excellent transparency. In addition, when at least part of or, preferably, the whole of the materials 141 except the conductive fiber 131 is removed, the conductive fiber 131 can be uniformly dispersed on the initial base layer 210 and thus have an excellent conductivity.
[130] The conductive fiber thin-film 130 is uniformly dispersed on the initial base layer
210 by vacuum filtering. For example, as shown in Fig. 13, the conductive fiber aqueous dispersion solution 140 is prepared by adding the conductive fiber 131 to the solvent 141 in which the surface active agent is dissolved. Examples of the surface active agent include Triton X-100, sodium dodecylbenzene sulfonate (Na-DDBS), cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS). For another example, the conductive fiber aqueous dispersion solution is prepared by adding the conductive fiber to the aqueous solution and applying ultrasonic waves to the solution, for example, for 1 to 120 minutes.
[131] However, the conductive fiber dispersion solution 140 may be prepared by other methods. For example, the conductive fiber dispersion solution 140 may be prepared by adding the conductive fiber 131 to an organic solvent, such as N-methylpyrrolidone (NMP), o-dichlorobenzene, dichloroethane, dimethylformamide (DMF) and chloroform.
[132] Subsequently, the conductive fiber dispersion solution 140 stored in the solution container 150 is filtered by the vacuum filter 160. In this case, the initial base layer 210 is mounted on a part of the vacuum filter 160, which faces the solution container 150, and the conductive fiber dispersion solution 140 is provided on the initial base layer 210. A negative pressure is applied from the vacuum filter 160 to the initial base layer 210.
[133] Accordingly, at least part of the materials except the conductive fiber 131 is removed through the pores 213 of the initial base layer 210, whereby the conductive fiber thin-film 130 is uniformly formed on the initial base layer 210. Subsequently, the conductive fiber thin-film 130 thus formed is cleaned with water. The conductive fiber thin-film may be prepared by other methods.
[134] Subsequently, as shown in Figs. 14 and 15, the conductive fiber thin-film 130 formed on the initial base layer 210 is moved to a final base layer 110. That is, the conductive fiber thin-film 130 is uniformly dispersed on the initial base layer 210 by vacuum filtering, and the conductive fiber thin-film 130 is moved to the final base layer 110, whereby the conductive composite material 100 is formed of the final base layer 110 and the conductive fiber thin-film 130 formed on the final base layer 110.
[135] For example, after the conductive fiber thin-film 130 is uniformly dispersed on the initial base layer 210, the initial base layer 210 and the final base layer 110 are tightly joined and then separated with more than a predetermined level of heat applied or with a binding member provided on a portion in which a pattern of the final base layer 110 is to be formed. As a result, the conductive fiber having the pattern is formed on the final base layer 110. Accordingly, it is easy to form the pattern compared to the conventional method for manufacturing the conductive composite material in which the transparent conductive thin-film is formed on the substrate by coating, spraying, etc.
[136] When an organic solvent is conventionally used to form the transparent conductive film on a substrate made of a polymer film, at least part of the substrate may melt due to the organic solvent. This may cause the evenness of the substrate to be deteriorated, resulting in a reduced conductivity. However, according to the present embodiment of the invention, the conductive composite material is prepared by moving the conductive fiber thin-film 130, which is placed on the initial base layer 210 using the organic solvent, to the final base layer 110 without contacting with the organic solvent, whereby the conductive composite material has an enhanced evenness and conductivity. After the conductive fiber thin-film 130 is moved, the initial base layer 210 can be reused to manufacture another conductive fiber thin-film.
[137] In addition, the conductive fiber thin-film 130 is thin in thickness and has a high conductivity, whereby the conductive composite material has an enhanced transparency.
[138] The final base layer 110 may be made of a transparent polymer, which increases the transparency of the conductive composite material. In this case, the final base layer 110 may be made of polyethylene terephtalate.
[139] The final base layer 110 is made of a material which is lower in softening point than the first base layer 210. The step of moving the conductive fiber thin-film 130 to the final base layer 110 is performed, as shown in Figs. 14 and 16, by pressing the final base layer 110 to the conductive fiber thin-film 130 and separating the first base layer 210 and the final base layer 110 from each other at a certain temperature between a softening point of the first base layer 210 and a softening point of the final base layer 110. That is, at a temperature higher than the softening point of the final base layer 110, the final base layer 110 is softened such that a different material tends to be inserted. However, since the temperature is lower than the softening point of the first base layer 210, the conductive fiber thin-film 130 is not fixed to the initial base layer 210 very securely. Accordingly, when the conductive fiber thin-film 130 placed on the initial base layer 210 is made contact with or pressed to the final base layer 110 at the temperature, the conductive fiber thin-film 130 is moved to the final base layer 110 with a high level of adhesion.
