WO2012008738A2 - 전도성 도료 조성물 및 이를 이용한 전도막의 제조방법 - Google Patents

전도성 도료 조성물 및 이를 이용한 전도막의 제조방법 Download PDF

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Publication number
WO2012008738A2
WO2012008738A2 PCT/KR2011/005109 KR2011005109W WO2012008738A2 WO 2012008738 A2 WO2012008738 A2 WO 2012008738A2 KR 2011005109 W KR2011005109 W KR 2011005109W WO 2012008738 A2 WO2012008738 A2 WO 2012008738A2
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WIPO (PCT)
Prior art keywords
coating
conductive
film
composition
paint composition
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Application number
PCT/KR2011/005109
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English (en)
French (fr)
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WO2012008738A3 (ko
Inventor
전성윤
도승회
이진서
한주희
Original Assignee
한화케미칼 주식회사
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Application filed by 한화케미칼 주식회사 filed Critical 한화케미칼 주식회사
Priority to CN201180034645.1A priority Critical patent/CN103108923B/zh
Priority to US13/809,769 priority patent/US20130207294A1/en
Priority to ES11807023.4T priority patent/ES2607961T3/es
Priority to EP11807023.4A priority patent/EP2594613B1/en
Priority to JP2013519583A priority patent/JP5727604B2/ja
Publication of WO2012008738A2 publication Critical patent/WO2012008738A2/ko
Publication of WO2012008738A3 publication Critical patent/WO2012008738A3/ko

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41F—PRINTING MACHINES OR PRESSES
    • B41F23/00—Devices for treating the surfaces of sheets, webs, or other articles in connection with printing
    • B41F23/04—Devices for treating the surfaces of sheets, webs, or other articles in connection with printing by heat drying, by cooling, by applying powders
    • B41F23/044—Drying sheets, e.g. between two printing stations
    • B41F23/0443—Drying sheets, e.g. between two printing stations after printing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C

Definitions

  • the present invention relates to a conductive paint composition and a method for producing a conductive film using the same.
  • the present invention relates to a conductive paint composition which has uniform and excellent conductivity and prevents deterioration of conductivity even if the late material included in the substrate is deformed.
  • metals such as silver, copper, nickel, indium tin oxide (ITO), antimony tin oxide (ATO), chromium, and zinc are deposited on the substrate by chemical / physical methods or surfactants or carbons.
  • ITO indium tin oxide
  • ATO antimony tin oxide
  • chromium chromium
  • zinc is deposited on the substrate by chemical / physical methods or surfactants or carbons.
  • Black or carbon fiber is coated or added to conductive materials, and conductive polymers are used to coat the substrate.
  • coating liquids with carbon nanotubes have been tried.
  • problems such as price, dispersion, transparency and stability. It is not commercialized due to the problem of mass production.
  • the carbon conductive resin is used as the conductive additive.
  • the object of the present invention is to provide an environmentally friendly water-based conductive coating composition, which is excellent in coating and has excellent conductivity and even during physical deformation.
  • conductive paint composition that prevents deterioration of electrical conductivity, and to provide conductive paint composition with excellent dispersibility and stability and excellent strength. It is used for antistatic, electrostatic dispersion, electrode and electromagnetic shielding (EMI). To provide excellent and economical conductive paint compositions.
  • EMI electromagnetic shielding
  • Another object of the present invention is to use the environmentally friendly water-based conductive paint composition according to the present invention, which is very good and uniform in conductivity and is capable of physical deformation.
  • the present invention provides a method of manufacturing a conductive film that prevents deterioration of electrical conductivity, and a method of manufacturing a conductive film used as an antistatic film, an electrode, and an electromagnetic shielding (EMI) shielding film.
  • a conductive film used as an antistatic film, an electrode, and an electromagnetic shielding (EMI) shielding film.
  • EMI electromagnetic shielding
  • the conductive paint compositions according to the present invention are hydrophilic polymer units and hydrophobic.
  • Block Copolymer Phosphorus Dispersant Conductive material that is a surface-modified carbon compound; Polymer Binder; and Water, an organic solvent, or a mixture thereof.
  • the surface-modified carbon compound imparts conductivity to the composition, wherein the carbon compound is selected from the group consisting of carbon fibers, carbon nanotubes, and graphene, or more. Nanotubes
  • At least one conductive additive selected from metal powder, metal coated inorganic powder, and metal fiber may be used as the conductive material by mixing with carbon nanotubes.
  • the carbon compound contained in the composition preferably contains carbon nanoleubes alone or carbon nanotubes and graphene, wherein the carbon nanotubes are 0.5 to 100 nm. Diameter and 0.1 to
  • the surface modified carbon compound of the present invention includes a carbon compound whose surface is oxidized by addition of an acid and / or an oxidizing agent or a carbon compound whose surface is oxidized by reactivity with an oxygen source including water under high temperature and high pressure.
  • the surface-modified carbon compound is obtained by subjecting the surface of the carbon compound to a sublime or supercritical condition using an oxidizing agent selected from one or more of oxygen, air, ozone, hydrogen peroxide and nitro compounds. It is obtained by oxidizing the surface of carbon compounds by mixing carboxylic acid, nitric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, hydrogen peroxide or a mixture thereof.
  • the surface-modified carbon compound obtained by using the sublime counting or supercritical counting conditions is 50 to 400 atm using an oxidizing agent selected from oxygen, air, ozone, hydrogen peroxide, nitro compounds, and mixtures thereof. Pressure of 100 to
  • the surface-modified carbon compound may be obtained by oxidizing the surface of carbon nanotubes by adding carboxylic acid, nitric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, hydrogen peroxide or a mixture thereof to the carbon compound.
  • carboxylic acid, nitric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, hydrogen peroxide or a mixture thereof may simply provide oxidation of the surface modification.
  • the surface modified carbon compound according to the present invention is surface modified (surface oxidation) to contain 0.01 to 10 parts by weight of oxygen, nitrogen, sulfur, or a mixture thereof based on 100 parts by weight of carbon.
  • the surface modified carbon compound may be a solvent, a dispersant and a polymer according to the present invention.
  • the block copolymer is a block copolymer composed of hydrophilic polymer units and hydrophobic polymer units, and is a dispersant for dispersing carbon compounds.
  • the block copolymer is a compound containing both a hydrophilic polymer and the hydrophobic polymer by polymerization, and then polymerizing a hydrophilic polymer with a hydrophilic monomer, and adjusting the pH to an alkaline region (P H 6 ⁇ 9), the polymerization It is a block copolymer obtained by carrying out the polymerization of hydrophobic polymers using hydrophobic monomers as a reaction place of the hydrophilic polymers.
  • the dispersant which is a block copolymer composed of a hydrophilic polymer unit and a hydrophobic polymer unit, may be prepared using the technique described in Korean Patent Publication No. 2001-0088773 or 2001-0084640.
  • the block copolymer comprising the hydrophilic polymer unit and the hydrophobic polymer unit has a feature of being a styrene-acrylic water-soluble resin, and the styrene content of the styrene-acrylic water-soluble resin is preferably 30 to 90% by weight.
  • the styrene-acrylic water-soluble resin has a weight average molecular weight of 1,000 to 100,000.
  • the composition according to the present invention contains a styrene-acrylic water-soluble resin together with a surface-modified carbon compound as a dispersant, and thus the surface coating and curing of a substance having a constant use and shape ( Dry) to impart antistatic, electrostatic dispersion, conductive or EMI shielding ability to the water, and further, after the conductive paint composition is applied and cured (dryed) on the surface of the base material before manufacturing the final product,
  • Dry a constant use and shape
  • the field of application of conductive paint compositions according to the present invention can be greatly expanded, which deteriorates the electrical properties of conductive paint compositions coated by forming a later material containing conductive paint compositions. Not by the features of the present invention.
