WO2010001786A1 - 導電性膜の製造方法、及び、導電性膜 - Google Patents
導電性膜の製造方法、及び、導電性膜 Download PDFInfo
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- WO2010001786A1 WO2010001786A1 PCT/JP2009/061531 JP2009061531W WO2010001786A1 WO 2010001786 A1 WO2010001786 A1 WO 2010001786A1 JP 2009061531 W JP2009061531 W JP 2009061531W WO 2010001786 A1 WO2010001786 A1 WO 2010001786A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
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- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
Definitions
- the present invention relates to a method for manufacturing a conductive film and a conductive film. More specifically, the present invention relates to a method for producing a conductive film that can be suitably used for a thin display such as a liquid crystal display, a plasma display, and electronic paper (digital paper), and a touch panel, and a conductive film.
- a thin display such as a liquid crystal display, a plasma display, and electronic paper (digital paper), and a touch panel, and a conductive film.
- Conductive films have been applied to various electrical devices, and in particular, in recent years, demand for thin displays such as liquid crystal displays, plasma displays, and electronic paper (digital paper) has increased, and they are applied to such applications.
- As a conductive film a film having excellent light transmittance and conductivity is demanded, and research and development are actively conducted.
- ITO indium tin oxide
- a conductive film made of indium tin oxide has an excellent balance between light transmittance and conductivity, and is used not only for a normal liquid crystal display or the like but also for a touch panel, for example.
- Examples of the shape of the light-transmitting conductive film include a shape of a conductive film using a light-transmitting and conductive material such as indium tin oxide, and a mesh-shaped conductive film. It is done.
- the mesh-like conductive film and the manufacturing method thereof include, for example, a metal ultrafine particle catalyst layer formed in a predetermined pattern on the transparent substrate surface and a metal layer formed on the metal ultrafine particle catalyst layer.
- a method for producing a transparent conductive film in which a metal layer is formed only on the pattern printing portion by performing an electroless plating process on the pattern-printed electroless plating catalyst (see, for example, Patent Document 1), provided on a support.
- the silver salt-containing layer containing the obtained silver salt is exposed and developed to form a metallic silver part and a light-transmitting part, and further, the metallic silver part is physically developed and / or plated.
- Metallic silver A method for producing a light-transmitting electromagnetic wave shielding film having a conductive metal portion and a light-transmitting portion that form a conductive metal portion in which conductive metal particles are held together (see, for example, Patent Document 2), a transparent substrate. And an electromagnetic shielding material comprising a fine line pattern formed thereon, wherein the fine line pattern is an electromagnetic shielding material comprising a metal plating film having metallic silver as a catalyst nucleus by physical development, a transparent substrate, and a physical development nucleus layer And a light-sensitive material having a silver halide emulsion layer in this order are exposed, and silver is deposited in an arbitrary fine line pattern on the physical development nucleus layer by physical development, and then provided on the physical development nucleus layer.
- An electromagnetic wave shielding material manufacturing method (see, for example, Patent Document 3) is disclosed in which a metal is plated using the physically developed metallic silver as a catalyst nucleus after the layer is removed.
- EMI shield film electromagnetic wave shielding film
- the mesh-like conductive film manufactured by such a method is used as an electromagnetic wave shielding film (EMI shield film) or the like, there is a need for further thinning in order to improve transmittance and prevent moire, There was a need for improvement.
- the light transmittance is low and it was difficult to use it for a transparent electrode for a display or the like.
- a complicated lithography process is required for pattern formation, there is room for improvement from the viewpoint of productivity.
- a method of forming a mesh-like conductive coating is a method of forming a transparent and conductive coating that includes metal nanopowder and includes (a) a metal in an organic solvent.
- the nanopowder is mixed with at least one component selected from the group consisting of binders, surfactants, additives, polymers, buffers, dispersants, and coupling agents to obtain a homogeneous mixture.
- a method of sintering the coated surface in order to form a coating having the same is disclosed (for example, see Patent Document 4).
- the thickness of the plated metal layer on at least one side is 1.5 ⁇ m or more, the total light transmittance of the conductive substrate is greater than 65%, and the surface specific resistance on at least one side of the conductive substrate is 0.5 ⁇ /
- a conductive substrate smaller than ⁇ (ohm / square) is disclosed (for example, see Patent Document 5).
- a linear polymer is dissolved in a solvent to prepare a polymer solution, and then the polymer solution is cooled to condense the above in the atmosphere.
- a method for manufacturing a honeycomb-shaped porous body in which a part of the droplets enter the inside from the surface of the polymer solution, then the solvent is evaporated, and then the condensed droplets are removed (for example, patent document) 6), and an organic film patterned into a honeycomb structure (for example, see Non-patent Document 1) is disclosed, but all of them use a polymer organic film. Application is not described.
- the linear part comprised of the conductive metal is connected in a two-dimensional network form on the substrate, and the ratio of the area occupied by the linear part to the area of the entire surface of the substrate is 20% or less.