[140] For another example, an additional adhesion layer having a higher level of adhesion than that of the initial base layer 210 to the conductive fiber thin-film 130 is formed on the surface of the final base layer 110, and the conductive fiber thin-film 130 placed on the initial base layer 210 is made contact with or pressed to the final base layer 110. For another example, the initial base layer having the conductive fiber thin-film formed thereon may be made contact with an additional final base layer having a higher surface energy than that of the initial base layer to move the conductive fiber thin-film.
[141] In addition, the conductive fiber thin-film placed on the initial base layer is moved onto the final base layer by heat-transfer printing to obtain a patterned conductive fiber thin-film.
[142] As shown in Fig. 16, the method according to the present embodiment of the invention may further include inserting at least part of the conductive fiber 131 of the conductive fiber thin-film 130 into at least part of the final base layer 110.
[143] Accordingly, the conductive composite material 100 includes the final base layer
110, the conductive fiber thin-film 130 made only of the conductive fiber, and the mixture layer 120 having the final base layer impregnated with the conductive fiber. For example, after more than a predetermined level of heat (normally more than a softening point) is applied to the final base layer 110, the final base layer 110 and the conductive fiber thin-film 130 are pressed with a pressing unit, such as a roller. That is, when the final base layer 110 is softened at a predetermined high temperature, the final base layer 110 and the conductive fiber thin-film 130 are pressed with a pressing unit, whereby part of the conductive fiber 131 impregnates part of the final base layer 110. Next, when the conductive composite fiber 100 is cooled down during a predetermined time, the final base layer 110 is hardened with the part of the conductive fiber 131 inserted therein. Therefore, the conductive fiber thin-film 130 is securely fixed to the final base layer 110.
[144] A method for manufacturing the conductive composite material will be described in detail.
[145] A carbon nanotube was used as the conductive fiber 130, and a polyethersulfone membrane with pores 213 each having a diameter of 0.2mm was used as the initial base layer 210.
[146] The step of fixing the conductive fiber thin-film 130 to the initial base layer 210 was performed using the vacuum filter shown in Fig. 13. Referring to Fig. 13, 0.0015 wt% carbon nanotube aqueous dispersion solution 140 was prepared by adding 15mg of a single- walled carbon nanotube 131 (mfg. by ILJIN Nanotech) to 11 of the aqueous solution 141 in which 1Og of SDS as a surface active agent was dissolved, and applying 4OkHz ultrasonic waves of 45W for 30 minutes.
[147] Next, 80ml of the carbon nanotube aqueous dispersion solution 140 from the container 150 was filtered by the large-sized vacuum filter 160 with a filtering area of 500cm2.
[148] In this case, the initial base layer 210 made of a polyethersulfone membrane with pores each having a diameter of 0.2mm is provided in the large-sized vacuum filter 160. A solvent except the carbon nanotube was filtered through the pores 213, such that a carbon nanotube film was uniformly formed on the initial base layer 210. Next, the carbon nanotube film thus formed was cleaned with water.
[149] Subsequently, a clean polyethylene terephtalate film was closely attached to the surface of the carbon nanotube thin-film formed of a composite material of the carbon nanotube/initial base layer, and then passed through the heat roller with a temperature of 8O0C. After that, the initial base layer was mechanically peeled off and the carbon nanotube film was moved to the polyethylene terephtalate film, whereby the transparent conductive composite material was prepared.
[150] The light transmissivity of the transparent conductive composite material thus manufactured was measured to be about 90% at 550nm by an ultraviolet- visible spectroscope. The surface resistance of the transparent electrode was measured to be less than 200Ω/sq by a surface resistance meter. In addition, the uniformity of surface resistance, i.e., the standard-deviation/average of surface resistance, was less than 7%.
[151] The adhesion stability of the carbon nanotube film was estimated at 5B (indicating that there is no carbon nanotube to be removed) by the tape test (ASTM D 3359-02).
[152] As described above, the transparent electrode manufactured according to the present embodiment of the invention was proved to be excellent in transparency, conductivity, uniformity of conductivity, flexibility, and adhesion stability of the carbon nanotube film.
[153] It will be apparent to those skilled in the art that various modifications and variation can be made in the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Industrial Applicability
[154] The present invention can effectively be applied to a conductive composite material, which is flexible and used in an electronic product such as a flat panel display, and a method for manufacturing the same.