  • antistatic materials electrostatic dissipative materials, conductive materials, electromagnetic shielding materials, electromagnetic wave absorbing materials, solar cell materials, fuel materials for fuel sensitization cells (DSSC), electric devices, cathode active materials for secondary batteries, cathode active materials and electrical using them Chemical devices, secondary batteries, fuel cells, solar cells, memory devices, hybrid capacitors (P-EDLC), or electrochemical devices that are capacitors, electronic devices, semiconductor devices, photoelectric devices, notebook parts materials, computer parts materials, mobile phone parts materials , PDA parts material, PSP parts material, game machine Component materials, housing materials, transparent electrode materials, opaque electrode materials, field emission display
  • FED field emission display
  • BLU back light unit
  • Liquid crystal display (LCD) materials plasma display panel (PDP) materials, light emitting diode (LED) materials, touch panel materials, electronic display panels, billboard materials, display materials, heating elements , Radiator, Plating material, Catalyst, Promoter, Oxidizer, Reducing agent, Automobile parts material, Ship parts material, Aircraft parts material, Protective tape material, Adhesive material, Tray material, Clean room material, Transport equipment parts material, Flame retardant Materials, Antibacterial materials, Metal composite materials, Non-ferrous metal composite materials, Medical device materials, Building materials, Floor materials, Wallpaper materials, Light source parts materials, Lamp materials, Optical equipment parts materials, Textile manufacturing materials, Clothing manufacturing materials, Electrical product manufacturing materials and
  • the final product may be manufactured by performing a shape processing.
  • the polymer binder controls the strength of the film formed when the composition is applied.
  • the viscosity of the composition is controlled.
  • the polymer binder is a resin that is solidified or cured by heat or light, and may be a heat or photocurable binder commonly used in an antistatic protective film.
  • emulsions containing urethane, epoxy, melamine, acetal, acrylic, acryl-styrene, vinyl acryl-based mulch, carbonate, styrene, ester, vinyl, polyphenylene ether resin, acrylonitrile- Butadiene-styrene, polysiloxanes, coupling agents containing metals in the center and having organic compound ligands and copolymers thereof may be used, and preferably, the polymeric binder is an acryl-urethane copolymer. Coalescing and reminding
  • the acrylic urethane copolymer preferably has a weight average molecular weight of 1,000 to 100,000.
  • the polymer binder may be a Korean Patent Application No. 10-2000-0009833 or
  • Emulsion resins prepared using the techniques described in 10-2000-0014086 may be used.
  • the medium may be one or more solvents selected from the group consisting of water, alcohols, ketones, amines, esters, amides, alkyl halogens, ethers, furans, sulfur-containing solvents, and mixtures thereof. Specifically, water, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, acetone, methyl ethyl ketone, cyclo nucleonone, nucleic acid, ethyl amine, triethylamine, Octadecyl amine, cyclo nucleic acid, ethyl acetate, acetone, dimethylformamide, dimethylacetamide, methylene chloride, chloroform, carbon tetrachloride, dimethyl sulfoxide, dioxin, nitromethane, toluene, xylene, dichlorobenzene, dimethylbenzene , Trimethyl
  • the medium is pure water or an aqueous system in which water and an organic solvent are mixed.
  • the medium contains an organic solvent, it is preferable to substantially contain 0.1 to 5% by weight of an organic solvent.
  • the organic solvent contained in the aqueous solvent is for forming a homogeneous conductive film.
  • the organic solvent contained in the aqueous solvent may be one or more selected from the group consisting of alcohols, ketones, amines, esters, amides, alkylhalogens, ethers, furans, sulfur-containing solvents, and mixtures thereof.
  • the conductive paint composition preferably contains 0.1 to 5% by weight of the carbon compound. If the surface-modified carbon compound content is less than 0.1% by weight, the conductivity may be reduced during molding, and 5% by weight. Exceeding% may lower the properties of the membrane coated with the composition, especially the film transparency.
  • the conductive coating composition contains 0.05 to 5% by weight of the dispersant. If the content of the dispersant is less than 0.05% by weight, there is a risk that the carbon nanolyuves will not be homogeneously dispersed, and 5% by weight. If exceeded, there is a risk of degrading the electrical conductivity and strength of the membrane.
  • the conductive paint composition preferably contains 5 to 15% by weight of the polymer binder.
  • the content of the polymer binder is less than 5% by weight, the adhesion between the conductive material and the film base material coated with the conductive material is applied. There is a risk of weakness, and if it exceeds 15% by weight, there is a risk of not being sufficiently cured by heat or light, and there is a risk of deteriorating electrical conductivity.
  • the conductive coating composition is 75 to 90% by costume group medium by weight.
  • the medium is less than 75% by weight and the danger of a coating of the composition is not easily carried out, in excess of 90% by weight In this case, there is a risk that the electrical conductivity and strength of the membrane will be reduced.
  • the conductive paint composition may optionally be a leveling agent, a wetting agent, a surfactant,
  • Dispersion stabilizers antisettling agents, pH adjusting agents, thickeners, slippers, antifoaming agents, adhesives, adhesives, thixothropic agents, antioxidants, crosslinkers, antifilming agents, anti-cratering agents, plasticizers, drying agents, It may further contain one or more additives selected from flame retardants, antiblocking agents, anticorrosion agents, coupling agents, floating agents and dyes and, for example, contain a leveling agent as an additive.
  • the leveling agent is typically used to produce a smooth surface in the paint composition.
  • the leveling agent to be used may be used, preferably, the leveling agent is a siloxane-based leveling agent including polydimethylsiloxane, polyether-modified polydimethylsiloxane, and polyether-modified siloxane.
  • the conductive paint composition contains 0.01 to 0.5% by weight of an additive.
  • the conductive coating composition according to the invention the stretching when stretched to a conductive film obtained by applying and curing the above-mentioned conductive coating composition into a film of 1 to 1000% elongation resolutely conductive film sheet resistance (sheet resistance) is ⁇ . ⁇ 2 - there are features 1.0 ⁇ 10 " ⁇ / ⁇ , more characteristically l.OxlO 7 - there is a 1.0 0 9 / ⁇ features.
  • the conductive paint composition according to the present invention can be used as a coating composition for antistatic, electrostatic dispersion, conductive, EMI shielding black electrode.
  • the conductive paint composition described above may be prepared by selectively adding an additive together with the dispersant, the conductive material, the polymer binder, and the medium, and the combination may be a mixer, a blade, a fluidizer, a paint shaker, an ultrasonic wave, a homogenizer. Niger, bead mill, pulverizer, and black one of the mills can be performed using more than one device.
  • the method for manufacturing a conductive film according to the present invention comprises the steps of: a) coating a conductive coating composition according to the present invention on at least one surface of the substrate to form a coating film; and b) applying hot air, heat or ultraviolet rays to the coating film. And applying to harden the coating film.
  • step b) c) forming a coating film by coating the coating composition on an opposite surface of the substrate; and d) applying hot air, heat, or ultraviolet rays to the coating film. Curing the coating film; further may be performed.
  • the conductive film may be formed on one region of the surface of the substrate, for example, on one surface of the substrate or on opposing surfaces, and may be formed on the entire surface of the substrate.
  • the substrate includes polyester, polystyrene, polycarbonate, polyimide,
  • One or more selected from the group consisting of metal oxide plates, ⁇ -deposited glass, PCBs, epoxy, semiconductor needles, semiconductor packages and their laminates may be used.
  • polyester Preferably polyester, polystyrene, polyimide, polycarbonate or polyolefin
  • the conductive film has a sheet or film shape and has an antistatic film, a conductive film and an electromagnetic wave (EMI). Shielding film or electrode.
  • EMI electromagnetic wave
  • the coatings include bar coating, gravure coating, microgravure coating,
  • the substrate is subjected to the corona treatment or UV ozone before the coating is carried out.
  • the conductive paint composition may be applied onto the substrate surface on which the treatment has been performed.
  • the substrate on which the conductive film is formed is stretched and
  • the present invention comprises the steps of: a) applying at least one surface of the conductive coating composition according to the present invention to form a coating film; b) hardening the coating film by applying hot air, heat or ultraviolet rays to the coating film; and e) heating and softening the substrate on which the conductive film is formed in the shape of a tray used when transferring or storing electronic components.
  • a method of forming a substrate comprising stretching and molding at an elongation of the substrate.