- An electrode is disclosed (for example, refer to Patent Document 7, which is a document published after the basic application of the present invention).
- a coating step in which conductive metal fine particles are dispersed in an organic solvent is coated on a transparent substrate and dried under high humidity to form a transparent electrode precursor, and the transparent electrode precursor
- a method for producing a transparent electrode is disclosed which includes a firing step for firing the material.
- silver nanoparticles are used, and the regularity of the network structure disappears on the surface of the transparent electrode from the SEM photograph of what was obtained after firing in FIG. 2, but a two-dimensional network was formed.
- the area of the opening was 92.8% of the entire surface even on the transparent electrode surface.
- the regularity of the network structure has certainly disappeared.
- the two-dimensional network it cannot be confirmed that it is formed, and it can only be seen that irregular irregularities are formed over the entire surface. In such a state, it is considered that the area of the opening is not sufficiently ensured.
- JP2003-109435A pages 1 and 2) JP 2004-221564 A (first and second pages)
- the silver film only forms irregularities on the entire surface, which means that there is no aperture ratio covering the entire surface, and transparency is not recognized. It is. Therefore, there is no prior art that discloses producing a mesh-like conductive film, and if such a problem can be solved, in a technical field using a conductive material such as a conductive film, a liquid crystal display, Various applications can be developed for plasma displays, electronic paper (digital paper), and the like, which can be said to have great technical significance.
- the present invention has been made in view of the above situation, and a mesh-like conductive film can be manufactured easily and inexpensively.
- a mesh-like conductive film can be manufactured easily and inexpensively.
- moire or the like occurs. It is an object of the present invention to provide a method for producing a non-conductive film and a conductive film.
- the inventor has made various studies on the formation of a conductive film using a conductive material such as a metal.
- a conductive film formed of a mesh-like line portion of a conductive material and a hole portion, the conductive film is formed. Attention has been paid to the fact that a conductive film having optical transparency and conductivity can be obtained.
- a method of forming a random network layer in which a plated metal layer is laminated on a metal fine particle layer has a problem that the cost increases.
- there is room for improvement in terms of productivity and in addition, by adding water in advance to the organic solvent dispersion and forming a pattern, the line width, the mesh cannot be made fine, Ink stability may deteriorate.
- a method for producing a conductive film including a step of evaporating the organic solvent while condensing the organic solvent dispersion containing the applied conductive fine particles on the surface of the coating film is provided.
- a mesh-like conductive film can be produced easily and inexpensively, and productivity can be improved.
- the conductive film produced by the above method has a small line width and a fine mesh, and has reached the present invention. If a mesh-like conductive film can be obtained, it will become a new method for imparting conductivity in conductive materials whose demand and applications have been rapidly expanding in recent years, and various application developments are expected.
- FIG. 1-1 is a conceptual diagram of a cross section of a coating film over time showing an example of a process of evaporating an organic solvent while condensing a coated organic solvent dispersion on the coating film surface.
- the coating film is formed without condensation on the surface of the organic solvent dispersion (hereinafter also referred to as “coating film”) applied to the substrate 11 by causing condensation. 12 and the organic solvent and water droplets evaporate to form a network-like conductive film. Since it is such a method, a manufacturing process becomes simple and low-cost, and productivity can also be improved.
- the present invention is a method for producing a network-like conductive film by applying an organic solvent dispersion containing conductive fine particles to a substrate, and the production method comprises applying a coated organic solvent dispersion to a coating film.
- This is a method for producing a conductive film including a step of evaporating an organic solvent while condensing on the surface.
- the present invention is also a mesh-like conductive film formed by a mesh-like line portion and a pore portion of a conductive substance, and the conductive film has an average area of the pore portion of 400 ⁇ m 2 or less.
- it is also a conductive film in which the line width of the mesh-like line portion is 5 ⁇ m or less.
- the method for producing a conductive film of the present invention is a method for producing a network-like conductive film by applying an organic solvent dispersion containing conductive fine particles to a substrate.
- film formation can be performed easily and at a lower cost as compared with a sputtering method, a plating method, and the like, and manufacturing costs can be reduced and productivity can be improved. it can.
- the film of the organic solvent dispersion applied on the substrate is also referred to as “coating film”.
- the arrangement form of the mesh-like line portions and the hole portions in the mesh-like conductive film may be random or may be regularly arranged. Examples thereof are as shown in FIGS. 6 to 10 described later.
- the method for producing the conductive film includes a step of evaporating the organic solvent while allowing the applied organic solvent dispersion to condense on the surface of the coating film. According to this, water droplets generated by condensation can be taken into the coating film while evaporating the organic solvent. Then, the organic solvent evaporates and the taken water droplets are dried, so that a hole corresponding to the taken water droplets can be formed. Thereby, the mesh-like line part formed from electroconductive fine particles and the void
- the conductive film formed by the above-described method for manufacturing a conductive film is preferably a mesh-like conductive film formed by a mesh-like line portion and a hole portion.