Claims

Claims
[I] A conductive composite material comprising: a base layer; a conductive fiber thin-film made of conductive fiber and formed on the base layer; and a mixture layer in which part of the conductive fiber is inserted into part of the base layer.
[2] The conductive composite material of claim 1, wherein the base layer is made of polymer.
[3] The conductive composite material of claim 1, wherein the base layer is made of material in which pores are removed upon applying more than a predetermined level of at least one of heat, pressure, light and voltage.
[4] The conductive composite material of claim 1, wherein the base layer is made of material in which pores are removed by coating a soluble organic solvent.
[5] The conductive composite material of claim 1, wherein the base layer is made of a polymer membrane, and at least part of the mixture layer is formed by inserting part of the conductive fiber into at least part of pores formed in the polymer membrane.
[6] The conductive composite material of claim 5, wherein the base layer is made of polycarbonate, polyethylene terephtalate (PET), polyamides, cellulose ester, regenerated cellulose, nylon, polypropylene, poly aery lonitrile, polysulfone, polyethersulfone, or polyvinylidenfluoride.
[7] The conductive composite material of claim 5, wherein the polymer membrane has pores each having a diameter of 0.01 to 10mm.
[8] The conductive composite material of claim 1, wherein the conductive fiber thin- film is made of carbon fiber.
[9] The conductive composite material of claim 8, wherein the carbon fiber is a carbon nanotube.
[10] The conductive composite material of claim 1, wherein the conductive fiber thin- film and the mixture layer have a total thickness of 1 to 500nm.
[I I] The conductive composite material of claim 1, wherein the conductive composite material has a resistance of 10 to 10 Ω/sq.
[12] The conductive composite material of claim 1, wherein the conductive fiber thin- film has a higher density per unit volume than the mixture layer.
[13] A method for manufacturing a conductive composite material, comprising: providing a membrane; forming a carbon nano-fiber film on the membrane by removing through pores of the membrane at least part of materials except carbon nano-fiber from a carbon nano-fiber dispersion solution; fixing the carbon nano-fiber film to the membrane; and making the membrane transparent.
[14] The method of claim 13, wherein making the membrane transparent is performed by removing the pores of the membrane.
[15] The method of claim 14, wherein making the membrane transparent is performed by applying at least one of heat, pressure, light and voltage to the membrane.
[16] The method of claim 14, wherein making the membrane transparent comprises: coating a soluble organic solvent on at least the membrane; and drying the membrane.
[17] The method of claim 16, wherein making the membrane transparent comprises: coating dimethylformamide (DMF) on the membrane/carbon nanotube; and passing the membrane/carbon nanotube through a heating roller.
[18] The method of claim 13, wherein the carbon nano-fiber comprises at least one of a single- walled carbon nanotube, a double-walled carbon nanotube, a multi- walled carbon nanotube, a carbon nanotube, and graphite.
[19] The method of claim 13, wherein the membrane is a polymer membrane.
[20] The method of claim 19, wherein the membrane is made of poly ethersulf one.
[21] The method of claim 19, wherein the membrane has pores each having a diameter of 0.01 to 10mm.
[22] The method of claim 13, wherein forming a carbon nano-fiber film on the membrane is performed by vacuum filtering, self-assembly technique, Langmuir-
Blodgett technique, solution casting, bar coating, dip coating, spin coating, or jet coating.
[23] The method of claim 13, further comprising stacking a transparent polymer film on at least one side of the conductive composite material after forming the carbon nano-fiber film on the membrane.
[24] The method of claim 13, wherein fixing the carbon nano-fiber film to the membrane comprises inserting at least part of a carbon nanotube forming the carbon nano-fiber film into at least part of the membrane.
[25] The method of claim 24, wherein inserting at least part of a carbon nanotube is performed during making the membrane transparent.
[26] A method for manufacturing a conductive composite material, comprising: providing a membrane; providing a conductive fiber dispersion solution; and forming a conductive fiber thin-film on the membrane by removing through the membrane at least part of materials except conductive fiber from the conductive fiber dispersion solution.
[27] The method of claim 26, wherein forming a conductive fiber thin-film on the membrane is performed by removing through pores of the membrane the at least part of materials except conductive fiber.
[28] The method of claim 26, further comprising removing pores of the membrane after forming a conductive fiber thin-film on the membrane.
[29] The method of claim 28, wherein removing pores of the membrane is performed by applying at least one of heat, pressure, light and voltage to the membrane.
[30] The method of claim 26, further comprising inserting at least part of the conductive fiber forming the conductive fiber thin-film into at least part of the membrane after forming the conductive fiber thin-film on the membrane.
[31] The method of claim 30, further comprising removing pores of the membrane during inserting at least part of the conductive fiber into at least part of the membrane.
[32] The method of claim 31 , wherein removing pores of the membrane during inserting at least part of the conductive fiber into at least part of the membrane is performed by heat-pressing the conductive fiber thin-film and the membrane.
[33] The method of claim 26, wherein forming a conductive fiber thin-film on the membrane comprises: positioning the conductive fiber dispersion solution on the membrane; and removing through pores of the membrane at least part of the materials except conductive fiber.