  • the conductive film is formed
  • the conductive film is prevented from being charged, electrostatic dispersed, conductive, and shielded, and the conductivity is uniformly maintained throughout the molded product.
  • the molding is a vacuum molding.
  • the mold is formed by heat-softening a substrate on which a conductive film formed by curing the coating film is formed.
  • Molding method of product is not particularly limited and can be manufactured through commonly used molding process. However, substrate having conductive film formed without separate molding process is required. Of course, can be used as a final product.
  • the molded article obtained by the molding includes antistatic material, electrostatic dispersion, conductive film, electromagnetic shielding material, electromagnetic wave absorbing material, solar cell, fuel sensing battery (DSSC) electrode, electrical and electronic device, secondary battery positive electrode active material, Cathode active materials and electrochemical devices using them, secondary batteries, fuel cells, solar cells, memory devices, electrochemical devices that are hybrid capacitors (P-EDLC) or capacitors, semiconductor devices, photoelectric devices, laptop parts, computer parts, mobile phone parts, PDA parts, PSP parts, game machine parts, housings, transparent electrodes, opaque electrodes, field emission displays (FED), back light units (BLUs), liquid crystal displays (LCDs), plasma display panels (PDP; plasma display panel), light emitting diode (LED), touch panel, display board, billboard, display, heating element, radiator, plating, catalyst, promoter, oxidizing agent, reducing agent, automobile parts, ship parts, port Machine components, masking tape, adhesive, tray, clean rooms, transportation equipment components, It can be used in flame retardant materials, anti
  • the conductive paint composition according to the present invention has the advantages of being an environmentally friendly water-based conductive paint composition that does not use strong acids, strong bases or organic solvents, and forms a very good and uniform conductive film upon application, and between the coated film and the substrate. It has excellent bonding strength and has the advantage of maintaining excellent electrical conductivity even when the coated film is physically deformed. It can impart antistatic, electrostatic dispersion, conductor, electrode or electromagnetic wave shielding ability to arbitrary materials, and conductive coating composition. It has the advantage of being able to mass produce in a short time at low cost.
  • Example 2 is a scanning electron micrograph of the conductive film prepared in Example 2,
  • FIG. 2 is a scanning electron micrograph observed after vacuum forming the conductive film prepared in Example 2.
  • FIG. 2 is a scanning electron micrograph observed after vacuum forming the conductive film prepared in Example 2.
  • CNT carbon nanotubes
  • the CNT solution was mixed with CNT solution at the flow rate, and the CNT solution (CNT mixture) mixed with oxygen was preheated to 150 to 200 ° C through a heat exchanger and introduced into the preheater at a Hg / min flow rate through a high pressure injection pump.
  • the mixture is 210 ° C and
  • the surface-modified product is injected into a surface reformer in a subcritical state of 240 atm, and the surface is modified.
  • the surface-modified product is transferred to a heat exchanger, and then first cooled to 100 ° C.
  • Surface modified 14.3 g of CNTs were obtained.
  • CNT dispersions were prepared by mixing and dispersing 75 g of a styrene / acrylic water-soluble resin (manufactured by Hanwha Chemical, product number Soluryl 160, and a weight average molecular weight of 15,000) and 895 g of pure water through a stirrer.
  • a styrene / acrylic water-soluble resin manufactured by Hanwha Chemical, product number Soluryl 160, and a weight average molecular weight of 15,000
  • a CNT-graphene dispersion was prepared in the same manner as in Preparation Example 7, except that 22.5 g was used.
  • a CNT-graphene dispersion was prepared in the same manner as in Preparation Example 7, except that 7.5 g of surface-modified CNT and 22.5 g of graphene were used.
  • the paint prepared by using a roll-to-gravure coating was coated on a polyester film with a thickness of 5 (wet thickness), and then put in a convection obon maintained at a temperature of 80 ° C. for 1 minute.
  • a dried and thermoset conductive film (coated film) was prepared.
  • Example 1 The same process as in Example 1 was performed except that 0.5 wt% of a leveling agent (BYK346) was added to the paint of Example 1.
  • BYK346 a leveling agent
  • the sample was prepared by the coating film manufacturing method. The measurement was made based on air as background in the UV / Vis spectrometer. The wavelengths in Table 1 are measured at 550 nm.
  • Measurement was performed according to JISK 7194 / ASTM D991 using Loresta GP (MCP-T600) manufactured by Mitsubishi.
  • FIG. 1 is a scanning electron micrograph of the conductive film prepared in Example 2, and as shown in FIG. 1, it can be seen that carbon nanotubes are spread evenly on the surface of the substrate, and between carbon nanotubes and the upper layer thereof. It was found that the binder and the leveling agent for the paint had a strong combination.
  • FIG. 2 is a scanning electron micrograph of the conductive film after vacuum molding, and evenly distributed even with tensile elongation of 400% after vacuum molding, which has uniform dispersion and has a uniform dispersibility. Know that they are tightly bound without Can be.
  • the composition according to the present invention is an environmentally friendly aqueous composition which does not use strong acids, strong bases, and organic solvents, has excellent dispersibility, and has a high bond strength with 400% of lead. It can be seen that the elongation does not cause interfacial desorption with the substrate and maintains excellent electrical conductivity.
  • Table 1 summarizes the results of measuring the surface resistance, the permeability, the surface hardness, and the surface resistance after molding of the conductive films prepared in Examples 1 and 2 and Comparative Example 1, and in Table 1 below.
  • the elongation was 400%.
  • the conductive films prepared in Examples 3 and 4 also had characteristics similar to those of the conductive films prepared in Examples 1 and 2.
  • the superior dispersibility of carbon nanotubes shows that it has excellent electrical conductivity of more than 10 7 orders as compared with the comparative example, and the excellent electrical conductivity is maintained by 400% of physical stretching.
  • the adhesion to the substrate is very good, and the adhesion strength is improved from 5B to 1H compared to the comparative example, and the leveling effect is improved by the addition of the leveling agent to improve the surface resistance. Able to know.

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Abstract

본발명은 균일한 전도성과 안정성을 가지는 전도성 도료 조성물 및 상기 전도성 도료 조성물을 이용한 전도막 제조 방법에 관한 것으로, 상세하게, 본 발명의 전도성 도료 조성물은 친수성 고분자 단위와 소수성 고분자단위로 이루어진 블록공중합체인 분산제; 표면 개질된 탄소화합물인 전도성 물질; 고분자 바인더; 및 물, 유기 용제 또는 이들의 혼합물인 매질;을 포함하는 특징이 있으며, 상기 전도성 도료 조성물은 기재에 전도막으로 도포 및 경화되어 상기 기재의 표면구조를 제어함으로써 균일한 대전방지, 정전분산 (ESD; Electrostatic dissipatoin), 도전성 전자기파 차폐 기능을 부여하는 특징이 있다.

Description

명세서
발명의명칭:전도성도료조성물및이를이용한전도막의
제조방법
기술분야
[1] 본발명은전도성도료조성물및이를이용한전도막의제조방법에관한
것으로，균일하고우수한전도성을가지며,기재에도포된후기재가변형되어도 전도도의열화가방지되는전도성도료조성물에관한것이다.
[2]
배경기술
[3] 각종생활용품,사무자동화기기,전기 ·전자제품，휴대폰등을비롯하여
전기 /전자부품및반도체소자의집적도가높아짐에따라먼지나파티클의 오염，정전기발생,전자파에의한제품의손상문제가크다.이와같은제품을 제조하는데사용되는각종부품들이조립,운반및운송,포장되는과정에서 발생되는먼지나파티클,정전기，전자파가미치는영향이매우크다.이러한 피해를줄이기위하여전기전도성을가지는물질로조립，운반，운송，포장에 쓰이는재료에대전방지，정전분산,도전성,전자파차폐의기능을부여한다.
[4] 종래에는전기전도성을가지는물질로은，구리，니켈，산화인듐주석 (ITO), 산화안티몬주석 (ATO),크롬，아연등의금속을기재에화학적 /물리적방법으로 증착하거나계면활성제나카본블랙혹은탄소섬유등을내첨혹은코팅하기도 하며，또한전도성고분자를사용하여기재에코팅하여사용하였다.또한최근 탄소나노튜브를적용한코팅액의제조가시도되고있으나가격,분산，투명성, 안정성등의문제와양산성이문제되어상용화되지못하고있다.