- the method for producing the conductive film includes a step of evaporating the organic solvent while allowing the applied organic solvent dispersion to condense on the surface of the coating film. Condensation on the coating film surface can be performed by adjusting the humidity near the coating film surface or the temperature difference between the atmosphere near the coating film surface and the coating film surface. That is, the conditions for condensation on the coating film surface may be used. In the present invention, since a mesh-like conductive portion and a void portion are formed on the surface of the coating film, this is caused by condensation on the coating film surface by the mechanism shown in FIG. 1-1. It is clear from a technical point of view that it is caused by evaporating the organic solvent.
- the method for producing a conductive film of the present invention includes a step of evaporating the applied organic solvent under conditions that cause dew condensation on the coating film surface.
- the conditions under which condensation occurs on the surface of the coating film are, for example, conditions in which the dew point of the atmosphere for evaporating the organic solvent is higher than the temperature of the coating film surface.
- the method for causing dew condensation is not particularly limited.
- a method of making the dew point of the atmosphere higher than the temperature of the coating film surface is suitable. These methods may be used in one method or a combination of a plurality of methods. By combining a plurality of methods, the conditions for evaporating the organic solvent can be controlled more precisely, and the form of the conductive film can be adjusted.
- the method for cooling the temperature of the coating film surface below the dew point of the atmosphere for evaporating the organic solvent is not particularly limited, but a method for forcibly cooling the coating film using a cooling element or the like, an organic solvent And a method of lowering the surface temperature of the coating film by latent heat of evaporation.
- a method of forcibly cooling a coating film using a cooling element etc. it is also preferable to cool the temperature of the coating film surface by cooling the board
- the temperature of the coating film surface lower than the temperature of the atmosphere in which the organic solvent is evaporated.
- a method of cooling the substrate coated with the organic solvent dispersion by using a cooling device such as a Peltier device is one of preferable methods.
- temperature control of the coating film surface and control of the atmosphere around the coating film for evaporating the organic solvent can be performed independently, so that more precise condition setting can be performed.
- the shape, transmittance, conductivity, etc. of the manufactured conductive film can be controlled, so that a conductive film of a suitable form can be formed according to various applications. .
- the step of evaporating the organic solvent is preferably a step of evaporating the organic solvent in a humidified atmosphere.
- the humidified atmosphere By setting the humidified atmosphere, dew condensation is likely to occur on the surface of the organic solvent dispersion.
- a method of setting the atmosphere at the time of evaporating the organic solvent as a humidified atmosphere and making the dew point higher than the temperature of the coating film surface a method of humidifying the entire surroundings where the organic solvent is evaporated, The attaching method is suitable. By using a humidified atmosphere, condensation tends to occur on the surface of the coating film.
- the shape and amount of water droplets taken into the coating film changes depending on the spraying speed, etc., so the organic solvent is evaporated by adjusting the spraying speed.
- the conditions to be adjusted can be adjusted. Thereby, the shape of the conductive film can be controlled, and its characteristics (light transmittance, conductivity, etc.) can be improved.
- the humidified atmosphere may be any atmosphere as long as the humidity is sufficient to cause condensation on the surface of the coating film of the organic solvent dispersion, that is, the same conditions as the humidification,
- the step of evaporating the organic solvent may be performed under a high humidity environment.
- the humidified atmosphere preferably has a relative humidity of 50% or more.
- the relative humidity is more preferably 55% or more, and still more preferably 60% or more.
- the upper limit of the wind speed for blowing the humidified gas is preferably 5 m / s (300 m / min) or less as the flow velocity.
- the flow rate that is more preferable as the upper limit of the wind speed for blowing the humidified gas is 3 m / s (180 m / min) or less, and more preferably 1 m / s (60 m / min) or less.
- the said wind speed it is preferable that it is 0.02 m / min or more.
- the flow rate more preferable as the lower limit of the wind speed is 0.1 m / min, more preferably 0.2 m / min or more, and particularly preferably 0.4 m / min or more.
- the upper limit of the time for blowing the humidified gas is preferably within one hour from the viewpoint of productivity. More preferably, it is within 40 minutes, and more preferably within 30 minutes.
- the lower limit of the time for blowing the humidified gas is preferably 1 minute or longer.
- the organic solvent may not be sufficiently evaporated, and water droplets may not be sufficiently taken into the organic solvent dispersion. More preferably, it is 5 minutes or more, More preferably, it is 10 minutes or more. For example, a suitable time is about 20 minutes (15 to 25 minutes).
- the relative humidity of the humidified gas to be blown is also preferably 50% or more, more preferably 55% or more, and particularly preferably 60% or more, as described above.
- FIG. 1-2 is a flowchart showing a process of evaporating the organic solvent while the applied organic solvent dispersion is condensed on the surface of the coating film.
- the organic solvent dispersion (hereinafter also referred to as “coating film”) applied to the substrate 11 is a method for cooling the substrate 11 on which the coating film 12 is formed or a humidified gas.
