WO2013047341A1 - 透明導電体およびその製造方法 - Google Patents
透明導電体およびその製造方法 Download PDFInfo
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- WO2013047341A1 WO2013047341A1 PCT/JP2012/074155 JP2012074155W WO2013047341A1 WO 2013047341 A1 WO2013047341 A1 WO 2013047341A1 JP 2012074155 W JP2012074155 W JP 2012074155W WO 2013047341 A1 WO2013047341 A1 WO 2013047341A1
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- WIPO (PCT)
- Prior art keywords
- carbon nanotube
- mass
- layer
- transparent conductor
- carbon nanotubes
- Prior art date
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- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 1
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- 239000010931 gold Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
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- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
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- 229920000767 polyaniline Polymers 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
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- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ARENMZZMCSLORU-UHFFFAOYSA-N propan-2-yl naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)OC(C)C)=CC=CC2=C1 ARENMZZMCSLORU-UHFFFAOYSA-N 0.000 description 1
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- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- OABYVIYXWMZFFJ-ZUHYDKSRSA-M sodium glycocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 OABYVIYXWMZFFJ-ZUHYDKSRSA-M 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
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- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3441—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
-
- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/30—Drying; Impregnating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/221—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Definitions
- the present invention relates to a transparent conductor and a method for producing the transparent conductor. More specifically, the present invention relates to a highly conductive transparent conductor and a simple manufacturing method thereof.
- the transparent conductor of the present invention is used as a material for forming display-related electrodes such as touch panels, liquid crystal displays, organic electroluminescence, and electronic paper that are mainly required to have a smooth surface.
- the carbon nanotubes have a substantially cylindrical shape formed by winding one surface of graphite.
- a single-walled carbon nanotube is a single-walled carbon nanotube
- a multi-walled carbon nanotube is a multi-walled carbon nanotube. What is wound in a layer is called a double-walled carbon nanotube.
- Carbon nanotubes themselves have excellent intrinsic conductivity and are expected to be used as conductive materials.
- Carbon nanotubes are obtained as a mixture of those having metallic properties and those having semiconducting properties during synthesis.
- the separation technique has many technical difficulties and has not been realized at present.
- the semiconducting carbon nanotube can be changed to the metallic carbon nanotube, it can be easily used as a conductive material. Therefore, a doping technique that enhances conductivity by chemically or electrochemically doping carbon nanotubes has attracted attention.
- Patent Document 1 is difficult to put into practical use from the viewpoint of productivity because a long time is required for the doping process and a rinse process is essential.
- Patent Document 2 is difficult to put into practical use from the viewpoint of productivity because the coating method is dip coating or spin coating, and the rinse treatment is essential.
- Patent Document 3 it is difficult to put it to practical use from the viewpoint of productivity because the coating method is a filtration method and a rinse treatment is essential.
- the present invention has been made in view of the above problems and situations, and a problem to be solved is to provide a highly conductive transparent conductor and a simple manufacturing method thereof.
- the inventors formed an overcoat layer or an undercoat layer containing a doping agent in contact with the conductive layer containing the carbon nanotubes, thereby performing a subsequent rinse treatment or the like.
- the present inventors have found a technique for forming a carbon nanotube transparent conductor that is simple and productive without any treatment, and has reached the present invention.
- a conductive laminated structure is formed on at least one side of a transparent substrate by applying a dispersion containing carbon nanotubes on a transparent substrate and drying to form a conductive layer.
- a method for producing a transparent conductor to be formed comprising: forming an undercoat layer containing a hole-doped compound in a proportion of 0.2 to 20% by mass on a transparent substrate before forming the conductive layer; and / or The step of forming an overcoat layer containing the hole-doped compound in a proportion of 0.2 to 20% by mass after forming the conductive layer is performed.
- the method for producing a transparent conductor of the present invention includes a step of forming an undercoat layer on a transparent substrate, a step of applying a dispersion containing carbon nanotubes and drying to form a conductive layer, and forming an overcoat layer Are performed in this order to form a transparent conductor having a conductive laminated structure on at least one side of the transparent substrate, and the hole coating compound is added to the undercoat layer and / or overcoat layer. It is contained in a ratio of 2 to 20% by mass.
- the hole dope compound is preferably a metal halide.
- the metal halide preferably contains chloroauric acid.
- the undercoat layer formed in the method for producing a transparent conductor of the present invention preferably has a water contact angle of 5 to 20 °.
- the transparent conductor of the present invention has an undercoat layer containing a hole-doped compound in a proportion of 0.2 to 20% by mass and a conductive layer containing carbon nanotubes in this order on at least one surface of a transparent substrate. It consists of what is characterized by this.
- the transparent conductor of the present invention has a conductive layer containing carbon nanotubes and an overcoat layer containing a hole-doped compound in a proportion of 0.2 to 20% by mass in this order on at least one surface of the transparent substrate. It consists of what is characterized by this.
- the transparent conductor of the present invention comprises an undercoat layer containing a hole-doped compound in a proportion of 0.2 to 20% by mass, a conductive layer containing carbon nanotubes, and a hole-doped compound on at least one surface of a transparent substrate.
- the hole dope compound is a metal halide.
- the metal halide preferably contains chloroauric acid.
- a transparent conductor having a surface resistance value of 10 to 50% lower than that before the doping process by the conventional manufacturing method can be obtained without performing the doping process after forming the conductive layer.
- the method for producing a transparent conductor of the present invention includes a step of forming an undercoat layer on a transparent substrate, a step of applying a dispersion containing carbon nanotubes and drying to form a conductive layer, and a step of forming an overcoat layer , In this order, is applied to a method for producing a transparent conductor that forms a conductive laminated structure on at least one surface of a transparent substrate.
- the undercoat layer is on the transparent substrate side with respect to the conductive layer, and the layer in contact with the conductive layer and the overcoat layer are on the surface side of the transparent conductor with respect to the conductive layer. The layer in contact with the conductive layer.
- a hole dope compound is contained in a proportion of 0.2 to 20% by mass.
- the transparent conductor of the present invention can be subjected to the doping treatment after the formation of the conductive layer.
- a transparent conductor having a surface resistance value of 10 to 50% lower than that before the doping treatment by the conventional manufacturing method can be obtained.
- the effect of improving the conductivity of transparent conductors can be achieved by changing carbon nanotubes with semiconductor properties, which are factors that lower conductivity, to carbon nanotubes with metallic properties by doping with hole-doped compounds.
- the hole dope compound contained in the undercoat layer and / or overcoat layer is less than 0.2% by mass, the effect of improving the conductivity will be insufficient, while the holes contained in the undercoat layer and / or overcoat layer will be insufficient. Even if the dope compound exceeds 20% by mass, the effect of improving the conductivity reaches its peak.
- the undercoat layer dry or wet coating can be applied as will be described in detail later.
- the undercoat layer preferably has a thickness of 1 to 500 nm.
- the conductive layer is provided by applying and drying a dispersion containing carbon nanotubes on the undercoat layer.
- a dispersant described later in the dispersion liquid containing the carbon nanotubes it is preferable to use a dispersant described later in the dispersion liquid containing the carbon nanotubes.
- the dispersion containing carbon nanotubes is preferably applied on the undercoat layer so that the mass of carbon nanotubes after drying is 1 to 40 mg / m 2 .
- overcoat layer forming step dry or wet coating can be applied as described in detail later.
- the overcoat layer is formed on the carbon nanotube layer containing carbon nanotubes in a ratio of 1 to 40 mg / m 2 by mass after drying, and the thickness is preferably 1 to 500 nm.
- the carbon nanotube is not particularly limited as long as it has a shape obtained by winding one surface of graphite into a cylindrical shape.
- Single-walled carbon nanotubes in which one surface of graphite is wound in one layer, wound in multiple layers. Any of the multi-walled carbon nanotubes that have been used can be applied. Among them, it is preferable that 50% or more of double-walled carbon nanotubes are included in the total number of carbon nanotubes.
- Double-walled carbon nanotubes are carbon nanotubes in which one surface of graphite is wound in two layers, and including 50% or more means that 50 or more of 100 carbon nanotubes are double-walled carbon nanotubes.
- the conductivity of the carbon nanotubes and the dispersibility of the carbon nanotubes in the coating dispersion liquid become extremely high. More preferably 75 or more out of 100, and most preferably 80 or more out of 100 are double-walled carbon nanotubes.