[5] 종래의금속증착방법은많이사용할수록전도성이향상되나장기안정성이 낮고원가에대한부담이크며，코팅막형성후성형과정에서금속층이깨지거나 갈라짐으로써사용하기어렵다.
[6] 또한계면활성제의경우높은전기전도성의구현이어려우며일정수준의 습도가필요하므로계절적인영향을받기쉽고성형후부품에 전이되는문제가 있다.이러한한계를극복하고자전도성고분자를도료화하여코팅막을 형성하고있으나전기적물성의효과기간이짧고，코팅부위에따른전도성의 불균일이심한단점이 있으며，코팅막이형성된기재는진공성형시일정이상 깊이또는복잡한모양의제품에서는전도성을구현하기어렵다.
[7] 한편，상기전도성 첨가제로서탄소나노류브를사용해상기전기전도성
열가소성수지에우수한전기전도성을부여하고자하는시도가
있었다 (대한민국등록특허제 0706652호)
[8] 그러나，탄소나노류브를물이나유기용제에분산시키기위하여강산이나 강염기를사용하여탄소나노류브의표면처리방법을적용하는데이과정에서 발생하는다량의폐수에의한환경적인부담과표면처리과정에서 탄소나노튜브가손상됨으로써 전기전도성을구현하기어려운기술적문제점이 존재한다.
[9]
발명의상세한설명
기술적과제
[10] 본발명의목적은친환경적인수계전도성도료조성물을제공하는것이며， 도포시매우우수하고균일한전도성을가지며물리적인변형시에도
전기전도도의열화가방지되는전도성도료조성물을제공하는것이며， 분산성과안정성이우수하고강도가우수한전도성도료조성물을제공하는 것이며,대전방지，정전분산，전극，전자파 (EMI)차폐용으로사용되며성능이 우수고，경제성있는전도성도료조성물을제공하는것이다.
[11] 본발명의다른목적은본발명에따른친환경적인수계전도성도료조성물을 이용하여매우우수하고균일한전도성을가지며물리적인변형시에도
전기전도도의열화가방지되는전도막의제조방법을제공하는것이며， 대전방지막,전극，전자파 (EMI)차폐막으로사용되는전도막의제조방법을 제공하는것이다.
[12]
과제해결수단
[13] 이하본발명의조성물및제조방법을상세히설명한다.이때，사용되는기술 용어및과학용어에있어서다른정의가없다면,이발명이속하는기술 분야에서통상의지식을가진자가통상적으로이해하고있는의미를가지며， 하기의설명및첨부도면에서본발명의요지를불필요하게흐릴수있는공지 기능및구성에대한설명은생략한다.또한,본명세서에서사용되는정도의 용어 "약 "실질적으로"등은언급된의미에고유한제조및물질허용오차가 제시될때그수치에서또는그수치에근접한의미로사용되고，본발명의 이해를돕기위해정확하거나절대적인수치가언급된개시내용을비양심적인 침해자가부당하게이용하는것을방지하기위해사용된다.
[14] 본발명에따른전도성도료조성물은친수성고분자단위와소수성
고분자단위로이루어진블록공중합체 (Block Copolymer)인분산제;표면개질된 탄소화합물인전도성물질;고분자바인더；및물,유기용제또는이들의 흔합물인매질;을포함한다.
[15] 상기표면개질된탄소화합물에의해상기조성물에전도성이부여되며，상기 탄소화합물은탄소섬유，탄소나노튜브및그라핀 (graphene)으로이루어진 군하나혹은그이상선택되는것이다.이때,상기탄소나노튜브는
단일벽 (Single-walled),이중벽 (Double walled),얇은다중벽 (Thin multi-walled), 다중벽 (Multi-walled)및다발형 (Roped)에서하나이상선택된탄소나노류브이다. [16] 본 발명에 있어，상기 탄소화합물 외 에도 금속분말，금속코팅 무기분말 및 금속섬유에서 하나 이상 선택된 전도성 첨 가제를 탄소나노튜브와 흔합하여 전도성 물질로 사용할 수 있다.
[17] 물리 적 변형 에 따른 전기 전도도 저하 방지 측면에서，상기 조성물에 함유되는 탄소화합물은 탄소나노류브 단독 또는 탄소나노튜브 및 그라핀을 함유하는 것이 바람직하며，상기 탄소나노튜브는 0.5 내지 lOOnm의 직 경 및 0.1 내지
1000/ m의 길이를 갖는 것이 바람직하다.
[ 18] 본 발명의 상기 표면 개 질된 탄소화합물은 산 및 /또는 산화제를 가하여 표면이 산화된 탄소화합물 또는 고온 고압하에서 물을 포함한 산소 공급원과의 반응성에 의해 표면이 산화된 탄소화합물을 포함한다.
[19] 상세하게, 상기 표면 개질된 탄소화합물은 산소，공기，오존，과산화수소수 및 니트로화합물에서 하나 이상 선택되는 산화제를 사용하여 아임 계수 또는 초임 계수 조건에서 상기 탄소화합물의 표면을 산화처 리하여 얻어지거나, 카르복실산, 질산，인산，황산，불산，염산，과산화수소수 또는 이들의 흔합물을 흔합하여 탄소화합물 표면을 산화시켜 얻어 진 것이다.
[20] 보다 상세하게，아임 계수 또는 초임 계수 조건을 이용하여 얻어 진 표면 개질된 탄소화합물은 산소, 공기 , 오존，과산화수소수, 니트로화합물 및 이들의 흔합물에서 선택되는 산화제를 사용하여 50 내지 400atm의 압력과 100 내지
600°C 온도 조건에서 탄소화합물의 표면을 산화처 리하여 얻어진 것 이다.
[21] 이를 통해, 아임 계 또는 초임 계 조건에서 유해하지 않으며，취급 및 폐수처 리 가 용이 한 산화제를 사용하여 환경 친화적으로 표면 개질된 탄소화합물을 얻을 수 있으며，상기의 아임 계수 또는 초임 계수 조건의 표면개질은 산화제가 용이하게 도입되어 탄소화합물의 표면개질 효과가 상승되며 그에 따른 분산성 이 증가하게 된다. 또한，탄소화합물을 연속적으로 대량 개질 가능하여，단 시 간 내에 저 비용으로 표면 개질된 탄소화합물을 대량 생산 할 수 있다.
[22] 상기 아임 계수 또는 초임 계수 조건을 이용한 탄소화합물의 표면 개질은
대한민국 특허출원 제 10-2008-0029333, 제 10-2008-0037685 또는 제
10-2008-0050048호에 기 재된 기술을 이용하여 수행될 수 있다.
[23] 다른 방법으로 상기 표면 개질된 탄소화합물은 탄소화합물에 카르복실산, 질산，인산，황산，불산，염산，과산화수소수 또는 이들의 흔합물을 첨 가하여 탄소나노튜브 표면의 산화작용으로 얻어 질 수 있는데，산화제의 도입으로 간단하게 표면개질의 산화가 제공될 수 있다.
[24] 본 발명 에 따른 상기 표면 개질된 탄소화합물은 탄소 100 중량부에 대하여 0.01 내지 10 중량부의 산소，질소, 황 또는 이들의 흔합물을 함유하도록 표면 개 질 (표면 산화)된 것이 다.
[25] 상기 표면 개 질된 탄소화합물은 본 발명 에 따른 용매，분산제 및 고분자
바인더와 매우 균질하고 효과적으로 흔합될 수 있으며，특히 고분자 바인더와의 분산성 이 현저하게 높아져 균일한 전도성 에 영향을 준다. 또한，그라핀， 탄소나노튜브와같이서로다른탄소화합물로전도성물질이이루어진 경우에도탄소화합물간의흔합이극히용이하게된다.
[26] 상기블록공중합체는친수성고분자단위와소수성고분자단위로이루어진 블록공중합체이며，탄소화합물을분산시키는분산제이다.