[34] A method for manufacturing a conductive composite material, comprising: providing a membrane; fixing a conductive fiber thin-film to the membrane; and making the membrane transparent.
[35] The method of claim 34, wherein the membrane is a polymer membrane.
[36] The method of claim 34, wherein fixing a conductive fiber thin-film to the membrane comprises: positioning a conductive fiber dispersion solution on the membrane; and removing through pores of the membrane at least part of materials except conductive fiber from the conductive fiber dispersion solution.
[37] The method of claim 34, wherein making the membrane transparent is performed by removing pores of the membrane.
[38] A method for manufacturing a conductive composite material, comprising: providing an initial base layer; providing a conductive fiber thin-film on the initial base layer; and moving the conductive fiber thin-film provided on the initial base layer to a final base layer.
[39] The method of claim 38, wherein the conductive fiber comprises at least one of a single-walled carbon nanotube, a double- walled carbon nanotube, a multi- walled carbon nanotube, a carbon nanotube, and graphite.
[40] The method of claim 38, wherein the initial base layer is made of a membrane.
[41] The method of claim 40, wherein providing a conductive fiber thin-film on the initial base layer comprises: providing a conductive fiber dispersion solution on the initial base layer; and removing through membrane pores of the initial base layer at least part of materials except conductive fiber from the conductive fiber dispersion solution.
[42] The method of claim 41, wherein providing a conductive fiber thin-film on the initial base layer comprises: positioning the initial base layer on a vacuum filter; positioning the conductive fiber dispersion solution on the initial base layer; and applying a negative pressure from the vacuum filter to the initial base layer.
[43] The method of claim 40, wherein the initial base layer is made of a polymer membrane.
[44] The method of claim 43, wherein the polymer membrane is made of polyethersulfone.
[45] The method of claim 38, wherein the final base layer is made of a transparent polymer.
[46] The method of claim 45, wherein the initial base layer is made of a polyethersulfone membrane, and the final base layer is made of polyethylene terephtalate.
[47] The method of claim 38, wherein the final base layer is made of a material lower in softening point than the initial base layer, and wherein moving the conductive fiber thin-film to a final base layer is performed by closely attaching the final base layer to the conductive fiber thin-film and separating the final base layer and the initial base layer from each other at temperatures between a softening point of the initial base layer and a softening point of the final base layer.
[48] The method of claim 38, wherein the final base layer is made of a material higher in surface energy than the initial base layer, and wherein moving the conductive fiber thin-film to a final base layer is performed by closely attaching the final base layer to the conductive fiber thin-film and separating the final base layer and the initial base layer from each other.
[49] The method of claim 38, wherein moving the conductive fiber thin-film to a final base layer comprises making the conductive fiber thin-film patternized by heat- transfer printing.
[50] The method of claim 38, further comprising inserting at least part of conductive fiber forming the conductive fiber thin-film into at least part of the final base layer after moving the conductive fiber thin-film to the final base layer.
[51] The method of claim 50, wherein inserting at least part of a conductive fiber into at least part of the final base layer is performed by heat-pressing the final base layer and the conductive fiber.
[52] A method for manufacturing a conductive composite material, comprising: providing an initial base layer made of a polymer membrane; positioning a carbon nanotube film on the initial base layer; and moving the carbon nanotube film to a final base layer.
[53] The method of claim 52, wherein the final base layer is made of a transparent polymer.
[54] The method of claim 52, wherein the final base layer is made of a material lower in softening point than the initial base layer, and wherein moving the carbon nanotube film to a final base layer is performed by closely attaching the final base layer to the carbon nanotube film and separating the final base layer and the initial base layer from each other at temperatures between a softening point of the initial base layer and a softening point of the final base layer.
[55] The method of claim 52, wherein the final base layer is made of a material higher in surface energy than the initial base layer, and wherein moving the conductive fiber thin-film to a final base layer is performed by closely attaching the final base layer to the conductive fiber thin-film and separating the final base layer and the initial base layer from each other.
[56] The method of claim 52, wherein moving the conductive fiber thin-film to a final base layer comprises making the conductive fiber thin-film patternized by heat- transfer printing.
[57] The method of claim 52, further comprising inserting at least part of carbon nanotube forming the carbon nanotube film into at least part of the final base layer after moving the carbon nanotube film to the final base layer.
[58] The method of claim 57, wherein inserting at least part of carbon nanotube into at least part of the final base layer is performed by heat-pressing the final base layer and the carbon nanotube.
PCT/KR2007/001643 2006-04-04 2007-04-04 Conductive composite material and method for manufacturing the same WO2007114645A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/295,859 US20090056854A1 (en) 2006-04-04 2007-04-04 Method for manufacturing conductive composite material