- the application of double-walled carbon nanotubes is also preferable because the original functions such as conductivity are not impaired even if the surface is functionalized by acid treatment or the like.
- the carbon nanotube conductive layer is not particularly limited as long as it contains carbon nanotubes.
- Examples of the method for forming the untreated conductive layer include a method of applying a carbon nanotube dispersion on a substrate, a method of directly growing carbon nanotubes on a substrate, and a method of transferring a carbon nanotube film onto a substrate.
- the coating method of the carbon nanotube dispersion liquid on the transparent substrate is preferable because a dispersion liquid can be easily obtained using a dispersant and a dispersion medium.
- the dispersant In order to disperse the carbon nanotubes in a solvent, it is preferable to use a dispersant.
- the dispersant is not limited to any kind such as a low molecular dispersant, a polymer dispersant, an ionic dispersant, and a nonionic dispersant as long as the carbon nanotube has a dispersibility.
- a polymer dispersant is preferable. Among them, a polymer or a low molecular weight anionic surfactant having a polysaccharide or an aromatic structure in the skeleton is particularly preferable because of excellent dispersibility.
- a polymer having a polysaccharide structure in the skeleton is referred to as a polysaccharide polymer
- a polymer having an aromatic structure in the skeleton is referred to as an aromatic polymer
- a low molecular weight anionic surfactant is referred to as an anionic surfactant.
- Examples of the polysaccharide polymer preferably used for the dispersant include carboxymethylcellulose and its derivatives, hydroxypropylcellulose and its derivatives, xylan and its derivatives. Among these, from the viewpoint of dispersibility, carboxymethyl cellulose or a derivative thereof is preferable, and further, use of a salt of carboxymethyl cellulose or a derivative thereof which is an ionic dispersant is preferable.
- examples of the cationic substance constituting the salt include alkali metal cations such as lithium, sodium and potassium, and alkaline earth such as calcium, magnesium and barium.
- Metal cation, ammonium ion, or onium ion of organic amines such as monoethanolamine, diethanolamine, triethanolamine, morpholine, ethylamine, butylamine, coconut oil amine, tallow amine, ethylenediamine, hexamethylenediamine, diethylenetriamine, polyethyleneimine, Alternatively, these polyethylene oxide adducts can be used, but are not limited thereto.
- aromatic polymer preferably used for the dispersant examples include aromatic polyamide resins, aromatic vinyl resins, styrene resins, aromatic polyimide resins, conductive polymers such as polyaniline, polystyrene sulfonic acid, and poly- ⁇ -methylstyrene.
- aromatic polyamide resins aromatic vinyl resins
- styrene resins aromatic polyimide resins
- conductive polymers such as polyaniline
- polystyrene sulfonic acid examples thereof include derivatives of polystyrene sulfonic acid such as sulfonic acid.
- derivatives of polystyrene sulfonic acid such as sulfonic acid.
- use of polystyrene sulfonic acid or a derivative thereof is preferable, and further, use of a salt of polystyrene sulfonic acid or a derivative thereof which is an ionic dispersant is preferable.
- anionic surfactant examples include octylbenzenesulfonate, nonylbenzenesulfonate, dodecylbenzenesulfonate, dodecyldiphenyletherdisulfonate, monoisopropylnaphthalenesulfonate, diisopropylnaphthalenesulfonate Salts, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, naphthalene sulfonate formalin condensate, sodium cholate, sodium deoxycholate, sodium glycocholate, cetyltrimethylammonium bromide and the like. Of these, sodium cholate or dodecylbenzene sulfonate is preferably used from the viewpoint of dispersibility.
- nonionic surfactants include sugar ester surfactants such as sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters, fatty acid ester surfactants such as polyoxyethylene resin acid esters and polyoxyethylene fatty acid diethyl , Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, ether surfactants such as polyoxyethylene / polypropylene glycol, polyoxyalkylene octyl phenyl ether, polyoxyalkylene nonyl phenyl ether, polyoxyalkyl dibutyl phenyl ether, poly Oxyalkyl styryl phenyl ether, polyoxyalkyl benzyl phenyl ether, polyoxyalkyl bisphenyl ether, polyoxyalkyl Aromatic anionic surfactants such as mill phenyl ether. Of these, aromatic nonionic surfactants are preferred because of their excellent dispersibility, dispersion stability, and high
- dispersants for example, when water is used as a solvent, it is preferable to disperse the carbon nanotubes with a polymer containing a carboxylic acid group, a sulfonic acid group, or a hydroxyl group that is a hydrophilic group. In particular, it is preferable to disperse the carbon nanotubes with carboxymethyl cellulose which is a polysaccharide polymer.
- the reason why the carbon nanotubes are uniformly dispersed in the dispersion medium can be considered as follows. Since carbon nanotubes form a strong bundle and entangle with each other to form a strong aggregate, it is very difficult to disperse in a dispersion medium in isolation. In order to disperse carbon nanotubes in a dispersion medium, it is necessary to interact with graphite of carbon nanotubes by ⁇ -electrons to dissolve bundles and aggregates, or to dissolve bundles and aggregates by hydrophobic interactions with carbon nanotubes. is there. In order to obtain a more isolated dispersion of carbon nanotubes, it is presumed that the polysaccharide polymer is acting effectively.
- examples of the cationic substance constituting the salt include alkali metal cations such as lithium, sodium and potassium, and alkaline earth metals such as calcium, magnesium and barium. Cation, ammonium ion, or onium ion of organic amine such as monoethanolamine, diethanolamine, triethanolamine, morpholine, ethylamine, butylamine, coconut oil amine, beef tallow amine, ethylenediamine, hexamethylenediamine, diethylenetriamine, polyethyleneimine, or these
- the present invention is not limited thereto.
- the weight average molecular weight of the dispersant is preferably 100 or more.
- the mass average molecular weight is 100 or more, the interaction with the carbon nanotube is possible, and the dispersion of the carbon nanotube becomes better.
- the mass average molecular weight the more the dispersing agent interacts with the carbon nanotube and the dispersibility is improved.
- the mass average molecular weight is preferably 10 million or less, and more preferably 1 million or less.
- the most preferred mass average molecular weight range is 10,000 to 500,000.
- aqueous or non-aqueous dispersion medium that can dissolve the dispersant can be used.
- Water is a preferred dispersion medium from the viewpoint of waste liquid treatment, environment and disaster prevention.
- Non-aqueous solvents include hydrocarbons (toluene, xylene, etc.), chlorine-containing hydrocarbons (methylene chloride, chloroform, chlorobenzene, etc.), ethers (dioxane, tetrahydrofuran, methyl cellosolve, etc.), ether alcohols (ethoxyethanol, methoxy) Ethoxyethanol, etc.), esters (methyl acetate, ethyl acetate, etc.), ketones (cyclohexanone, methyl ethyl ketone, etc.), alcohols (ethanol, isopropanol, phenol, etc.), lower carboxylic acids (acetic acid, etc.), amines (triethylamine, triethylamine, etc.) Methanolamine, etc.), nitrogen-containing polar solvents (N, N-dimethylformamide, nitromethane, N-methylpyrrolidone, etc.), sulfur compounds (dimethyl sulfoxide,
- the method for preparing the dispersion used in the present invention is not particularly limited.
- Dispersion means during the preparation include mixing and dispersing machines commonly used for coating production of carbon nanotubes and a dispersant in a dispersion medium (for example, a ball mill, a bead mill, a sand mill, a roll mill, a homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, an ultrasonic device, an atomizer. A lighter, a dissolver, a paint shaker, etc.).
- the method of dispersing using an ultrasonic device is preferable because the dispersibility of the carbon nanotubes in the obtained coating dispersion liquid is good.
- the coating dispersion obtained as described above is coated on a substrate and then dried to form an untreated conductive layer.
- Resin, glass, etc. can be mentioned as a raw material of a base material.
- the resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, Polymethyl methacrylate, alicyclic acrylic resin, cycloolefin resin, triacetyl cellulose and the like can be used.
- the glass ordinary soda glass can be used.
- these several base materials can also be used in combination.
- the resin film may be provided with a hard coat.
- the type of the substrate is not limited to the above, and an optimum one can be selected from durability, cost, etc. according to the application.