- the coating film By setting the conditions for causing condensation on the surface of the coating film by the method of spraying, as shown in FIG. 1-2 (b), condensation occurs on the surface of the coating film.
- the water droplets 13 generated by the condensation are taken into the coating film 12 as shown in FIGS.
- FIG. 2 is a schematic plan view showing the form of the film after the organic solvent evaporates, in which a mesh-like line portion 15 including a metal is formed around the formed hole portion 14. Thus, a permeable conductive film is formed.
- a mesh-like line portion 15 including a metal is formed around the formed hole portion 14.
- the method of evaporating the organic solvent by cooling the substrate 21 and the coating film 22 using the Peltier device 20 and spraying the humidified gas on the coated organic solvent dispersion is as follows. It is one of the suitable forms of the manufacturing method of the electroconductive film of this invention. That is, the manufacturing method preferably includes a step of cooling the substrate and the coating film, blowing a humidified gas onto the coating film, and evaporating the organic solvent while causing condensation on the coating film surface.
- the conductive fine particles generally mean conductive particles having an average particle diameter of 100 ⁇ m or less, and the particle diameter of the conductive fine particles is not particularly limited, but the average particle diameter is 1 ⁇ m or less. It is preferable. By setting the average particle diameter to 1 ⁇ m or less, the line width of the conductive mesh-like line portion can be reduced, the transparent portion of the transparent conductive film can be widened, and the aperture ratio is improved. Become. Thereby, the transmittance
- the average particle diameter of the conductive fine particles is more preferably 500 nm or less, still more preferably 100 nm or less, particularly preferably 50 nm or less, and most preferably 10 nm or less.
- the conductivity of the formed mesh-like line portion having conductivity can be increased.
- the melting point is lowered by reducing the particle size, so that the particles can be fused together at a low firing temperature to develop conductivity.
- the coefficient of variation is preferably within 30%, more preferably within 20%, and even more preferably within 15%.
- the average particle diameter is a number average particle diameter obtained from a TEM image (transmission electron microscope observation image) or SEM image (scanning electron microscope observation image); a crystallite diameter obtained by a powder X-ray diffraction measurement method; An average radius obtained from an inertia radius obtained by an X-ray small angle scattering method or the like and a scattering intensity thereof can be used. Especially, it is preferable that it is the number average particle diameter obtained by a SEM image (scanning electron microscope observation image).
- the shape of the conductive fine particles is not limited to a spherical shape, and is, for example, an elliptical spherical shape, a cubic shape, a rectangular parallelepiped shape, a pyramid shape, a needle shape, a columnar shape, a rod shape, a cylindrical shape, a flake shape, a plate shape (for example, a hexagonal plate shape). It can also be suitably used in the shape of a thin piece such as a string or the like.
- the conductive fine particles are not particularly limited as long as the conductive fine particles contain a conductive material, and examples thereof include fine particles of metals, conductive inorganic oxides, carbon-based materials, carbide-based materials, and the like.
- Various metals can be used as the metal, and any form such as a single metal, an alloy, and a solid solution may be used.
- the metal element is not particularly limited.
- various metal elements such as platinum, gold, silver, copper, aluminum, chromium, cobalt, and tungsten can be used, but a metal having high conductivity is preferable.
- the metal having high conductivity preferably contains at least one selected from the group consisting of platinum, gold, silver and copper. Further, the metal is preferably a metal having high chemical stability.
- the metal preferably contains at least one selected from the group consisting of platinum, gold and silver.
- the inorganic oxide having conductivity include indium oxides such as indium tin oxide, transparent conductive materials such as zinc oxide oxides, and non-transparent inorganic oxides having conductivity.
- the carbon-based material include carbon black.
- the carbide-based material examples include silicon carbide, chrome carbide, and titanium carbide.
- conductive fine particles that can be used non-conductive fine particles are surrounded by a conductive substance (metal, conductive inorganic oxide, carbon-based material, carbide-based material, etc.) that forms the conductive fine particles.
- fine particles eg, fine particles having a core-shell structure of a core “nonconductive material” and a shell “conductive material”.
- the non-conductive fine particles are not particularly limited, and non-conductive fine particles formed of various substances can be used.
- oxide fine particles such as silver oxide and copper oxide are dispersed in an organic solvent and applied, and then the coating film is placed in a reducing atmosphere to form a metal such as silver and copper. It can also be used after reducing. That is, the method for producing the conductive film is one of preferred embodiments including a step of reducing the oxide fine particles by applying the oxide fine particles dispersed in an organic solvent and then placing the oxide fine particles in a reducing atmosphere. .
- the organic solvent dispersion is a dispersion in which conductive fine particles are dispersed in an organic solvent, and may contain a substance other than the organic solvent and the conductive fine particles.
- the organic solvent is not particularly limited, and various organic solvents can be used.