[27] 상기블록공중합체는중합에의해친수성고분자와소수성고분자를모두 함유하는화합물이며，친수성모노머를이용하여친수성고분자를중합하고 알칼리영역 (PH 6~9)으로산도를조절한후，중합된친수성고분자를반웅 장소로하여소수성모노머를이용한소수성고분자의중합이다시수행되어 얻어진블록공중합체이다.
[28] 상기친수성고분자단위와소수성고분자단위로이루어진블록공중합체인 분산제는대한민국공개특허제 2001-0088773호또는 2001-0084640호에기재된 기술을이용하여제조될수있다.
[29] 상기친수성고분자단위와소수성고분자단위로이루어진블록공중합체는 스티렌-아크릴계수용성수지인특징이 있으며,상기스티렌-아크릴계수용성 수지의스티렌함량은 30내지 90중량 %인것이바람직하며,상기
스티렌-아크릴계수용성수지는중량평균분자량이 1,000내지 100,000인것이 바람직하다.
[30] 상기스티렌-아크릴계수용성수지를분산제로상술한표면개질된
탄소화합물과함께사용함으로써，탄소화합물의분산성을획기적으로증진시킬 수있으며，조성물의도포시매우균일한막 (도포막)을형성할수있으며,균일한 전기전도도를갖는막 (도포막)올제조할수있으며，도포된 (및경화된)막이높은 연신율로연신되며,연신된막의전기전도도변화가방지되는특징이 있다.
[31] 상술한바와같이，본발명에따른조성물은표면개질된탄소화합물과함께 스티렌-아크릴계수용성수지를분산제로함유함에따라，일정용도와형상을 갖는물 (物)의표면에도포및경화 (건조)되어상기물에대전방지，정전분산， 도전성또는 EMI차폐능을부여할수있으며，나아가,최종산물을제조하기전 원기재의표면에상기전도성도료조성물을도포및경화 (건조)한후에원 기재를형상가공하여최종산물을제조할수있는장점이있다.
[32] 상술한장점에의해,본발명에다른전도성도료조성물의웅용분야가매우 확대될수있는데，이는전도성도료조성물을기재에도포한후기재를형상 가공하여도도포된전도성도료조성물의전기적특성이열화되지않는본 발명의특징에의한것이다.
[33] 이에따라대전방지소재,정전분산소재，전도성소재，전자파차폐재，전자파 흡수재，태양전지용재료，연료감웅용전지 (DSSC)용전극재료，전기소자, 이차전지용양극활물질，음극활물질및이를이용한전기화학소자，이차전지， 연료전지，태양전지，메모리소자,하이브리드캐패시터 (P-EDLC),또는 캐퍼시터인전기화학소자，전자소자,반도체소자，광전소자,노트북부품재료, 컴퓨터부품재료，핸드폰부품재료， PDA부품재료, PSP부품재료，게임기용 부품 재료, 하우징 재료，투명 전극 재료，불투명 전극 재료, 전계방출디스플레이
(FED;field emission display)재료, BLU(back light unit)재료,
액정표시 장치 (LCD;liquid crystal display) 재료，플라즈마표시 패 널 (PDP;plasma display panel ) 재료，발광다이오드 (LED;luminescent diode) 재료, 터치패 널 재료， 전광판 재료，광고판 재료，디스플레이 소재，발열체，방열체，도금 재료，촉매, 조촉매，산화제, 환원제，자동차 부품 재료, 선박 부품 재료，항공기기 부품 재료， 보호테이프 재료, 접착제 재료，트레이 재료, 클린룸 재료，운송 기 기 부품 재료， 난연 소재，항균 소재，금속 복합 재료，비 철 금속 복합재료，의료 기기용 재료， 건축 재료，바닥재 재료，벽지 재료，광원 부품 재료, 램프 재료, 광학기 기 부품 재료, 섬유제조용 재료，의류제조용 재료，전기제품제조용 재료 및
전자제품제조용 재료에서 선택된 기 재에 본 발명에 따른 전도성 도료 조성물을 도포하여 막을 형성한 후，형상 가공을 수행하여 최종 산물을 제조할 수 있다.
[34] 상기 고분자 바인더는 조성물의 도포시 형성되는 막의 강도를 조절하고
조성물의 점도를 제어한다. 상기 고분자 바인더는 열 또는 광에 의해 고화 혹은 경화되는 수지로서，대전방지 보호 필름에 통상적으로 사용되는 열 또는 광 경화형 바인더 이 면 무방하다. 일 예로，우레탄，에폭시，멜라민，아세탈，아크릴， 아크릴 -스티 렌을 포함한 에멀젼, 비 닐아크릴계 에 멀견, 카보네 이트, 스티 렌, 에스테르，비 닐，폴리페닐렌에 테르 수지 , 아크릴로니트릴-부타디 엔-스티 렌, 폴리실록산, 중심에 금속을 함유하고 유기화합물 리간드가 있는 커플링제 및 이들의 공중합체로 이루어진 군에서 하나 이상 선택을 사용할 수 있으며， 바람직하게, 상기 고분자 바인더는 아크릴-우레탄 공중합체이 며 , 상기
아크릴-우레탄 공중합체는 중량평균분자량이 1,000 내지 100,000인 것이 바람직하다.
[35] 상기 고분자 바인더는 대한민국 특허출원 제 10-2000-0009833 또는 제
10-2000-0014086호에 기 재된 기술을 이용하여 제조된 에멀젼 수지를 이용할 수 있다.
[36] 상기 매질은 물，알코올，케톤, 아민，에스테르，아미드，알킬 할로겐, 에 테르， 퓨란，황 함유 용제 및 이들의 흔합물로 이루어진 군에서 하나 이상 선택된 용매를 사용할 수 있다. 구체적으로는 물，메틸알콜, 에 틸알콜，프로필알콜, 부틸알콜, 이소프로필알콜, 이소부틸알콜，에틸렌글리콜，아세톤, 메틸에틸케톤, 사이클로 핵사논，핵산, 디 에 틸아민，트리 에틸아민，옥타데실 아민，사이클로 핵산，에틸아세테이트，아세톤，디 메틸폼아미드，디 메틸아세트아미드, 메틸렌 클로라이드，클로로포름, 사염화탄소，디 메틸설폭사이드，다이옥신，니트로메탄， 를루엔，자이 렌，디클로로벤젠, 디메틸벤젠, 트리 메틸 벤젠, 메틸나프탈렌， 테트라하이드로퓨란， N-메틸 -2-피를리돈, 피리딘, 아크릴로니트릴，아닐린, 솔비를，카비를，카비롤아세테이트, 메틸샐로졸브 및 에 틸샐로졸브로 이루어 진 군으로부터 하나 이상 선택된 것이 다ᅳ
[37] 보다 바람직하게, 상기 매질은 순수한 물 또는 물과 유기용제가 흔합된 수계 용매이다.상기매질이유기용제를함유하는경우，실질적으로 0.1중량 %내지 5 중량 %의유기용제를함유하는것이바람직하다.상기수계용매에함유되는 유기용제는균질한전도막을형성시키기위한것으로，상기수계용매에 함유되는유기용제는알코올，케톤，아민，에스테르，아미드，알킬할로겐, 에테르，퓨란，황함유용제및이들의흔합물로이루어진군에서하나이상 선택된용매를사용할수있다.구체적으로는메틸알콜,에틸알콜，프로필알콜， 부틸알콜,이소프로필알콜，이소부틸알콜，에틸렌글리콜，아세톤，메틸에틸케톤, 사이클로핵사논，핵산，디에틸아민,트리에틸아민，옥타데실아민，사이클로 핵산,에틸아세테이트，아세톤，디메틸품아미드，디메틸아세트아미드，메틸렌 클로라이드,클로로포름，사염화탄소，디메틸설폭사이드,다이옥신,니트로메탄, 를루엔，자이렌,디클로로벤젠,디메틸벤젠,트리메틸벤젠,메틸나프탈렌, 테트라하이드로퓨란， N-메틸 -2-피롤리돈,피리딘,아크릴로니트릴,아닐린， 솔비를，카비를，카비를아세테이트，메틸샐로졸브및에틸셀로졸브로이루어진 군으로부터하나이상선택된것이바람직하다.