- the thickness of the transparent substrate is not particularly limited, but is preferably between 10 ⁇ m and 1000 ⁇ m when used for display-related electrodes such as touch panels, liquid crystal displays, organic electroluminescence, and electronic paper.
- the dispersion liquid for coating obtained by the above method is applied to the substrate, and then the dispersion medium is dried to fix the carbon nanotubes on the substrate to form an untreated conductive layer.
- the method for applying the carbon nanotube dispersion on the substrate is not particularly limited.
- Known application methods such as spray coating, dip coating, spin coating, knife coating, kiss coating, gravure coating, slot die coating, screen printing, inkjet printing, pad printing, other types of printing, or roll coating can be used .
- the application may be performed in a plurality of times, or two different application methods may be combined.
- the most preferred application method is roll coating.
- the coating thickness (wet thickness) when applying the coating dispersion on the substrate also depends on the concentration of the coating dispersion, so consider the coating amount of carbon nanotubes necessary to obtain the desired surface resistance. And adjust as appropriate.
- the coating amount of the carbon nanotube can be adjusted as appropriate in order to achieve various uses that require electrical conductivity. For example, when the coating amount of the carbon nanotube is 1 mg / m 2 to 40 mg / m 2 , the surface resistance value can be 1 ⁇ 10 0 to 1 ⁇ 10 4 ⁇ / ⁇ . Furthermore, when the coating amount is 40 mg / m 2 or less, the surface resistance value can be 1 ⁇ 10 1 ⁇ / ⁇ or less.
- the surface resistance value can be 1 ⁇ 10 2 ⁇ / ⁇ or less. Furthermore, if the application amount is 20 mg / m 2 or less, it can be 1 ⁇ 10 3 ⁇ / ⁇ or less, and if the application amount is 10 mg / m 2 or less, it can be 1 ⁇ 10 4 ⁇ / ⁇ or less.
- a wetting agent When applying the carbon nanotube dispersion on the substrate, a wetting agent may be added to the application dispersion in order to suppress uneven application. Since water is selected as the dispersion medium of the carbon nanotube dispersion liquid in the production of the transparent conductor, a wetting agent such as a surfactant or alcohol is added to the carbon nanotube when coating on a substrate having a non-hydrophilic surface. By adding to the dispersion, the coating dispersion can be applied on the substrate without the coating dispersion being repelled.
- the wetting agent alcohol is preferable, and methanol, ethanol, propanol, and isopropanol are preferable among alcohols. Lower alcohols such as methanol, ethanol and isopropanol are highly volatile and can be easily removed when the substrate is dried after coating. In some cases, a mixture of alcohol and water may be used.
- hole-doped compounds can be broadly classified into four types: non-metal non-halides, non-metal halides, metal non-halides, and metal halides.
- non-metal non-halides include sulfuric acid, nitric acid, nitromethane and the like.
- Specific non-metal halides include chlorosulfonic acid, tetrafluorotetracyanoquinodimethane (F 4 -TCNQ), N-phenylbistrifluoromethanesulfonylimide, and the like.
- the metal species contained in the metal non-halide and metal halide is not particularly limited, but preferably contains at least one metal component selected from the group consisting of silver, gold, copper, platinum, nickel, iridium, and palladium. .
- Specific metal non-halides include silver nitrate (AgNO 3 ), nickel (I) nitrate (Ni (NO 3 ) 2 ⁇ 6H 2 O), and the like.
- Specific metal halides include gold chloride (AuCl 3 ), chloroauric acid (HAuCl 4 ), (C 4 H 9 ) 3 PAuCl, platinum chloride (PtCl 4 ), and tetrachloroplatinic acid (H 2 PtCl 4 ). , Hexachloroplatinic acid (H 2 PtCl 6 ), cupric chloride (CuCl 2 ), palladium chloride (PdCl 2 ), ferric chloride (FeCl 3 ), iridium chloride (IrCl 3 ), bis (trifluoromethanesulfonyl) imide Examples thereof include silver (Ag-TFSI).
- metal halides are preferable from the viewpoint of improving the conductivity.
- chloroauric acid is particularly preferable from the viewpoint of effect.
- an undercoat layer is provided on a transparent substrate.
- the material for the undercoat layer is preferably a highly hydrophilic material. Specifically, a material having a water contact angle in the range of 5 to 20 ° is preferable. Specifically, it is preferable to use an inorganic oxide. More preferred are titania, alumina, and silica. These substances are preferable because they have a hydrophilic group (—OH group) on the surface and high hydrophilicity can be obtained. Furthermore, the undercoat layer is more preferably a composite of silica fine particles and polysilicate.
- the above hydrophilic functional groups may be exposed by surface hydrophilization treatment.
- the surface hydrophilization method include physical treatment such as corona treatment, plasma treatment and flame treatment, and chemical treatment such as acid treatment and alkali treatment. Of these, corona treatment and plasma treatment are preferred. By these operations, it is possible to obtain a surface property that falls within the range of the water contact angle.
- the method for providing the undercoat layer on the transparent substrate is not particularly limited.
- Known wet coating methods such as spray coating, dip coating, spin coating, knife coating, kiss coating, gravure coating, slot die coating, roll coating, bar coating, screen printing, inkjet printing, pad printing, other types of printing, etc. Is available.
- a dry coating method may be used.
- physical vapor deposition such as sputtering or vapor deposition, chemical vapor deposition, or the like can be used.
- the application may be performed in a plurality of times, or two different application methods may be combined.
- a preferred application method is wet gravure coating or bar coating.
- the hole dope compound applied when the hole dope compound is contained in the undercoat layer is not particularly limited as long as it is the compound described above.
- the concentration range of the hole dope compound to be contained in the undercoat layer is 0.2 to 20% by mass, preferably 2 to 20% by mass, more preferably 2 to 10% by mass from the viewpoint of the doping effect. .
- a method for producing the undercoat layer containing such a hole dope compound is not particularly limited.
- a wet coating method is employed, and a method of adding the hole dope compound to the coating liquid to be used is used. Can be mentioned.
- the thickness of the undercoat layer is not particularly limited. A thickness that can effectively obtain an antireflection effect due to optical interference is preferable because the light transmittance is improved.
- the value is 10 nm to 300 nm, more preferably 50 nm to 200 nm.
- the contact angle of water can be measured using a commercially available contact angle measuring device.
- the contact angle is measured according to JIS R3257 (1999) by dropping 1 to 4 ⁇ L of water onto the surface of the undercoat layer with a syringe in an atmosphere of room temperature 25 ° C. and relative humidity 50%, and observing the liquid droplets from a horizontal section. Then, the angle formed by the tangent of the droplet edge and the film plane is obtained.
- a transparent film can be formed on the upper surface of this layer.
- the transparent conductivity, heat resistance stability and moist heat resistance can be further improved, which is preferable.
- An organic material and an inorganic material can be used as the overcoat layer material, but an inorganic material is preferable from the viewpoint of resistance value stability.
- the inorganic material include metal oxides such as silica, tin oxide, alumina, zirconia, and titania. Silica is preferable from the viewpoint of resistance value stability.
- the method for providing the overcoat layer on the carbon nanotube layer is not particularly limited.
- Known wet coating methods such as spray coating, dip coating, spin coating, knife coating, kiss coating, roll coating, gravure coating, slot die coating, bar coating, screen printing, inkjet printing, pad printing, other types of printing, Or can be used.
- a dry coating method may be used.
- physical vapor deposition such as sputtering or vapor deposition, chemical vapor deposition, or the like can be used.
- the operation of providing the overcoat layer on the carbon nanotube layer may be performed in a plurality of times, or two different kinds of methods may be combined. Preferred methods are gravure coating and bar coating which are wet coating.
- an organic silane compound is preferably used, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxy.
- a silica sol prepared by hydrolyzing an organic silane compound such as tetraalkoxysilane such as silane dissolved in a solvent as a coating solution the wet coating is performed, and when the solvent is dried, dehydration condensation between silanol groups occurs.
- the method of forming a silica thin film is mentioned.
- the film thickness of the overcoat layer is controlled by adjusting the silica sol concentration in the coating solution and the coating thickness at the time of coating.
- the overcoat layer thickness is preferably 5 nm to 200 nm.