- the organic solvent include aromatic carbons such as benzene hydrocarbons such as benzene, toluene, o-xylene, m-xylene, p-xylene, mixed xylene, ethylbenzene, hexylbenzene, dodecylbenzene, and phenylxylylethane.
- Hydrogen paraffinic hydrocarbons such as n-hexane and n-decane, isoparaffinic hydrocarbons such as Isopar (Isopar manufactured by Exxon Chemical), olefinic hydrocarbons such as 1-octene and 1-decene, cyclohexane and decalin Aliphatic hydrocarbons such as naphthenic hydrocarbons such as: Kerosene, petroleum ether, petroleum benzine, ligroin, industrial gasoline, coal tar naphtha, petroleum naphtha, solvent naphtha and other petroleum and coal-derived hydrocarbon mixtures; dichloromethane, chloroform , Carbon tetrachloride, 1,2-di Loroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, trichlorofluoroethane, tetrabromoethane, dibromotetrafluoroethane, tetrafluorod
- Ketones alcohols such as methanol, ethanol, isopropanol, octanol, methyl cellosolve; dimethyl silicone oil, methyl Silicone oils such as E alkenyl silicone oil; fluorine-based solvents hydrofluoroether like; carbon disulfide and the like are preferable.
- These organic solvents may be used alone or in combination of two or more.
- a hydrophobic organic solvent is preferable.
- a hydrophobic organic solvent water droplets can be taken into the organic solvent dispersion in a more stable form when placed in a humidified atmosphere.
- the organic solvent is preferably a nonpolar organic solvent. By being nonpolar, it becomes difficult to dissolve in water, which is a polar molecule, so that the form of water droplets taken into the coating film can be more suitably maintained.
- Nonpolar organic solvents include aromatic hydrocarbon solvents having about 6 to 10 carbon atoms such as benzene, toluene, xylene, hexane and cyclohexane; halogenated hydrocarbon solvents such as chloroform and dichloromethane; aliphatic hydrocarbon solvents A solvent etc. can be used preferably.
- aromatic hydrocarbon solvents having about 6 to 10 carbon atoms such as benzene, toluene, xylene, hexane and cyclohexane; halogenated hydrocarbon solvents such as chloroform and dichloromethane; aliphatic hydrocarbon solvents A solvent etc. can be used preferably.
- Benzene, toluene, hexane, cyclohexane and the like are more preferable from the viewpoint of the evaporation rate of the organic solvent and the solubility of water, that is, from the viewpoint that the evaporation rate is relatively fast, water droplets are easily con
- the organic solvent may be a mixed solvent of a polar solvent and a nonpolar solvent.
- a mixed solvent of an aromatic hydrocarbon solvent and a ketone solvent, a mixed solvent of an aromatic hydrocarbon and an amide solvent, or the like may be used.
- the specific gravity of the organic solvent is preferably not more than the specific gravity of water.
- the specific gravity of the organic solvent is preferably 1.00 or less, more preferably 0.95 or less, and still more preferably 0.90 or less at room temperature (20 ° C.). .
- the viscosity of the organic solvent is preferably 2 mPa ⁇ s or less at room temperature (20 ° C.). When water is taken into the applied organic solvent dispersion, if the viscosity of the organic solvent is too high, water droplets may not be taken in sufficiently.
- the organic solvent dispersion preferably contains an amphiphilic compound for water and the organic solvent.
- an amphiphilic compound By containing an amphiphilic compound, it becomes easy to maintain the shape of water droplets taken into the coating film by a surface active function in a suitable form, and for example, aggregation of water droplets can be controlled.
- the amphiphilic compound may be an amphiphilic low molecular compound or an amphiphilic polymer compound, and is not particularly limited. As a form that can further exhibit the surface active function, an amphiphilic polymer compound is preferable.
- the content of the amphiphilic compound is preferably 0.001 to 25% by mass with respect to 100% by mass of the organic solvent dispersion. By setting it as content of such a range, the form of the water droplet taken in in the apply
- the amount is less than 0.001% by mass, it is difficult to grow and transport water droplets on the surface of the coating film, and the aperture ratio may be lowered. If it exceeds 25% by mass, water droplets aggregate on the surface of the coating film, and there is a possibility that pores are not sufficiently formed. Moreover, there exists a possibility that electroconductivity may become difficult to express.
- the content of the amphiphilic compound is more preferably 0.001 to 15% by mass, still more preferably 0.001 to 5% by mass, and particularly preferably 0.01 to 1% by mass.
- the amphiphilic compound is preferably a compound having both a hydrophilic group and a hydrophobic group.
- the amphiphilic compound is added to prevent water droplets attached to the organic solvent dispersion coated on the substrate from fusing together.
- the amphiphilic compound is not particularly limited as long as it is a compound having an affinity for both water and an organic solvent.
- the hydrophobic group include a hydrocarbon having 5 to 20 carbon atoms. And nonpolar groups such as a group, a phenyl group, and a phenylene group.