[38] 상기전도성도료조성물은 0.1내지 5중량 %의상기탄소화합물을함유하는 것이바람직하다.상기의표면개질된탄소화합물함량이 0.1증량 %미만이면 성형시전도성이저하될위험이 있으며， 5중량 %를초과하면조성물을도포한 막의물성이저하될우려가있으며특히막의투명성을매우저하시킨다.
[39] 상기 전도성도료조성물은 0.05내지 5중량 %의상기분산제를함유하는것이 바람직하다.상기분산제의함량이 0.05중량 %미만이면탄소나노류브가 균질하게분산되지않을위험이있으며， 5중량 %를초과하면막의전기전도도와 강도를저해할위험이 있다.
[40] 상기전도성도료조성물은 5내지 15중량 %의상기고분자바인더를함유하는 것이바람직하다.상기고분자바인더의함량이 5중량 %미만인경우상기 전도성도료조성물이도포된막이기재와전도성재료와의부착성이약하게될 위험이있으며 , 15중량 %를초과하면열또는광에의해충분히경화되지않을 위험이있으며，전기전도도를저해할위험이있다.
[41] 상기전도성도료조성물은 75내지 90중량 %의상기매질을함유하는것이 바람직하다.상기매질이 75중량 %미만인경우조성물의도포가용이하게 수행되지않을위험이있으며 ,90중량 %를초과하는경우막의전기전도도와 강도가저하될위험이있다.
[42] 상기전도성도료조성물은선택적으로레벨링제，습윤제，계면활성제，
분산안정제，침강방지제 , pH조절제 ,증점제,슬립제，소포제,점착제，접착제 , 칙소부여제 (thixothropic agent),산화방지제，가교제，피막방지제,크레터링 방지제 (anti-cratering agent),가소제,건조제，난연제，블로킹방지제，부식방지제, 커플링제,부유제 (floating agent)및염료에서하나이상선택된첨가제를더 함유할수있으며，일예로，레벨링제를첨가제로더함유한다.
[43] 상기레벨링제는도료조성물에서매끈한표면을제조하기위해통상적으로 사용하는레벨링제면사용가능하나,바람직하게상기레벨링제는 폴리디메틸실록산，폴리에테르변성폴리디메틸실록산，폴리에테르변성 실록산을포함하는실록산계레벨링제이다.
[44] 이때,상기전도성도료조성물은 0.01내지 0.5중량 %의첨가제를함유하는 것이바람직하다.
[45] 본발명에따른전도성도료조성물은상술한전도성도료조성물을막으로 도포하고경화하여얻어진전도막이 1내지 1000%의연신율로연신될때연신된 전도막의면저항 (sheet resistance)이 Ι.ΟχΙΟ2- 1.0χ10"Ω /口인특징이 있으며,보다 특징적으로 l.OxlO7- 1.0 09 /口인특징이 있다.
[46] 본발명에따른전도성도료조성물은대전방지，정전분산，도전성， EMI차폐 흑은전극용도료조성물로사용될수있다.
[47] 상술한전도성도료조성물은상기분산제,전도성물질,고분자바인더，및 매질과함께선택적으로첨가제를흔합하여제조될수있으며,상기흔합은 믹서，블레이드,플루다이저 ,페인트쉐이커，초음파，호모제나이저，비드밀， 펄버라이저,를밀중 1종흑은그이상의장치를사용하여수행될수있다.
[48] 본발명에따른전도막제조방법은 a)기재의적어도일면에상술한본발명에 따른전도성도료조성물을도포하여도포막을형성하는단계;및 b)상기 도포막에열풍，열또는자외선을인가하여상기도포막을경화하는단계;를 포함하여수행된다.
[49] 이때，상기 b)단계후， c)상기기재의일면에대향하는대향면에상기도료 조성물을도포하여도포막을형성하는단계;및 d)상기도포막에열풍，열또는 자외선을인가하여상기도포막을경화하는단계;가더수행될수있다.
[50] 상기전도막은기재의표면의일영역，일예로，기재의일표면또는대향하는 양표면에형성될수있으며，기재의표면전체에형성될수있다.
[51] 상기기재는폴리에스테르，폴리스티렌，폴리카보네이트，폴리이미드，
폴리설포네이트，폴리아세탈，폴리아크릴，폴리비닐，폴리페닐렌에테르수지, 폴리올레핀，아크릴로니트릴-부타디엔 -스티렌공중합체，폴리아릴레이트， 폴리아미드，폴리아미드이미드，폴리아릴설폰，폴리에테르이미드,
폴리에테르설폰，폴리페닐렌설피드,불소계，폴리이미드，폴리에테르케톤, 폴리벤족사졸，폴리옥사디아졸，폴리벤조티아졸，폴리벤지미다졸，폴리피리딘， 폴리트리아졸，폴리피를리딘，폴리디벤조퓨란,폴리설폰，폴리우레아， 폴리포스파젠및액정중합체고분자，유리，수정，석영，글래스웨이퍼， 실리콘웨이퍼,이차전지용양극활물질，음극활물질，금속판，
산화금속판， ΠΌ증착유리， PCB,에폭시，반도체침，반도체패키지및이들의 적층체로이루어진군에서하나이상선택된것을사용할수있으며，
폴리에스테르，폴리스티렌，폴리이미드，폴리카보네이트또는폴리올레핀인 것이바람직하다ᅳ
[52] 상기전도막은시트또는필름형상이며 ,대전방지막，도전막，전자파 (EMI) 차폐막또는전극이다.
[53] 상기도포는바 (Bar)코팅，그라비아코팅，마이크로그라비아코팅，
플렉소코팅,나이프코팅,스프레이코팅，슬롯다이코팅，를코팅，스크린코팅， 잉크젯프린팅,캐스팅，딥 (Dip)코팅，플로우코팅，커튼코팅 ,콤마코팅 ,키스코팅， 패드프린팅및스핀코팅에서선택된어느한방법또는한가지이상의방법을 병행하여이루어지며，상기도포는를투롤방식의그라비아코팅을이용하여 수행되는것이바람직하다.
[54] 이때，상기도포가이루어지기전，상기기재에코로나처리또는 UV오존
처리가수행된후，상기처리가수행된기재표면상에 전도성도료조성물의 도포가이루어질수있다.
[55] 본발명에따른제조방법에있어,상기전도막이형성된기재를연신및
성형하는단계;가더수행될수있다.즉，본발명은 a)기재의적어도일면에 상술한본발명에따른전도성도료조성물을도포하여도포막을형성하는단계 ; b)상기도포막에열풍，열또는자외선을인가하여상기도포막을경화하는 단계;및 e)전자부품을이송하거나보관시사용되는트레이의형상으로，상기 전도막이형성된기재를가열연화하여 300내지 500%의연신율로연신및 성형하는단계를포함하는기재의성형방법을포함한다.
[56] 본발명에따른전도성도료조성물의특징에의해,상기전도막이형성된
기재를성형함으로써기재 (및전도막)가늘어나고,복잡한모양으로성형되어도 전도막의대전방지，정전분산,도전성 ,ΕΜΙ차폐기능이유지되며성형품전체에 전도성이균일하게유지되는것이다.
[57] 상기성형은진공성형인것이바람직하다.상세하게 ,상기도포막을경화시켜 제조된전도막이형성된기재를가열연화시켜금형과기재사이를
진공방식으로처리하여연신과정을거쳐성형체를제조한다.제품의성형 방식은특히한정되지는않으며일반적으로사용되는성형공정올통해제조될 수있다.그러나,별도의성형과정을거치지않고전도막이형성된기재자체를 최종품으로사용할수있음은물론이다.