- the hole dope compound applied when a hole dope compound is contained in the overcoat layer is not particularly limited as long as it is the aforementioned compound.
- the concentration range of the hole dope compound contained in the overcoat layer is 0.2 to 20% by mass from the viewpoint of the doping effect. More preferably, it is 2 to 10% by mass.
- a method for producing such an overcoat layer containing a hole dope compound is not particularly limited.
- a wet coating method is employed, and a method of adding a hole dope compound to a coating liquid to be used is used. Can be mentioned.
- the total light transmittance is preferably in the range of 80% to 93%. More preferably, it is in the range of 90% to 93%.
- the surface resistance value is preferably in the range of 1 ⁇ 10 0 to 1 ⁇ 10 4 ⁇ / ⁇ . More preferably, the surface resistance value is in the range of 1 ⁇ 10 0 to 1 ⁇ 10 3 ⁇ / ⁇ .
- Such surface resistance value and total light transmittance can be adjusted by the coating amount of carbon nanotubes. That is, when the coating amount of the carbon nanotube is small, both the surface resistance value and the total light transmittance are high, and when the coating amount is large, both are low.
- the transparent conductivity the lower the surface resistance value and the higher the total light transmittance, the better the characteristics. Therefore, the two have a trade-off relationship. In order to compare the transparent conductivity, it is necessary to fix one index and then compare the other index.
- the ratio of the total light transmittance of the transparent conductive laminate before and after the carbon nanotube application that is, the total light transmittance of the transparent conductive laminate after the carbon nanotube application is determined before the carbon nanotube application.
- the value divided by the total light transmittance (hereinafter referred to as the total light transmittance of the carbon nanotube layer) is used. This is an index representing the transparent conductivity of the carbon nanotube layer alone.
- the transparent conductor of the present invention can be preferably used as a display-related electrode such as a touch panel, a liquid crystal display, organic electroluminescence, and electronic paper.
- a probe was brought into close contact with the central portion on the carbon nanotube layer side of a transparent conductor sampled to 5 cm ⁇ 10 cm, and the resistance value was measured at room temperature by a four-terminal method.
- the apparatus used was a resistivity meter MCP-T360 manufactured by Dia Instruments, and the probe used was a 4-probe probe MCP-TPO3P manufactured by Dia Instruments.
- undercoat layer containing hole dope compound 1% by weight of gold chloride was added to the above-mentioned coating solution for preparing a silica film (Mega Aqua hydrophilic DM coat DM-30-26G-N1 manufactured by Ryowa Co., Ltd.) Acid aqueous solution (prepared by dissolving chloroauric acid manufactured by Wako Pure Chemical Industries, Ltd. in pure water.
- Examples of catalyst preparation for carbon nanotubes About 24.6 g of iron (III) ammonium citrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 6.2 kg of ion-exchanged water. About 1000 g of magnesium oxide (MJ-30 manufactured by Iwatani Chemical Industry Co., Ltd.) was added to this solution, and after vigorously stirring for 60 minutes with a stirrer, the suspension was introduced into a 10 L (liter) autoclave container. . At this time, 0.5 kg of ion exchange water was used as a washing solution. In a sealed state, it was heated to 160 ° C. and held for 6 hours.
- iron (III) ammonium citrate manufactured by Wako Pure Chemical Industries, Ltd.
- magnesium oxide MJ-30 manufactured by Iwatani Chemical Industry Co., Ltd.
- the autoclave container was allowed to cool, the slurry-like cloudy substance was taken out from the container, excess water was filtered off by suction filtration, and a small amount of water contained in the filtered material was dried by heating in a 120 ° C. drier. From the obtained solid content, particles having a particle size in the range of 20 to 32 mesh were collected while being finely divided in a mortar on a sieve.
- the granular catalyst body shown on the left was introduced into an electric furnace and heated at 600 ° C. for 3 hours in the atmosphere. The bulk density was 0.32 g / mL (milliliter). Further, when the filtrate was analyzed by an energy dispersive X-ray analyzer (EDX), iron was not detected. From this, it was confirmed that the added iron (III) ammonium citrate was supported on the entire amount of magnesium oxide. Furthermore, from the EDX analysis result of the catalyst body, the iron content contained in the catalyst body was 0.39% by mass.
- the contact time (W / F) obtained by dividing the mass of the solid catalyst body by the flow rate of methane at this time was 169 minutes ⁇ g / L (liter), and the linear velocity of the gas containing methane was 6.55 cm / second. .
- the quartz reaction tube was cooled to room temperature while the introduction of methane gas was stopped and nitrogen gas was passed through at 16.5 L (liter) / min.
- a carbon nanotube-containing composition containing a catalyst body and carbon nanotubes (hereinafter, this composition is referred to as a catalyst-attached carbon nanotube composition) was taken out from the reactor. .
- this catalyst-attached carbon nanotube composition was stirred in 2000 mL (milliliter) of a 4.8N hydrochloric acid aqueous solution for 1 hour to dissolve the catalyst metal iron and the carrier MgO.
- the obtained black suspension was filtered, and the filtered product was again put into 400 mL (milliliter) of a 4.8N hydrochloric acid aqueous solution to remove MgO, and then filtered again. This operation was repeated three times to obtain a carbon nanotube composition from which the catalyst was removed (hereinafter, this composition is referred to as a catalyst-removed carbon nanotube composition).
- the catalyst-removed carbon nanotube composition was added to about 300 times the mass of concentrated nitric acid (1st grade Assay 60-61%, manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, the mixture was heated to reflux with stirring in an oil bath at about 140 ° C. for 25 hours.
- the nitric acid solution containing carbon nanotubes after heating to reflux was diluted with ion-exchanged water three times and suction filtered. After rinsing with ion-exchanged water until the suspension of the filtered product became neutral, the carbon nanotubes were stored in a wet state containing water (hereinafter, the wet bon nanotubes were simply referred to as the carbon nanotube composition). To write.)
- the carbon nanotube composition was observed with a high-resolution transmission electron microscope, the ratio of double-walled carbon nanotubes to the total number of carbon nanotubes contained was 90%.
- Carbon nanotube dispersion liquid 1 25 mg of carbon nanotubes (carbon nanotube composition obtained above containing 25 mg of carbon nanotubes in terms of dry mass), 1% by mass sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., Cellogen 5A (mass average molecular weight 8) )) 7.5 g of aqueous solution, 6.7 g of zirconia beads (Toray Co., Ltd., “Traceram”, bead size: 0.8 mm) were added to the container, and 28 mass% aqueous ammonia solution (Kishida Chemical Co., Ltd.) ) To adjust the pH to 10. The dispersant / carbon nanotube mass ratio in this dispersion is 3. This container was shaken for 2 hours using a vibration mill to prepare a carbon nanotube paste.
- this carbon nanotube paste was diluted with ion-exchanged water so that the concentration of carbon nanotubes was 0.15% by mass, and adjusted to pH 10 with 28% by mass ammonia aqueous solution again with respect to 10 g of the diluted solution.
- the aqueous solution was dispersed with an ultrasonic homogenizer at an output of 20 W for 1.5 minutes under ice cooling.
- the liquid temperature during dispersion was adjusted to 10 ° C. or lower.
- the obtained liquid was centrifuged at 10,000 G for 15 minutes with a high-speed centrifuge to obtain 9 g of a carbon nanotube dispersion.
- Carbon nanotubes 25 mg (carbon nanotube composition obtained above containing 25 mg of carbon nanotubes in terms of dry mass), 1% by mass sodium carboxymethyl cellulose (Daiichi Kogyo Seiyaku Co., Ltd., Cellogen 7A (mass average molecular weight 19) )) 7.5 g of aqueous solution, 6.7 g of zirconia beads (Toray Co., Ltd., “Traceram”, bead size: 0.8 mm) were added to the container, and 28 mass% aqueous ammonia solution (Kishida Chemical Co., Ltd.) ) To adjust the pH to 10. The dispersant / carbon nanotube mass ratio in this dispersion is 3. This container was shaken for 2 hours using a vibration mill to prepare a carbon nanotube paste.
- this carbon nanotube paste was diluted with ion-exchanged water so that the concentration of carbon nanotubes was 0.15% by mass, and adjusted to pH 10 with 28% by mass ammonia aqueous solution again with respect to 10 g of the diluted solution.