- examples of the hydrophilic group include a hydroxyl group, a carboxyl group, an amino group, a carbonyl group, a sulfo group, an ester group, an amide group, and an ether group.
- amphiphilic compounds examples include anionic surfactants such as sodium alkyl sulfate, cationic surfactants such as alkyl ammonium chloride, nonionic surfactants such as polyoxyethylene alkyl ether and sorbitan fatty acid ester, octylamine, Examples thereof include alkylamines such as dodecylamine and amphiphilic polymers. From the viewpoint of solubility in organic solvents and water, nonionic surfactants and amphiphilic polymers are preferred. These amphiphilic compounds may be used alone or in combination of two or more.
- amphiphilic polymer a polymer having polyacrylamide as a main chain skeleton, a hydrophilic group and a hydrophobic group in the side chain, and co-polymerization of hydrophobic (meth) acrylate and hydrophilic (meth) acrylate
- Polymer, copolymer of polystyrene and hydrophilic (meth) acrylate, octadecyl isocyanate-modified polyethyleneimine (Epomin RP-20, manufactured by Nippon Shokubai Co., Ltd.) has a hydrophilic group in the main chain and a hydrophobic group in the side chain
- a main chain skeleton obtained by polycondensation of a block copolymer of polyethylene glycol and polypropylene glycol having a hydrophobic group and a hydrophilic group, or dichlorodiphenyl sulfone and a sodium salt of bisphenol A Polysulfone having a diphenylenedimethylmethylene group which is
- the amphiphilic polymer preferably has a weight average molecular weight of 5000 or more. If the weight-average molecular weight is 5000 or more, the pattern structure is less likely to collapse during solvent evaporation or firing. More preferably, the weight average molecular weight is 10,000 or more, still more preferably 50,000 or more, and particularly preferably 90000 or more.
- the number average molecular weight of the amphiphilic polymer is preferably 3000 or more. When the number average molecular weight is 3,000 or more, the pattern structure is not easily collapsed during solvent evaporation or firing.
- the number average molecular weight of the amphiphilic polymer is more preferably 5000 or more, further preferably 10,000 or more, and particularly preferably 20000 or more.
- the weight average molecular weight and the number average molecular weight are measured using, for example, gel permeation chromatography (GPC) HLC-8120 (manufactured by Tosoh Corporation) as a measuring device, and TSK-GEL GMHXL-L (manufactured by Tosoh Corporation) as a column. It can be measured as a molecular weight in terms of polystyrene.
- GPC gel permeation chromatography
- polymer having polyacrylamide as a main chain skeleton and a hydrophilic group and a hydrophobic group in a side chain include, for example, the following formula:
- n and m are the same or different and represent the number of repeating structural units
- CAP dodecylacrylamide
- the ratio of n to m (n / m) is preferably 1 to 15, more preferably 2 to 12, and still more preferably 3 to 10.
- hydrophobic (meth) acrylate examples include normal hexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, heptyl (meth) acrylate, benzyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl.
- hydrophilic (meth) acrylate examples include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate.
- hydrophobic radical polymerizable monomer such as hydrophobic (meth) acrylamide or styrene is used instead of the hydrophobic (meth) acrylate, and hydrophilic (meth) acrylamide, N is used instead of the hydrophilic (meth) acrylate.
- hydrophilic (meth) acrylamide, N is used instead of the hydrophilic (meth) acrylate.
- -Hydrophilic radically polymerizable monomers such as vinylpyrrolidone may be used.
- Each of the hydrophobic (meth) acrylate and the hydrophilic (meth) acrylate may be used alone or in combination of two or more. Moreover, a different component may be included.
- the organic solvent dispersion preferably has a conductive fine particle content of 0.05 to 10% by mass with respect to 100% by mass of the organic solvent dispersion.
- a conductive fine particle content of 0.05 to 10% by mass with respect to 100% by mass of the organic solvent dispersion.
- electroconductive fine particles may aggregate in an organic-solvent dispersion, and may be in the state which is not fully disperse
- the content of conductive fine particles is more preferably 0.1 to 10% by mass, and still more preferably 0.2 to 10% by mass.
- the organic solvent dispersion preferably has a moisture content before coating of 10% by mass or less.
- the organic solvent dispersion before coating contains a large amount of water, the water in the organic solvent dispersion becomes large water droplets due to surface tension, and the mesh may not be made fine. More preferably, the water content before coating is 5% by mass or less.
- the organic solvent dispersion is applied to a substrate.
- substrate is not specifically limited, What is necessary is just to be able to apply
- the substrate for example, various substrates such as a glass substrate, a plastic substrate, a single crystal substrate, a semiconductor substrate, and a metal substrate can be used.
- a transparent substrate such as a glass substrate or a transparent plastic substrate is preferably used as the substrate.
- the transparent substrate is a substrate having a high visible light transmittance. For example, the visible light transmittance at a wavelength of 400 to 700 nm is preferably 50% or more.
- the transmittance is 70% or more, and more preferably 80% or more.