[58] 상기성형에의해얻어진성형체는대전방지물，정전분산물，전도성막,전자파 차폐물，전자파흡수물，태양전지，연료감웅용전지 (DSSC)용전극,전기 전자 소자,이차전지용양극활물질，음극활물질및이를이용한전기화학소자， 이차전지，연료전지,태양전지,메모리소자，하이브리드캐패시터 (P-EDLC)또는 캐퍼시터인전기화학소자，반도체소자,광전소자，노트북부품，컴퓨터부품， 핸드폰부품， PDA부품， PSP부품,게임기용부품，하우징，투명전극，불투명 전극，전계방출디스플레이 (FED;field emission display), BLU(back light unit), 액정표시장치 (LCD;liquid crystal display),플라즈마표시패널 (PDP;plasma display panel ),발광다이오드 (LED;luminescent diode),터치패널,전광판,광고판, 디스플레이，발열체,방열체,도금，촉매，조촉매,산화제，환원제,자동차부품， 선박부품，항공기기부품，보호테이프，접착제,트레이，클린룸，운송기기부품， 난연소재，항균소재，금속복합소재，비철금속복합소재，의료기기，건축재， 바닥재，벽지，광원부품，램프，광학기기，섬유，의류제조용천또는전기전자 부품에사용될수있다.
[59]
발명의효과
[60] 본발명에따른전도성도료조성물은강산，강염기나유기용매를사용하지 않는친환경적인수계전도성도료조성물인장점이있으며，도포시매우 우수하고균일한전도성막을형성하며，도포된막과기재간의결합력이 우수하고,도포된막이물리적으로변형되어도매우우수한전기전도도특성이 유지되는장점이있으며,임의의기재에대전방지，정전분산，전도체,전극또는 전자파차폐능을부여할수있으며 ,전도성도료조성물을저가로단시간내에 대량생산가능한장점이있다.
[61]
도면의간단한설명
[62] 도 1은실시예 2에서제조된전도막의주사전자현미경사진이며，
[63] 도 2는실시예 2에서제조된전도막을진공성형한후관찰한주사전자현미경 사진이다.
[64]
발명의실시를위한형태
[65] 제조예 1
[66] 전처리조에서탄소나노튜브 (CNT,직경약 20nm,길이약 20im) 15g을증류수 985g과순환펌프로흔합하여 CNT수용액을준비하였다.
[67] 250atm으로압축된기상상태의산소가열교환기의전단에서 0.4g/min의
유속으로 CNT수용액과흔합되었으며，산소와흔합된 CNT수용액 (CNT 흔합액)은열교환기를통해 150내지 200oC로예열되어,고압주입펌프를통해 Hg/min유속으로예열조에투입되었다.예열된 CNT흔합액은 210°C및
240atm의아임계수상태의표면개질반웅기에주입되어표면개질되고，상기 표면개질된생성물은다시열교환기로이송되어 100°C로 1차냉각후,다시 넁각장치를통해약 25°C의온도로냉각되어,표면개질된 14.3g의 CNT를얻었다.
[68] 제조예 2
[69] 산화제로산소대신공기를사용하는것을제외하고,제조예 1과동일하게
제조하였다.
[70] 제조예 3
[71] 산화제로산소대신오존을사용하는것을제외하고,제조예 1과동일하게
제조하였다.
[72] 제조예 4
[73] 산화제로산소대신 50%과산화수소수용액 3.4g을첨가하는것을제외하고, 제조예 1과 동일하게 제조하였다.
[74] 제조예 5
[75] 탄소나노류브 (CNT) 0.2g, 황산 600g 및 질산 200g을 흔합한 후， 60°C에서
12시간 동안 가열 하고, 여과장치를 통해 고형분을 여과하고 순수물로 세척하여 표면개질된 CNT를 제조하였다.
[76] 제조예 6
[77] 탄소나노튜브 (CNT) 대신 그라핀 (두께 약 5A, 폭 약 15nm) l lg을 사용한 것을 제외하고，제조예 1과 동일하게 제조하였다.
[78] 제조예 7
[79] 상기 의 제조예 1과 동일한 방법으로 제조된 표면개 질된 CNT 30g과
스티 렌 /아크릴계 수용성 수지 (제조사 한화케미칼，제품번호 Soluryl 160, 중량평균분자량 15,000)인 분산제 75g과 순수물 895g을 교반기를 통하여 흔합 및 분산하여 CNT분산액을 제조하였다.
[80] 채조예 8
[81] 표면개질된 CNT 30g 대신, 상기의 제조예 1과 동일한 방법으로 제조된
' 표면개질된 CNT 7.5g과 제조예 6과 동일한 방법으로 제조된 표면개질된 그라핀
22.5g을 사용한 것을 제외하고, 제조예 7과 동일한 방법으로 CNT-그라핀 분산액을 제조하였다.
[82] 체조예 9
[83] 표면개 질된 CNT 30g 대신, 상기의 제조예 1과 동일한 방법으로 제조된
표면개질된 CNT 7.5g과 그라핀 22.5g을 사용한 것을 제외하고, 제조예 7과 동일한 방법으로 CNT-그라핀 분산액을 제조하였다.
[84]
[85] 심 시 예 1
[86] 상기의 제조예 7에서 제조된 CNT분산액 100g, 아크릴-우레탄 공중합체 (제조사 Air Products, 제품번호 Hybridur 580)인 고분자 바인더 100g 및 순수물 800g을 고속 교반기에서 완전한 분산상태를 이루도록 교반하여 전도성 도료를 제조하였다.
[87] 롤투를 방식의 그라비아 코팅을 이용하여 제조된 도료를 폴리에스테르 필름 위 에 5 의 두께 (wet 두께)로 코팅한 후 80°C의 온도를 유지하고 있는 컨백션 오본에 1분간 넣어 용매가 건조되고 열경화된 전도막 (코팅 막)을 제조하였다.
[88]
[89] 심 시 예 2
[90] 실시 예 1의 도료에 레벨링 제 (BYK346)를 0.5중량 % 추가한 것을 제외하고, 실시 예 1와 동일하게 실시하였다.
[91]
[92] 심시 예 3
[93] CNT분산액 대신, 상기의 제조예 8에서 제조된 CNT-그라핀 분산액 100g을 사용한것을제외하고，실시예 1와동일하게실시하였다.
[94]
[95] 심시예 4
[96] CNT분산액대신，상기의제조예 9에서제조된 CNT-그라핀분산액 100g을
사용한것을제외하고，실시예 1와동일하게실시하였다.
[97]
[98] 비교예 1
[99] 표면개질된탄소나노류브대신표면개질되지않은 CNT 30g을사용하는것을 제외하고，제조예 6및실시예 1과동일하게실시하였다.
[100]
[101] *시험방법 *
[102] 1.투과도측정
[103] Beckman사의자외선 /가시광선분광기 (UV/vis spectroscopy), DU650모델을
사용했다.시료는코팅막제조방법에의해제조된시료를사용하였다.상기 UV/Vis분광기에서백그라운드 (background)로공기 (air)를기준으로측정하였다ᅳ 표 1에있는파장은 550nm에서의측정값이다.
[104] 2ᅳ표면경도측정
[105] Toyoseiki사의 Pencil scratch hardness tester를사용하여 ASTM D3363방법에
따라측정하였다.
[106] 3.진공성형물제조
[107] 실시예및비교예에의해제조된전도막이형성된기재를전기로혹은열풍을 이용하여가열연화시켜성형용금형과상기시편사이를진공으로흡입하여 금형으로모양으로진공성형하였다.상기진공성형을거치면서기재와 코팅층이연신되며，초기기재의두께와진공성형후줄어든두께를비교하여 연신율 (연신율=초기기재두께 /성형후기재두께 *100(%))을계산하였다.
[108] 4.주사전자현미경 (Scanning Electron Microscope;SEM)
[109] 주사전자현미경은 Hitachi사의 S4800모델이며제조된전도막을백금으로
도금한후측정하였다.
[110] 5.표면저항측정
[111] 미쪼비시사의 Loresta GP(MCP-T600)를사용하여 JISK 7194/ASTM D991에 따라측정하였다.
[112] 도 1은실시예 2에서제조된전도막의주사전자현미경사진으로，도 1에서알 수있듯이，기재의표면에매우고르게탄소나노튜브가퍼져있음을알수 있으며,탄소나노튜브사이와그상층에바인더및도료용레벨링제가견고한 결합을하고있음을확인할수있었다.