- the aqueous solution was dispersed with an ultrasonic homogenizer at an output of 20 W for 1.5 minutes under ice cooling.
- the liquid temperature during dispersion was adjusted to 10 ° C. or lower.
- the obtained liquid was centrifuged at 10,000 G for 15 minutes with a high-speed centrifuge to obtain 9 g of a carbon nanotube dispersion.
- overcoat layer formation (1) Formation of an overcoat layer containing no hole dope compound In a 100 mL plastic container, 20 g of ethanol was added, and 40 g of n-butyl silicate was added and stirred for 30 minutes. Then, after adding 10 g of 0.1N hydrochloric acid aqueous solution, the mixture was stirred for 2 hours and allowed to stand at 4 ° C for 12 hours. This solution was diluted with a mixed solution of toluene, isopropyl alcohol, and methyl ethyl ketone so that the solid concentration was 1% by mass to prepare a coating solution for forming an overcoat layer.
- the overcoat layer-forming coating solution was applied onto the carbon nanotube layer using the wire bar # 8, and then dried in a 125 ° C. dryer for 1 minute to form an overcoat layer.
- an overcoat layer containing a hole dope compound As a coating liquid for forming the above-mentioned overcoat layer, a 1% by mass aqueous chloroauric acid solution (chloroauric acid manufactured by Wako Pure Chemical Industries, Ltd. is used as pure water). 1% by weight iron chloride aqueous solution (prepared by dissolving iron chloride manufactured by Wako Pure Chemical Industries, Ltd.
- the content of the hole dope compound in the solid content of Lomethanesulfonyl) imide silver solution prepared by dissolving Sigma-Aldrich bis (trifluoromethanesulfonyl) imide silver in isopropyl alcohol. The same applies hereinafter
- the undercoat containing the hole dope compound was prepared in the same manner as in the preparation example of (1) except that the coating liquid for overcoat layer formation was prepared and used. A coat layer was formed.
- Example 1 According to the undercoat layer formation example, an undercoat layer having a chloroauric acid content of 20% by mass was formed. A carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion liquid 1. An overcoat layer was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 2 to 3 Comparative Example 1
- a transparent conductor was produced in the same manner as in Example 1 except that the combination of the formation of the undercoat layer, the carbon nanotube dispersion, and the overcoat layer was changed to the combinations shown in Table 1. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 4 According to the undercoat layer formation example, an undercoat layer having a chloroauric acid content of 20% by mass was formed. A carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion 2. An overcoat layer was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 5 Comparative Example 2
- a transparent conductor was produced in the same manner as in Example 4 except that the combination of formation of the undercoat layer, carbon nanotube dispersion, and overcoat layer was changed to the combinations shown in Table 1. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 9 According to the undercoat layer formation example, an undercoat layer having an iron chloride content of 20% by mass was formed. A carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion 2. An overcoat layer was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 10 According to the undercoat layer formation example, an undercoat layer was formed. A carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion liquid 1. An overcoat layer having a chloroauric acid content of 10% by mass was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 11 and 12 Comparative Example 3
- a transparent conductor was produced in the same manner as in Example 10 except that the combination of formation of the undercoat layer, carbon nanotube dispersion, and overcoat layer was changed to the combinations shown in Table 1. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 13 According to the undercoat layer formation example, an undercoat layer was formed. A carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion 2. An overcoat layer having a chloroauric acid content of 20% by mass was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 14 to 17 A transparent conductor was produced in the same manner as in Example 13 except that the combination of formation of the undercoat layer, carbon nanotube dispersion, and overcoat layer was changed to the combinations shown in Table 1. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 18 According to the undercoat layer formation example, an undercoat layer was formed. A carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion 2. An overcoat layer having a bis (trifluoromethanesulfonyl) imide silver content of 10% by mass was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 19 According to the undercoat layer formation example, an undercoat layer having a chloroauric acid content of 10% by mass was formed. A carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion liquid 1. An overcoat layer having a chloroauric acid content of 1% by mass was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- an undercoat layer was formed.
- a carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion liquid 1.
- An overcoat layer was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 20 According to the undercoat layer formation example, an undercoat layer having a chloroauric acid content of 10% by mass was formed. A carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion 2. An overcoat layer having a chloroauric acid content of 10% by mass was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 21 According to the undercoat layer formation example, an undercoat layer having a chloroauric acid content of 2% by mass was formed. A carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion 2. An overcoat layer containing 0.2% by mass of chloroauric acid was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 22 According to the undercoat layer formation example, an undercoat layer having a bis (trifluoromethanesulfonyl) imide silver content of 10% by mass was formed. A carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion 2. An overcoat layer having a bis (trifluoromethanesulfonyl) imide silver content of 10% by mass was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 23 According to the corona-treated substrate formation example, a hydrophilized PET film was produced. A carbon nanotube layer was formed using the carbon nanotube dispersion liquid 2 on the hydrophilized PET. An overcoat layer containing 10% by mass of an aqueous chloroauric acid solution was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- a hydrophilized PET film was produced.
- a carbon nanotube layer was formed using the carbon nanotube dispersion liquid 2 on the hydrophilized PET.
- An overcoat layer was provided on the carbon nanotube layer by the method of the overcoat layer formation example to produce a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Example 24 According to the undercoat layer formation example, an undercoat layer having a chloroauric acid content of 10% by mass was formed. A carbon nanotube layer was formed on the undercoat layer using the carbon nanotube dispersion 2 to prepare a transparent conductor. Thereafter, the surface resistance value and the total light transmittance were measured.
- Table 1 shows the content, hole dope compound content in the overcoat layer, surface resistance, and total light transmittance.
- Example 23 when the undercoat layer is not provided and the chloroauric acid content in the overcoat layer is 10 mass% (Example 23), the surface resistance is about 47% as compared with the case where it is not contained (Comparative Example 4). It can be seen that the value is decreasing. Further, when no overcoat layer is provided and the amount of chloroauric acid mixed in the undercoat layer is 10% by mass (Example 24), the surface resistance is about 45% as compared with the case where it is not contained (Comparative Example 2) It can be seen that the value is decreasing.
- Table 2 shows the water contact angles of the undercoat layers in Examples 1 to 3 and Comparative Example 1.
- the water contact angle of the undercoat layer mixed with 2 to 20% by mass of chloroauric acid is 5.88 to 18.86 °, and the contact angle increases as the mixing amount increases. Recognize.
- the transparent conductor according to the present invention can be used as various conductive materials.