- Use of a glass substrate or a plastic substrate is also preferable from the viewpoint of cost reduction.
- the plastic substrate include ester films such as polyethylene terephthalate and polyethylene naphthalate; acrylic films; cycloolefin films; olefin films; resin films such as polyamide, polyphenylene sulfide, and polycarbonate.
- a substrate having a hydrophilic surface is preferably used as the substrate on which the organic solvent dispersion is applied. Since the surface of the substrate is hydrophilic, water droplets can be easily brought into contact with the substrate, the penetration rate of the pores can be increased, and formation of an excessive polymer / particle film on the bottom surface of the pores can be prevented.
- the shape of the hole can be a conductive film having a high aperture ratio.
- the substrate having a hydrophilic surface preferably has a water contact angle of 90 ° or less. By being 90 ° or less, the shape of the water droplets taken into the organic solvent dispersion can be adjusted, and the shape of the pores can be made to have a high aperture ratio.
- the substrate on which the organic solvent dispersion is applied has been subjected to a hydrophilic treatment on the substrate surface.
- a hydrophilic treatment method is not particularly limited, but for example, a method of immersing in an alkaline solution is preferable. Although it does not specifically limit as an alkaline solution, A potassium hydroxide solution, a sodium hydroxide solution, etc. can be used preferably.
- a saturated potassium hydroxide ethanol solution or the like can be preferably used.
- the hydrophilization treatment include corona discharge treatment, plasma treatment, and UV-ozone treatment. It is preferable to select a preferable method as appropriate depending on the type of the substrate, the type of the organic solvent dispersion, and the like. Moreover, the value of the preferable contact angle mentioned above can be used for the contact angle of the board
- the manufacturing method preferably includes a step of baking a film obtained by evaporating the organic solvent. After evaporating the organic solvent, there is a possibility that the substance contained in the organic solvent dispersion such as the organic solvent remains in the mesh line portion where the conductive fine particles are present. There is a possibility that the conductive fine particles are separated from each other and the conductivity cannot be obtained. By performing the baking, even when the organic solvent is contained in the dried film, the organic solvent can be sufficiently evaporated and high conductivity can be obtained. Moreover, by conducting baking, the conductive fine particles can be bonded to each other to increase the conductivity.
- the firing temperature is not particularly limited, and varies depending on the metal material, the content of the conductive fine particles, the type of the organic solvent, the film thickness, and the like, and is performed under appropriate conditions under each condition.
- the firing temperature is preferably 400 ° C. or lower.
- the firing temperature is high, the conductive fine particles cannot be aggregated and bonded, and there is a possibility that sufficient conductivity cannot be obtained. More preferably, it is 300 degrees C or less as a calcination temperature, More preferably, it is 200 degrees C or less.
- the firing time is preferably within 2 hours, more preferably within 1 hour, and even more preferably within 30 minutes.
- the method for producing the conductive film preferably includes a step of performing electroless plating after the step of evaporating the organic solvent while allowing the applied organic solvent dispersion to condense on the coating film surface.
- the conductivity of the obtained conductive film can be further improved.
- the present invention is also a conductive film manufactured by the above manufacturing method.
- the conductive film becomes a network-like conductive film formed by a mesh-like line portion and a hole portion of a conductive substance, and is light transmissive and conductive. It can be set as the transparent conductive film which has. That is, the transparent conductive film produced by the above production method is also one aspect of the present invention. And by using the said manufacturing method, it becomes possible to manufacture the electroconductive film which has a light transmittance simply and cheaply.
- the form of the conductive film it is preferable that the average area of the pores is 400 ⁇ m 2 or less and the line width of the mesh-like line part is 5 ⁇ m or less.
- the average area of the pores is small and the line width of the mesh-like line part is narrow, a highly conductive and mesh-like conductive film can be formed.
- a more preferable form of the conductive film manufactured by the above manufacturing method is the same as the preferable form of the network-like conductive film described later. That is, the average area of the pores is more preferably 300 ⁇ m 2 or less, still more preferably 200 ⁇ m 2 or less, and particularly preferably 100 ⁇ m 2 or less.
- the hole portion preferably has an average maximum ferret diameter of 20 ⁇ m or less, and more preferably 10 ⁇ m or less.
- the aperture ratio due to the pores is preferably 60% or more, whereby a conductive film with improved light transmittance can be obtained.
- the aperture ratio due to the voids is more preferably 65% or more, further preferably 70% or more, particularly preferably 80% or more, and most preferably 90% or more.
- the line width of the mesh-like line portion is more preferably 2 ⁇ m or less, and further preferably 1 ⁇ m or less.
- the maximum ferret diameter is the maximum between two parallel lines drawn so as to be in contact with the outline of each hole, and is called the maximum ferret diameter. The average maximum ferret diameter is measured for each hole. The average of the maximum ferret diameter is called the average maximum ferret diameter.
- the present invention further relates to a network-like conductive film formed by a mesh-like line portion and a hole portion of a conductive substance, and the conductive film has an average area of the hole portion of 400 ⁇ m 2 or less.