[113] 도 2는진공성형후전도막을관찰한주사전자현미경사진으로,진공성형후 400%의연신율로인장될때에도매우고른탄소나노류브가분포되어 있어 균일한분산성을가지며，기재와의계면에서들뜸없이강하게결합된것을알 수있다.
[114] 도 1및도 2에서알수있듯이 ,본발명에따른조성물은강산이나강염기및 유기용매를사용하지않는친환경적인수계조성물이면서도，극히우수한 분산성을가지며기재와의결합력이매우높고， 400%의연신률에서도기재와의 계면탈착이발생하지않으며우수한전기전도성이유지됨을알수있다.
[115] 하기의표 1은실시예 1,2및비교예 1에서제조된전도막의표면저항,투과도, 표면경도및성형후의표면저항을측정한결과를정리한것으로，하기의표 1에서진공성형시연신율은 400%이었다.이때，실시예 3및실시예 4에서 제조된전도막또한실시예 1및실시예 2에서제조된전도막과유사한특성을 가졌다.
[116] [표 1]
Figure imgf000013_0001
[118] 상기표 1에서알수있듯이，본발명에따른전도막 (코팅막)의경우,
탄소나노튜브의우수한분산성에의해비교예에비해 107오더이상의우수한 전기전도도를가짐을알수있으며， 400%의물리적연신에의해서도우수한 전기전도도가유지됨을알수있다.
[119] 또한,본발명의조성물의경우,기재에의부착력이매우우수하여비교예에 비해부착력이 5B에서 1H로향상됨을알수있으며，레벨링제의 첨가로레벨링 효과가개선되어표면저항이개선됨을알수있다.
[120] 이상에서설명한본발명은전술한실시예및첨부된도면에의해한정되는 것이아니고，본발명의기술적사상을벗어나지않는범위내에서여러가지 치환,변형및변경이가능함은본발명이속하는기술분야에서통상의지식을 가진자에게있어서명백할것이다.
[121] 따라서，본발명의사상은설명된실시예에국한되어정해져서는아니되며， 후술하는특허청구범위뿐아니라이특허청구범위와균등하거나둥가적변형。 있는모든것들은본발명사상의범주에속한다고할것이다.

Claims

청구범위
친수성 고분자 단위와 소수성 고분자단위로 이루어진
블록공중합체인 분산제; 표면 개질된 탄소화합물인 전도성 물질; 고분자 바인더；및 물, 유기 용제 또는 이들의 흔합물을 함유하는 매질;을 포함하는 전도성 도료 조성물.
제 1항에 있어서 ,
상기 분산제는 스티 렌-아크릴계 수용성 수지 인 것을 특징으로 하는 전도성 도료 조성물.
제 1항에 있어서，
상기 탄소화합물은 탄소섬유, 단일벽 탄소나노튜브, 이중벽 탄소나노튜브, 얇은벽 탄소나노튜브，다중벽 탄소나노튜브 및 그라핀으로 이루어진 군에서 하나 또는 둘 이상 선택되는 것을 특징으로 하는 전도성 도료 조성물.
제 1항에 있어서 ,
상기 고분자 바인더는 아크릴 -우레탄 공중합체인 것을 특징으로 하는 전도성 도료 조성물.
제 3항에 있어서 ,
상기 표면 개질된 탄소화합물은 산소, 공기，오존, 과산화수소수 및 니트로화합물에서 하나 이상 선택되는 산화제를 사용하여 아임 계수 또는 초임 계수 조건에서 상기 탄소화합물의 표면을 산화처 리하여 얻어진 것을 특징으로 하는 전도성 도료 조성물. 제 3항에 있어서，
상기 표면 개질된 탄소화합물은 탄소화합물과 카르복실산，질산， 인산, 황산，불산, 염산, 과산화수소수 또는 이들의 흔합물을 흔합하여 탄소화합물 표면을 산화시켜 얻어진 것을 특징으로 하는 전도성 도료 조성물.
제 1항에 있어서 ,
상기 표면 개질된 탄소화합물은 탄소 100 증량부에 대하여 0.01 내지 10 중량부의 산소, 질소，황 또는 이들의 흔합물을 함유하도록 표면 개질된 것을 특징으로 하는 전도성 도료 조성물.
제 1항에 있어서 ,
상기 탄소화합물은 탄소나노류브, 그라핀 또는 이들의 흔합물을 함유하며 , 상기 탄소나노류브는 0.5 내지 lOOnm의 직 경 및 0.1 내지 1000 의 길이를 갖는 것을 특징으로 하는 전도성 도료 조성물. 제 1항에 있어서 ,
상기 전도성 도료 조성물은 0.05 내지 5 중량 %의 상기 분산제를 함유하는 것을 특징으로 하는 전도성 도료 조성물. 제 1항에있어서,
상기전도성도료조성물은 0.1내지 5중량 %의상기탄소 화합물을함유하는것을특징으로하는전도성도료조성물. 제 1항에있어서,
상기전도성도료조성물은 5내지 15중량 %의상기고분자 바인더를함유하는것을특징으로하는전도성도료조성물. 제 1항에 있어서,
상기전도성도료조성물은 75내지 90중량 %의상기매질을 함유하는것을특징으로하는전도성도료조성물ᅳ
제 1항에 있어서,
상기전도성도료조성물은실록산계레벨링제를첨가제로더 함유하는것을특징으로하는전도성도료조성물.
제 13항에있어서，
상기전도성도료조성물은 0.01내지 0.5중량 %의첨가제를 함유하는것을특징으로하는전도성도료조성물.
a)기재의적어도일면에상기제 1항내지제 14항에서선택된 어느한항의전도성도료조성물을도포하여도포막을형성하는 단계;및
b)상기도포막에열풍，열또는자외선을인가하여상기도포막을 경화하는단계;
를포함하는전도막제조방법.
제 15항에있어서，
b)단계후,
c)상기기재의일면에대향하는대향면에상기도료조성물을 도포하여도포막을형성하는단계;및
d)상기도포막에열풍,열또는자외선을인가하여상기도포막을 경화하는단계;를더포함하는것을특징으로하는전도막제조 방법.
제 15항에있어서,
상기기재는폴리에스테르，폴리스티렌，폴리이미드,
폴리카보네이트또는폴리올레핀인것을특징으로하는전도막 제조방법 .
제 15항에 있어서，
상기전도막은시트또는필름형상이며，상기 전도막은
대전방지막,도전막,전자파 (EMI)차폐막또는전극인것을 특징으로하는전도막제조방법.
제 15항에있어서，
상기도포는바 (Bar)코팅 ,그라비아코팅 ,마이크로그라비아코팅 , 플렉소코팅,나이프코팅,스프레이코팅,슬롯다이코팅，를코팅 스크린코팅,잉크젯프린팅，캐스팅,딥 (Dip)코팅,플로우코팅， 커튼코팅,콤마코팅,키스코팅,패드프린팅및스핀코팅에서 선택된어느한방법또는한가지이상의방법을병행하여 이루어는것을특징으로하는전도막제조방법.
[청구항 20] 제 19항에있어서,
상기도포는를투롤방식의그라비아코팅을이용하여수행되는 것을특징으로하는전도막제조방법.
[청구항 21] 제 15항에있어서，
상기방법은전자부품을이송하거나보관시사용되는트레이의 형상으로,상기전도막이형성된기재를가열연화하여 300내지
500%의연신율로연신및성형하는단계;를더포함하는것을 특징으로하는전도막제조방법 .
PCT/KR2011/005109 2010-07-12 2011-07-12 전도성 도료 조성물 및 이를 이용한 전도막의 제조방법 WO2012008738A2 (ko)

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TWI433902B (zh) 2014-04-11
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US20130207294A1 (en) 2013-08-15
EP2594613A4 (en) 2014-07-23
EP2594613B1 (en) 2016-09-21
JP2013537570A (ja) 2013-10-03
KR20120006458A (ko) 2012-01-18
JP5727604B2 (ja) 2015-06-03
CN103108923B (zh) 2016-03-23

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