Abstract
Description
カーボンナノチューブは、実質的にグラファイトの1枚面を巻いて筒状にした形状を有するものであれば特に限定されず、グラファイトの1枚面を1層に巻いた単層カーボンナノチューブ、多層に巻いた多層カーボンナノチューブのいずれもが適用できる。中でもカーボンナノチューブ全数のうち2層カーボンナノチューブを50%以上含むことが好ましい。2層カーボンナノチューブはグラファイトの1枚面を2層に巻いたカーボンナノチューブであり、これを50%以上含むとは、カーボンナノチューブ全100本中50本以上が2層カーボンナノチューブであることをいう。カーボンナノチューブ全数のうち2層カーボンナノチューブを50%以上含むとカーボンナノチューブの導電性ならびに塗布用分散液中でのカーボンナノチューブの分散性が極めて高くなる。さらに好ましくは100本中75本以上、最も好ましくは100本中80本以上が2層カーボンナノチューブである。また、2層カーボンナノチューブの適用は、酸処理などによって表面が官能基化されても導電性などの本来の機能が損なわれない点からも好ましい。
カーボンナノチューブ導電層はカーボンナノチューブを含むものであれば特に限定されない。未処理導電層の形成方法として、例えば、基材上へのカーボンナノチューブ分散液の塗布法、基板上へのカーボンナノチューブ直接成長法、基材上へのカーボンナノチューブ膜の転写法などが挙げられる。その中でも、分散剤と分散媒を用いて簡便に分散液を得られることから、透明基材上へのカーボンナノチューブ分散液の塗布法が好ましい。
カーボンナノチューブを溶媒中で分散させるために、分散剤を用いることが好ましい。分散剤は、本発明の分散性が得られる限りカーボンナノチューブの分散能があれば、低分子分散剤、高分子分散剤、またイオン性分散剤、非イオン性分散剤など種類を問わないが、分散性、分散安定性から高分子分散剤であることが好ましい。その中で、多糖類または芳香族の構造を骨格中に有するポリマーまたは低分子のアニオン性界面活性剤は、特に分散性に優れるため好ましい。以下、多糖類の構造を骨格中に有するポリマーを多糖類ポリマー、芳香族の構造を骨格中に有するポリマーを芳香族性ポリマー、低分子のアニオン性界面活性剤をアニオン性界面活性剤と記す。かかる分散剤がカーボンナノチューブを分散媒中に均一に孤立して分散させる理由は、次のように考えられる。カーボンナノチューブは、強固な束(バンドル)や、互いに絡まり合った強固な凝集体を形成するため、溶媒中に孤立して分散させることが非常に困難である。カーボンナノチューブを溶媒中で孤立分散させるためには、カーボンナノチューブのグラファイトとπ電子相互作用し束や凝集を解すること、もしくはカーボンナノチューブとの疎水性相互作用により束や凝集を解くことが必要である。より孤立したカーボンナノチューブ分散液を得るために、多糖類ポリマーや芳香族性ポリマーが有効に作用しているものと推測される。
分散剤の質量平均分子量は100以上が好ましい。質量平均分子量が100以上であればカーボンナノチューブとの相互作用が可能となりカーボンナノチューブの分散がより良好となる。カーボンナノチューブの長さにもよるが、質量平均分子量が大きいほど分散剤がカーボンナノチューブと相互作用し分散性が向上する。例えば、ポリマーの場合であれば、ポリマー鎖が長くなるとポリマーがカーボンナノチューブにからみつき非常に安定な分散が可能となる。しかし、質量平均分子量が大きすぎると逆に分散性が低下するので、質量平均分子量は好ましくは1000万以下であり、さらに好ましくは、100万以下である。最も好ましい質量平均分子量範囲は1万~50万である。
分散媒としては、上記分散剤を溶解できる水系、また非水系の分散媒を用いることができる。廃液の処理や環境や防災上の観点から、水が好ましい分散媒である。
本発明において用いる分散液の調製方法は、特に限定されない。調製時の分散手段としては、カーボンナノチューブと分散剤を分散媒中で塗装製造に慣用の混合分散機(例えばボールミル、ビーズミル、サンドミル、ロールミル、ホモジナイザー、超音波ホモジナイザー、高圧ホモジナイザー、超音波装置、アトライター、デゾルバー、ペイントシェーカー等)を用いて混合することが挙げられる。中でも、超音波装置を用いて分散する方法が、得られる塗布用分散液中のカーボンナノチューブの分散性が良好であることから好ましい。
以上のようにして得た塗布用分散液を基材上に塗布した後、乾燥させて未処理導電層を形成する。基材の素材としては、樹脂、ガラスなどを挙げることができる。樹脂としては、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)などのポリエステル、ポリカーボネート(PC)、ポリメチルメタクリレート(PMMA)、ポリイミド、ポリフェニレンスルフィド、アラミド、ポリプロピレン、ポリエチレン、ポリ乳酸、ポリ塩化ビニル、ポリメタクリル酸メチル、脂環式アクリル樹脂、シクロオレフィン樹脂、トリアセチルセルロースなどを用いることができる。ガラスとしては、通常のソーダガラスを用いることができる。また、これらの複数の基材を組み合わせて用いることもできる。例えば、樹脂とガラスを組み合わせた基材、2種以上の樹脂を積層した基材などの複合基材を用いてもよい。樹脂フィルムにハードコートを設けたようなものであっても良い。基材の種類は上記に限定されることはなく、用途に応じて耐久性やコスト等から最適なものを選ぶことができる。透明基材の厚みは特に限定されるものではないが、タッチパネル、液晶ディスプレイ、有機エレクトロルミネッセンス、電子ペーパーなどのディスプレイ関連の電極に用いる場合、10μm~1000μmの間にあることが好ましい。
カーボンナノチューブ導電層の形成工程では、上記方法により得た塗布用分散液を基材に塗布し、その後分散媒を乾燥させてカーボンナノチューブを基材上に固定して未処理導電層を形成する。
塗布用分散液を基材上に塗布する際の塗布厚み(ウェット厚み)は塗布用分散液の濃度にも依存するため、所望の表面抵抗値が得るのに必要なカーボンナノチューブの塗布量を考慮して適宜調整すればよい。カーボンナノチューブの塗布量は、導電性を必要とする種々の用途を達成するために、適宜調整可能である。例えば、カーボンナノチューブの塗布量が1mg/m2~40mg/m2であれば表面抵抗値は1×100~1×104Ω/□とすることができる。さらに、塗布量を40mg/m2以下とすれば表面抵抗値を1×101Ω/□以下とすることができる。塗布量を30mg/m2以下とすれば表面抵抗値を1×102Ω/□以下とすることができる。さらに、塗布量が20mg/m2以下であれば、1×103Ω/□以下、塗布量が10mg/m2以下であれば1×104Ω/□以下とすることができる。
カーボンナノチューブ分散液を基材上に塗布する際、塗布ムラを抑制するため、塗布用分散液中に濡れ剤を添加しても良い。透明導電体の製造ではカーボンナノチューブ分散液の分散媒に水を選択しているので、非親水性の表面を有する基材上に塗布する場合には界面活性剤やアルコール等の濡れ剤をカーボンナノチューブ分散液に添加することで、基材上で前記塗布用分散液がはじかれることなく塗布用分散液を塗布することができる。濡れ剤としては、アルコールが好ましく、アルコールの中でもメタノール、エタノール、プロパノール、イソプロパノールが好ましい。メタノール、エタノール、イソプロパノールなどの低級アルコールは揮発性が高いために塗布後の基材乾燥時に容易に除去可能である。場合によってはアルコールと水の混合液を用いても良い。
ホールドープ化合物とは、カーボンナノチューブへホールドープ(=カーボンナノチューブから電子を引き抜くこと)することで、カーボンナノチューブの導電性を向上させる化合物のことをいう。
具体的な非金属ハロゲン化物としては、クロロスルホン酸、テトラフルオロテトラシアノキノジメタン(F4-TCNQ)、N-フェニルビストリフルオロメタンスルホニルイミドなどがあげられる。
本発明においては透明基材上にアンダーコート層を設ける。アンダーコート層の素材としては、親水性の高い素材であることが好ましい。具体的には、水接触角が5~20°の範囲にある素材が好ましい。具体的には無機酸化物を用いることが好ましい。より好ましくは、チタニア、アルミナ、シリカである。これらの物質は、表面に親水基(-OH基)を有しており、高い親水性が得られるため好ましい。さらに、アンダーコート層が、シリカ微粒子とポリシリケートの複合物であることがより好ましい。
本発明において、アンダーコート層を透明基材上に設ける方法は特に限定されない。既知の湿式コーティング方法、例えば吹き付け塗装、浸漬コーティング、スピンコーティング、ナイフコーティング、キスコーティング、グラビアコーティング、スロットダイコーティング、ロールコーティング、バーコーティング、スクリーン印刷、インクジェット印刷、パット印刷、他の種類の印刷などが利用できる。また、乾式コーティング方法を用いてもよい。乾式コーティング方法としては、スパッタリング、蒸着などの物理気相成長や化学気相成長などが利用できる。また塗布は、複数回に分けて行ってもよく、異なる2種類の塗布方法を組み合わせても良い。好ましい塗布方法は、湿式コーティングであるグラビアコーティング、バーコーティングである。
アンダーコート層にホールドープ化合物を含有せしめる場合に適用するホールドープ化合物は前述の化合物であれば特に限定されない。アンダーコート層に含有せしめるホールドープ化合物の濃度範囲は、ドーピング効果の点より0.2~20質量%であり、好ましくは2~20質量%であり、より好ましくは、2~10質量%である。
アンダーコート層厚みは特に限定されない。光学干渉による反射防止効果が有効に得られる厚みであれば、光線透過率が向上するため好ましい。その値は10nm~300nmより好ましくは50nm~200nmである。
水の接触角は市販の接触角測定装置を用いて測定することができる。接触角の測定は、JIS R3257(1999)に準じ、室温25℃、相対湿度50%の雰囲気下で、アンダーコート層表面に1~4μLの水をシリンジで滴下し、液滴を水平断面から観察し、液滴端部の接線と膜平面とのなす角を求める。
本発明においてはカーボンナノチューブ層形成後、この層の上面に透明被膜を形成しうる。オーバーコート層を形成することにより、さらに透明導電性や耐熱性安定性、耐湿熱安定性が向上できるため好ましい。