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2006-0030685 2006-04-04
KR1020060030685A KR100791999B1 (en) 2006-04-04 2006-04-04 Method for manufacturing conductive composite material
KR1020060030684A KR100791998B1 (en) 2006-04-04 2006-04-04 Method for manufacturing conductive composite material
KR1020060030683A KR100791997B1 (en) 2006-04-04 2006-04-04 Conductor
KR10-2006-0030684 2006-04-04
KR10-2006-0030683 2006-04-04

Publications (1)

Publication Number Publication Date
WO2007114645A1 true WO2007114645A1 (en) 2007-10-11

Family

ID=38563869

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2007/001643 WO2007114645A1 (en) 2006-04-04 2007-04-04 Conductive composite material and method for manufacturing the same

Country Status (2)

Country Link
US (1) US20090056854A1 (en)
WO (1) WO2007114645A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010130986A1 (en) * 2009-05-14 2010-11-18 Dupont Teijin Films U.S. Limited Partnership Transparent conductive composite films
WO2011053236A1 (en) * 2009-10-28 2011-05-05 Lunavation Ab A light-emitting electrochemical device, a system comprising such a device and use of such a device
WO2012063024A1 (en) 2010-11-12 2012-05-18 Dupont Teijin Films U.S. Limited Partnership Reflective conductive composite film
JP2013535843A (en) * 2010-08-07 2013-09-12 イノバ ダイナミックス, インコーポレイテッド Device component having surface embedded additive and related manufacturing method
EP3159162A4 (en) * 2014-06-12 2018-02-07 Toyo Ink SC Holdings Co., Ltd. Resin composition, layered product, and process for producing layered product
WO2018223293A1 (en) * 2017-06-06 2018-12-13 深圳创怡兴实业有限公司 Electroconductive flocking roller and preparation method therefor