本発明において、オーバーコート層をカーボンナノチューブ層上に設ける方法は特に限定されない。既知の湿式コーティング方法、例えば吹き付け塗装、浸漬コーティング、スピンコーティング、ナイフコーティング、キスコーティング、ロールコーティング、グラビアコーティング、スロットダイコーティング、バーコーティング、スクリーン印刷、インクジェット印刷、パット印刷、他の種類の印刷、またはなどが利用できる。また、乾式コーティング方法を用いてもよい。乾式コーティング方法としては、スパッタリング、蒸着などの物理気相成長や化学気相成長などが利用できる。またオーバーコート層をカーボンナノチューブ層上に設ける操作は、複数回に分けて行ってもよく、異なる2種類の方法を組み合わせても良い。好ましい方法は、湿式コーティングであるグラビアコーティング、バーコーティングである。
オーバーコート層にホールドープ化合物を含有せしめる場合に適用するホールドープ化合物は前述の化合物であれば特に限定されない。オーバーコート層中に含有せしめるホールドープ化合物の濃度範囲は、ドーピング効果の点より0.2~20質量%である。より好ましくは、2~10質量%である。
上述のようにして透明導電性に優れる透明導電積層体を得ることができる。全光線透過率としては、80%~93%の範囲にあることが好ましい。より好ましくは90%~93%の範囲である。表面抵抗値は、1×100~1×104Ω/□の範囲にあることが好ましい。より好ましくは表面抵抗値が1×100~1×103Ω/□の範囲である。かかる表面抵抗値、全光線透過率は、カーボンナノチューブ塗布量により調整することができる。すなわち、カーボンナノチューブ塗布量が少ないと、表面抵抗値、全光線透過率とも高くなり、塗布量が多いと両者とも低くなる。透明導電性としては、表面抵抗値が低く、全光線透過率が高い方が特性として優れているので、両者はトレードオフの関係にある。透明導電性を比較するためには、どちらかの指標を固定化してその上でもう一方の指標を比較する必要がある。
本発明の透明導電体は、例えば、タッチパネル、液晶ディスプレイ、有機エレクトロルミネッセンス、電子ペーパーなどのディスプレイ関連の電極として好ましく用いることができる。
5cm×10cmにサンプリングした透明導電体のカーボンナノチューブ層側の中央部にプローブを密着させて、4端子法により室温下で抵抗値を測定した。使用した装置は、ダイアインスツルメンツ(株)製の抵抗率計MCP-T360型、使用したプローブはダイアインスツルメンツ(株)製の4探針プローブMCP-TPO3Pである。
JIS-K7361(1997年)に基づき、日本電色工業(株)製の濁度計NDH2000を用いて測定した。
室温25℃、相対湿度50%の雰囲気下で、膜表面に1~4μLの水をシリンジで滴下した。接触角計(協和界面化学社製、接触角計CA-X型)を用いて、液滴を水平断面から観察し、液滴端部の接線と膜平面とのなす角を求めた。
(1)ホールドープ化合物を含有しないアンダーコート層の形成
約30nmの親水シリカ微粒子とポリシリケートを含むシリカ膜作製用塗液((株)菱和社製 メガアクア親水DMコート DM-30-26G-N1)をアンダーコート層形成用の塗液として用いた。
上記のシリカ膜作製用塗液((株)菱和社製 メガアクア親水DMコート DM-30-26G-N1)に、1質量%の塩化金酸水溶液(和光純薬工業(株)製塩化金酸を純水に溶解して調製した。以下同じ)、1質量%の塩化鉄水溶液(和光純薬工業(株)製塩化鉄を純水に溶解して調製した。以下同じ)、または、1質量%のビス(トリフルオロメタンスルホニル)イミド銀溶液(シグマアルドリッチ製ビス(トリフルオロメタンスルホニル)イミド銀をイソプロピルアルコールに溶解して調製した。以下同じ)を固形分中のホールドープ化合物の質量含有率が表1に記載の含有率となるように25℃において添加し、アンダーコート層形成用の塗液を調製して用いた他は、(1)の作成例と同様にして、ホールドープ化合物を含有するアンダーコート層を形成した。
東レ(株)製“ルミラー”U46に、コロナ表面改質評価装置(春日電機(株),TEC-4AX)を用い、電極と透明基材間に1mmの距離を隔てた上で出力100W、速度6.0m/分で電極を移動させる操作を5回行った。この処理により基材表面の親水性が増し、水接触角が56°から43°に低下した。
約24.6gのクエン酸鉄(III)アンモニウム(和光純薬工業(株)社製)をイオン交換水6.2kgに溶解した。この溶液に、酸化マグネシウム(岩谷化学工業(株)社製MJ-30)を約1000g加え、撹拌機で60分間激しく撹拌処理した後に、懸濁液を10L(リットル)のオートクレーブ容器中に導入した。この時、洗い込み液としてイオン交換水0.5kgを使用した。密閉した状態で160℃に加熱し6時間保持した。その後オートクレーブ容器を放冷し、容器からスラリー状の白濁物質を取り出し、過剰の水分を吸引濾過により濾別し、濾取物中に少量含まれる水分は120℃の乾燥機中で加熱乾燥した。得られた固形分から篩い上で、乳鉢で細粒化しながら、20~32メッシュの範囲の粒径のものを回収した。左記の顆粒状の触媒体を電気炉中に導入し、大気下600℃で3時間加熱した。かさ密度は0.32g/mL(ミリリットル)であった。また、濾液をエネルギー分散型X線分析装置(EDX)により分析したところ鉄は検出されなかった。このことから、添加したクエン酸鉄(III)アンモニウムは全量酸化マグネシウムに担持されたことが確認できた。さらに触媒体のEDX分析結果から、触媒体に含まれる鉄含有量は0.39質量%であった。
触媒調製例に従い調製した固体触媒体132gを、鉛直方向に設置した反応器の中央部の石英焼結板上に導入した。反応管内温度が約860℃になるまで、触媒体層を加熱しながら、反応器底部から反応器上部方向へ向けてマスフローコントローラーを用いて窒素ガスを16.5L(リットル)/分で供給し、触媒体層を通過するように流通させた。その後、窒素ガスを供給しながら、さらにマスフローコントローラーを用いてメタンガスを0.78L(リットル)/分で60分間導入して触媒体層を通過するように通気し、反応させた。この際の固体触媒体の質量をメタンの流量で割った接触時間(W/F)は、169分・g/L(リットル)、メタンを含むガスの線速は6.55cm/秒であった。メタンガスの導入を止め、窒素ガスを16.5L(リットル)/分で通気させながら、石英反応管を室温まで冷却した。
カーボンナノチューブ25mg(乾燥質量換算で25mgのカーボンナノチューブを含有する前記で得られたカーボンナノチューブ組成物)、1質量%カルボキシメチルセルロースナトリウム(第一工業製薬(株)社製、セロゲン5A(質量平均分子量8万))水溶液7.5g、ジルコニアビーズ(東レ(株)社製、“トレセラム”、ビーズサイズ:0.8mm)6.7gを容器に加え、28質量%アンモニア水溶液(キシダ化学(株)社製)を用いてpH10に調整した。この分散液中の分散剤/カーボンナノチューブの質量比は3である。この容器を振動ミルを用いて2時間振盪させ、カーボンナノチューブペーストを調製した。
カーボンナノチューブ25mg(乾燥質量換算で25mgのカーボンナノチューブを含有する前記で得られたカーボンナノチューブ組成物)、1質量%カルボキシメチルセルロースナトリウム(第一工業製薬(株)社製、セロゲン7A(質量平均分子量19万))水溶液7.5g、ジルコニアビーズ(東レ(株)社製、“トレセラム”、ビーズサイズ:0.8mm)6.7gを容器に加え、28質量%アンモニア水溶液(キシダ化学(株)社製)を用いてpH10に調整した。この分散液中の分散剤/カーボンナノチューブの質量比は3である。この容器を振動ミルを用いて2時間振盪させ、カーボンナノチューブペーストを調製した。
前記カーボンナノチューブ分散液にイオン交換水を添加して、0.055質量%(実施例1~3,10~12,19、および、比較例1,3,4)または0.04質量%(実施例4~9,13~18,20~23、および、比較例2,5)に調整後、前記アンダーコート層を設けた基材にワイヤーバー#4(実施例10~12、および比較例3)、または#5(実施例1~9,13~24、および、比較例1,2,4,5)を用いて塗布、80℃乾燥機内で1分間乾燥させカーボンナノチューブ組成物を固定化した(以降、カーボンナノチューブ組成物を固定化したフィルムを、カーボンナノチューブ塗布フィルムと記す。)。なお、各塗布条件に対応するカーボンナノチューブの塗布量は表1の通りであった。
(1)ホールドープ化合物を含有しないオーバーコート層の形成
100mLポリ容器中に、エタノール20gを入れ、n-ブチルシリケート40gを添加し30分間撹拌した。その後、0.1N塩酸水溶液を10g添加した後2時間撹拌を行い4℃で12時間静置した。この溶液をトルエンとイソプロピルアルコールとメチルエチルケトンの混合液で固形分濃度が1質量%となるように希釈しオーバーコート層形成用の塗液を調製した。
上記のオーバーコート層形成用の塗液として、1質量%の塩化金酸水溶液(和光純薬工業(株)製塩化金酸を純水に溶解して調製した。以下同じ)、1質量%の塩化鉄水溶液(和光純薬工業(株)製塩化鉄を純水に溶解して調製した。以下同じ)、および1質量%のビス(トリフルオロメタンスルホニル)イミド銀溶液(シグマアルドリッチ製ビス(トリフルオロメタンスルホニル)イミド銀をイソプロピルアルコールに溶解して調製した。以下同じ)を固形分中のホールドープ化合物の質量含有率が表1に記載の含有率となるように25℃において添加し、オーバーコート層形成用の塗液を調製して用いた他は、(1)の作成例と同様にして、ホールドープ化合物を含有するアンダーコート層を形成した。