Families Citing this family (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101464763B (en) * 2007-12-21 2010-09-29 清华大学 Production method of touch screen
CN101458596B (en) * 2007-12-12 2011-06-08 北京富纳特创新科技有限公司 Touch screen and display device
CN101470559B (en) * 2007-12-27 2012-11-21 清华大学 Touch screen and display equipment
CN101470560B (en) * 2007-12-27 2012-01-25 清华大学 Touch screen and display equipment
CN101458609B (en) * 2007-12-14 2011-11-09 清华大学 Touch screen and display device
CN101676832B (en) * 2008-09-19 2012-03-28 清华大学 Desktop computer
CN101419518B (en) * 2007-10-23 2012-06-20 清华大学 Touch panel
CN101458604B (en) * 2007-12-12 2012-03-28 清华大学 Touch screen and display device
CN101458603B (en) * 2007-12-12 2011-06-08 北京富纳特创新科技有限公司 Touch screen and display device
CN101656769B (en) * 2008-08-22 2012-10-10 清华大学 Mobile telephone
CN101620454A (en) * 2008-07-04 2010-01-06 清华大学 Potable computer
CN101470566B (en) * 2007-12-27 2011-06-08 清华大学 Touch control device
CN101458594B (en) * 2007-12-12 2012-07-18 清华大学 Touch screen and display device
CN101419519B (en) * 2007-10-23 2012-06-20 清华大学 Touch panel
CN101458600B (en) * 2007-12-14 2011-11-30 清华大学 Touch screen and display device
CN101470558B (en) * 2007-12-27 2012-11-21 清华大学 Touch screen and display equipment
CN101655720B (en) * 2008-08-22 2012-07-18 清华大学 Personal digital assistant
CN101458602B (en) * 2007-12-12 2011-12-21 清华大学 Touch screen and display device
CN101458608B (en) * 2007-12-14 2011-09-28 清华大学 Touch screen preparation method
CN101458599B (en) * 2007-12-14 2011-06-08 清华大学 Touch screen, method for producing the touch screen, and display device using the touch screen
CN101458606B (en) 2007-12-12 2012-06-20 清华大学 Touch screen, method for producing the touch screen, and display device using the touch screen
CN101458593B (en) * 2007-12-12 2012-03-14 清华大学 Touch screen and display device
CN101458595B (en) * 2007-12-12 2011-06-08 清华大学 Touch screen and display device
CN101458605B (en) * 2007-12-12 2011-03-30 鸿富锦精密工业(深圳)有限公司 Touch screen and display device
CN101458597B (en) * 2007-12-14 2011-06-08 清华大学 Touch screen, method for producing the touch screen, and display device using the touch screen
CN101458598B (en) * 2007-12-14 2011-06-08 清华大学 Touch screen and display device
CN101458975B (en) * 2007-12-12 2012-05-16 清华大学 Electronic element
CN101458607B (en) * 2007-12-14 2010-12-29 清华大学 Touch screen and display device
CN101458601B (en) * 2007-12-14 2012-03-14 清华大学 Touch screen and display device
CN101464757A (en) * 2007-12-21 2009-06-24 清华大学 Touch screen and display equipment
CN101464765B (en) * 2007-12-21 2011-01-05 鸿富锦精密工业(深圳)有限公司 Touch screen and display equipment
CN101470565B (en) * 2007-12-27 2011-08-24 清华大学 Touch screen and display equipment
US8574393B2 (en) 2007-12-21 2013-11-05 Tsinghua University Method for making touch panel
CN101464764B (en) * 2007-12-21 2012-07-18 清华大学 Touch screen and display equipment
CN101464766B (en) * 2007-12-21 2011-11-30 清华大学 Touch screen and display equipment
CN101552052B (en) * 2008-04-01 2013-03-27 索尼株式会社 Conducting film and manufacturing method thereof, electronic device and manufacturing method thereof
US8237677B2 (en) * 2008-07-04 2012-08-07 Tsinghua University Liquid crystal display screen
US8390580B2 (en) * 2008-07-09 2013-03-05 Tsinghua University Touch panel, liquid crystal display screen using the same, and methods for making the touch panel and the liquid crystal display screen
CN101924816B (en) * 2009-06-12 2013-03-20 清华大学 Flexible mobile phone
CN102656007A (en) * 2009-11-30 2012-09-05 南洋理工学院 Porous film sensor
WO2011099831A2 (en) * 2010-02-12 2011-08-18 성균관대학교산학협력단 Flexible transparent heating element using graphene and method for manufacturing same
KR20130016243A (en) * 2010-03-25 2013-02-14 도판 인사츠 가부시키가이샤 Conductive film and manufacturing method thereof
CN102214021B (en) * 2010-04-02 2013-05-29 北京富纳特创新科技有限公司 Touch display device
CN102802109B (en) * 2011-05-27 2014-10-08 清华大学 Preparation method for thermophone element
CN102800419B (en) * 2011-05-27 2014-07-09 清华大学 Method for preparing graphene conductive film structure
CN102794945B (en) * 2011-05-27 2014-08-20 清华大学 Method for preparing graphene carbon nano tube composite membrane structure
KR101286211B1 (en) * 2012-02-16 2013-07-15 고려대학교 산학협력단 Method of fabricating light emitting device and light emitting device fabricated by using the same
TWI450821B (en) * 2012-05-03 2014-09-01 Taiwan Textile Res Inst Transparent electrode with flexibility and method for manufacturing the same
CN103838455B (en) * 2012-11-23 2016-12-21 北京富纳特创新科技有限公司 Resistive touch screen
ITTO20121083A1 (en) * 2012-12-14 2014-06-15 Plastic Components And Modules Auto Motive S P A COMPOSITE MATERIAL FOR THE REALIZATION OF A COMPONENT OR A STRUCTURAL PART, PARTICULARLY FOR THE INSTALLATION OF A VEHICLE ON BOARD, TO INTEGRATE DEVICES AND ELECTRICAL CONNECTIONS.
KR20160040457A (en) 2013-07-31 2016-04-14 사빅 글로벌 테크놀러지스 비.브이. Process for making materials with micro- or nanostructured conductive layers
KR101586902B1 (en) * 2014-04-09 2016-01-19 인트리 주식회사 Light transmitting conductor comprising pattern of nanostructure and method of manufacturing the same
KR102238180B1 (en) 2014-08-05 2021-04-08 엘지디스플레이 주식회사 Flexible display device and method of fabricating the same
US10535792B2 (en) * 2014-10-28 2020-01-14 N&B Co., Ltd. Transparent conductor and preparation method for same
DE112016001679T5 (en) * 2015-05-08 2017-12-21 Ningbo Sinyuan Industry Group Co., Ltd. Wave heat conversion structure and its application
KR20200022226A (en) * 2018-08-22 2020-03-03 경희대학교 산학협력단 Oxide semiconductor thin film transistor and method of manufacturing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4983452A (en) * 1987-07-22 1991-01-08 Chisso Corporation Electroconductive thermoplastic sheet and method of forming same
KR20050115230A (en) * 2003-01-30 2005-12-07 에이코스 인코포레이티드 Articles with dispersed conductive coatings
EP1619524A1 (en) * 2003-04-28 2006-01-25 Takiron Co., Ltd. Electromagnetic-shielding light diffusion sheet