アンダーコート層形成例に従って、塩化金酸含有率が20質量%であるアンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液1を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上にオーバーコート層形成例の手法でオーバーコート層を設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層の形成、カーボンナノチューブ分散液、オーバーコート層の形成の組み合わせを、表1に示す組み合わせとした以外は、実施例1と同様にして透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層形成例に従って、塩化金酸含有率が20質量%であるアンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液2を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上にオーバーコート層形成例の手法でオーバーコート層を設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層の形成、カーボンナノチューブ分散液、オーバーコート層の形成の組み合わせを、表1に示す組み合わせとした以外は、実施例4と同様にして透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層形成例に従って、塩化鉄含有率が20質量%であるアンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液2を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上にオーバーコート層形成例の手法でオーバーコート層を設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層形成例に従って、アンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液1を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上に塩化金酸含有率が10質量%であるオーバーコート層をオーバーコート層形成例の手法で設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層の形成、カーボンナノチューブ分散液、オーバーコート層の形成の組み合わせを、表1に示す組み合わせとした以外は、実施例10と同様にして透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層形成例に従って、アンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液2を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上に塩化金酸含有率が20質量%であるオーバーコート層をオーバーコート層形成例の手法で設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層の形成、カーボンナノチューブ分散液、オーバーコート層の形成の組み合わせを、表1に示す組み合わせとした以外は、実施例13と同様にして透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層形成例に従って、アンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液2を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上にビス(トリフルオロメタンスルホニル)イミド銀含有率が10質量%であるオーバーコート層をオーバーコート層形成例の手法で設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層形成例に従って、塩化金酸含有率が10質量%であるアンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液1を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上に塩化金酸含有率が1質量%であるオーバーコート層をオーバーコート層形成例の手法で設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層形成例に従って、アンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液1を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上にオーバーコート層形成例の手法でオーバーコート層を設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層形成例に従って、塩化金酸含有率が10質量%であるアンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液2を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上に塩化金酸含有率が10質量%であるオーバーコート層をオーバーコート層形成例の手法で設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層形成例に従って、塩化金酸含有率が2質量%であるアンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液2を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上に塩化金酸が0.2質量%であるオーバーコート層をオーバーコート層形成例の手法で設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層形成例に従って、ビス(トリフルオロメタンスルホニル)イミド銀含有率が10質量%であるアンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液2を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上にビス(トリフルオロメタンスルホニル)イミド銀含有率が10質量%であるオーバーコート層をオーバーコート層形成例の手法で設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
コロナ処理基材形成例に従って、親水化処理を施したPETフィルムを作製した。親水化処理PETにカーボンナノチューブ分散液2を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上に塩化金酸水溶液が10質量%であるオーバーコート層をオーバーコート層形成例の手法で設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
コロナ処理基材形成例に従って、親水化処理を施したPETフィルムを作製した。親水化処理PETにカーボンナノチューブ分散液2を用いて、カーボンナノチューブ層を形成した。カーボンナノチューブ層上にオーバーコート層形成例の手法でオーバーコート層を設け、透明導電体を作製した。その後、表面抵抗値、全光線透過率の測定を行った。
アンダーコート層形成例に従って、塩化金酸含有率が10質量%であるアンダーコート層を形成した。アンダーコート層上にカーボンナノチューブ分散液2を用いて、カーボンナノチューブ層を形成し、透明導電体を作成した。その後、表面抵抗値、全光線透過率の測定を行った。
Claims (10)
- 透明基材上にカーボンナノチューブを含む分散液を塗布し乾燥させて導電層を形成することで透明基材の少なくとも片面に導電性の積層構造を形成する透明導電体の製造方法であって、
導電層を形成する前にホールドープ化合物を0.2~20質量%の割合で含むアンダーコート層を透明基材上に形成する工程、および/または、導電層を形成した後にホールドープ化合物を0.2~20質量%の割合で含むオーバーコート層を形成する工程を実施することを特徴とする透明導電体の製造方法。 - 透明基材上にアンダーコート層を形成する工程、カーボンナノチューブを含む分散液を塗布し乾燥させて導電層を形成する工程、オーバーコート層を形成する工程、をこの順で行うことで透明基材の少なくとも片面に導電性の積層構造を形成する透明導電体の製造方法であって、アンダーコート層および/またはオーバーコート層にホールドープ化合物を0.2~20質量%の割合で含有せしめることを特徴とする透明導電体の製造方法。
- 前記アンダーコート層の水接触角が5~20°である、請求項2に記載の透明導電体の製造方法。
- 前記ホールドープ化合物が金属ハロゲン化物である、請求項1~3のいずれかに記載の透明導電体の製造方法。
- 前記金属ハロゲン化物が塩化金酸を含む、請求項4に記載の透明導電体の製造方法。
- 透明基材の少なくとも片面に、ホールドープ化合物を0.2~20質量%の割合で含むアンダーコート層と、カーボンナノチューブを含む導電層とをこの順で有することを特徴とする透明導電体。
- 透明基材の少なくとも片面に、カーボンナノチューブを含む導電層と、ホールドープ化合物を0.2~20質量%の割合で含むオーバーコート層とをこの順で有することを特徴とする透明導電体。
- 透明基材の少なくとも片面に、ホールドープ化合物を0.2~20質量%の割合で含むアンダーコート層と、カーボンナノチューブを含む導電層と、ホールドープ化合物を0.2~20質量%の割合で含むオーバーコート層とをこの順で有することを特徴とする透明導電体。
- 前記ホールドープ化合物が金属ハロゲン化物である、請求項6~8のいずれかに記載の透明導電体。
- 前記金属ハロゲン化物が塩化金酸を含む、請求項9に記載の透明導電体。
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- 2012-09-21 EP EP12834716.8A patent/EP2738776A4/en not_active Withdrawn
- 2012-09-21 KR KR1020147004682A patent/KR20140068891A/ko not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
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EP2738776A4 (en) | 2015-04-01 |
CN103858183A (zh) | 2014-06-11 |
EP2738776A1 (en) | 2014-06-04 |
KR20140068891A (ko) | 2014-06-09 |
JPWO2013047341A1 (ja) | 2015-03-26 |
US20140248494A1 (en) | 2014-09-04 |
TW201320108A (zh) | 2013-05-16 |
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