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7956525B2 (en) * 2003-05-16 2011-06-07 Nanomix, Inc. Flexible nanostructure electronic devices
US7261852B2 (en) * 2002-07-19 2007-08-28 University Of Florida Research Foundation, Inc. Transparent electrodes from single wall carbon nanotubes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4983452A (en) * 1987-07-22 1991-01-08 Chisso Corporation Electroconductive thermoplastic sheet and method of forming same
KR20050115230A (en) * 2003-01-30 2005-12-07 에이코스 인코포레이티드 Articles with dispersed conductive coatings
EP1619524A1 (en) * 2003-04-28 2006-01-25 Takiron Co., Ltd. Electromagnetic-shielding light diffusion sheet

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102421600A (en) * 2009-05-14 2012-04-18 杜邦帝人薄膜美国有限公司 Transparent conductive composite films
WO2010130986A1 (en) * 2009-05-14 2010-11-18 Dupont Teijin Films U.S. Limited Partnership Transparent conductive composite films
US9199438B2 (en) 2009-05-14 2015-12-01 Dupont Teijin Films U.S. Limited Partnership Transparent conductive composite films
CN102421600B (en) * 2009-05-14 2015-03-25 杜邦帝人薄膜美国有限公司 Transparent conductive composite films
EP2500171A3 (en) * 2009-05-14 2015-08-05 DuPont Teijin Films U.S. Limited Partnership Transparent conductive composite film
US9159943B2 (en) 2009-10-28 2015-10-13 Lunalec Ab Light-emitting electrochemical device, a system comprising such a device and use of such a device
WO2011053236A1 (en) * 2009-10-28 2011-05-05 Lunavation Ab A light-emitting electrochemical device, a system comprising such a device and use of such a device
EP3651212A3 (en) * 2010-08-07 2020-06-24 Tpk Holding Co., Ltd Device components with surface-embedded additives and related manufacturing methods
JP2013535843A (en) * 2010-08-07 2013-09-12 イノバ ダイナミックス, インコーポレイテッド Device component having surface embedded additive and related manufacturing method
WO2012063024A1 (en) 2010-11-12 2012-05-18 Dupont Teijin Films U.S. Limited Partnership Reflective conductive composite film
US20140008106A1 (en) * 2010-11-12 2014-01-09 Dupont Teijin Films U.S. Limited Partnership Reflective Conductive Composite Film
US9554460B2 (en) 2010-11-12 2017-01-24 Dupont Teijin Films U.S. Limited Partnership Reflective conductive composite film
CN103282204A (en) * 2010-11-12 2013-09-04 杜邦帝人薄膜美国有限公司 Reflective conductive composite film
EP3159162A4 (en) * 2014-06-12 2018-02-07 Toyo Ink SC Holdings Co., Ltd. Resin composition, layered product, and process for producing layered product
WO2018223293A1 (en) * 2017-06-06 2018-12-13 深圳创怡兴实业有限公司 Electroconductive flocking roller and preparation method therefor

Also Published As

Publication number Publication date
US20090056854A1 (en) 2009-03-05

Similar Documents

Publication Publication Date Title
US20090056854A1 (en) Method for manufacturing conductive composite material
WO2007004758A1 (en) Method for manufacturing transparent electrode and transparent electrode man¬ ufactured thereby
AU2009260690B2 (en) Carbon nanotube-transparent conductive inorganic nanoparticles hybrid thin films for transparent conductive applications
KR101624303B1 (en) Electrode of polymer nanofiber coated with aluminum thin film and manufacturing method thereof
EP2154598B1 (en) Transparent conductive polycarbonate film coated with carbon nanotubes and touch panel using the same
TWI450823B (en) Substrate with transparent conductive film manufacturing method thereof and touch panel using the same
KR101559494B1 (en) Flexible transparent conductive thin film and method of preparing the same
US20090129004A1 (en) Electrically conducting and optically transparent nanowire networks
KR100902561B1 (en) Method for manufacturing transparent electrode
US20050266162A1 (en) Carbon nanotube stripping solutions and methods
TW200927451A (en) Transparent conductors having stretched transparent conductive coatings and methods for fabricating the same
KR20100088155A (en) Method for producing carbon nanotube-containing conductor
KR20140058762A (en) Hard coating film and cover window using the same
JP2008288189A (en) Method of forming transparent conductive film containing carbon nanotube and binder, and transparent conductive film formed thereby
Kim et al. Electrically and mechanically enhanced Ag nanowires-colorless polyimide composite electrode for flexible capacitive sensor
KR100791999B1 (en) Method for manufacturing conductive composite material
Havel et al. Transparent Thin Films of Multiwalled Carbon Nanotubes Self‐Assembled on Polyamide 11 Nanofibers
WO2009131257A1 (en) Conductive polymer transparent electrode and fabricating method thereof
KR100791998B1 (en) Method for manufacturing conductive composite material
EP3294543B1 (en) Carbon nanotube based hybrid films for mechanical reinforcement of multilayered, transparent-conductive, laminar stacks
CN101868071A (en) Line heat source
KR100791997B1 (en) Conductor
CN101868070A (en) Line heat source
US9067393B2 (en) Method of transferring carbon conductive film
Ki et al. Fabrication of transparent conductive carbon nanotubes/polyurethane-urea composite films by solvent evaporation-induced self-assembly (EISA)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07745806

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 12295859

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC; EPO FORM 1205A DATED 15.12.2008

122 Ep: pct application non-entry in european phase

Ref document number: 07745806

Country of ref document: EP

Kind code of ref document: A1