- the conductive film is also a conductive film in which the line width of the mesh-like line portion is 5 ⁇ m or less. Since the average area of the pores is small and the line width of the mesh-like line part is narrow, a mesh-like transparent conductive film having high light transmittance and high uniformity can be formed. For example, as described above, when used in electronic paper or the like, a voltage can be uniformly applied to microcapsules that perform display.
- the mesh When the mesh is wide (the area of the pores is large), when the voltage is applied by a conductive film to change the color of the microcapsules, the pores must be fine if the mesh is not fine. The entire microcapsule is contained in the part, and no voltage is applied to such a capsule. Further, the finer mesh makes the conductivity more uniform. According to this, for example, when used for a touch panel, the accuracy of position recognition increases.
- a network-like conductive film can be formed using the above-described method for manufacturing a conductive film.
- the arrangement form of the mesh-like line portions and the hole portions in the conductive film may be random or regularly arranged.
- the term “random” means that the mesh-like line portions and the hole portions are not arranged based on a certain rule.
- the average area of the pores is 400 ⁇ m 2 or less, and the line width of the mesh-like line part is 5 ⁇ m or less, which means that the mesh of the conductive film is fine.
- the average area of the pores exceeds 400 ⁇ m 2 , the in-plane uniformity of the conductive film is not sufficient, and for example, there is a possibility that variations in light transmission and conductivity occur.
- the function as a conductive film may be insufficient due to the occurrence of a portion where no voltage is applied.
- the average area of the pores is more preferably 300 ⁇ m 2 or less, still more preferably 200 ⁇ m 2 or less, and particularly preferably 100 ⁇ m 2 or less.
- the hole portion preferably has an average maximum ferret diameter of 20 ⁇ m or less, and more preferably 10 ⁇ m or less.
- the line width of the mesh-like line portion is 5 ⁇ m or less, and the thin line width can suppress moire that may occur, for example, in a display or the like. When the line width of the mesh-like line portion exceeds 5 ⁇ m, the aperture ratio becomes small and the light transmittance may not be sufficient.
- the line width of the mesh-like line portion is more preferably 2 ⁇ m or less, and further preferably 1 ⁇ m or less. As described above, the light transmittance and conductivity of the conductive film can be controlled to more preferable values by controlling the average area of the hole portions and the line width of the mesh-like line portions.
- the conductive film preferably has an aperture ratio of 60% or more due to the pores. Since the light transmittance can be improved by increasing the aperture ratio, it can be suitably used for a display such as electronic paper. If it is less than 60%, sufficient light transmittance cannot be obtained, and there is a possibility that sufficient characteristics as a conductive film having transparency cannot be exhibited.
- the opening ratio due to the pores is more preferably 65% or more, further preferably 70% or more, particularly preferably 80% or more, and most preferably 90% or more.
- the aperture ratio, line width, average area of pores, and average maximum ferret diameter can be determined by the following methods.
- the image observed with a microscope (this is called the “original image”) is binarized into black and white using the above-mentioned image processing software so that the conductive part is black and the other part (mesh opening) is white. To do.
- the binarization threshold value the peak values of white and black are obtained from the tone histogram, and set to the intermediate value.
- black and white inversion processing of the binarized image is performed (this image is referred to as “binarized image”). At this time, the area ratio of the black portion with respect to the entire area is obtained and set as the aperture ratio.
- the area of the white part of a binarized image is calculated
- thinning processing image is performed (this image is referred to as “thinning processing image”).
- the area of the white part of the thinned image is obtained, and this is defined as the length (L) of the conductive part.
- the black portion of the binarized image is extracted (this image is referred to as “extracted image”).
- this image is referred to as “extracted image”.
- voids on the boundary are excluded.
- pores having an area of 1 ⁇ m 2 or less are also excluded.
- the area of each element and the maximum ferret diameter are measured and averaged to obtain the average area of the hole portion and the average maximum ferret diameter of the hole portion, respectively.
- the thickness of the mesh line portion is preferably 200 nm or more. When the thickness is 200 nm or more, sufficient conductivity can be obtained even if the line width is reduced. When the film thickness of the conductive film is less than 200 nm, the conductivity is low, and the characteristics as the conductive film may not be sufficiently exhibited. More preferably, the thickness of the mesh line portion is 1 ⁇ m or more. In addition, the thickness of a mesh line part is calculated
- the coating film was observed at a magnification of 50 times with a laser microscope (VK-9700, manufactured by Keyence Corporation), the maximum step of the coating film was measured at 10 positions from the observed image, and the average value was measured as conductivity. The maximum film thickness.
- the conductive film preferably has a light transmittance of 20% or more for visible light (wavelength: 400 to 700 nm). By increasing the light transmittance, for example, it can be suitably used for a display device such as electronic paper.
- the light transmittance is more preferably 40% or more, still more preferably 60% or more, and particularly preferably 80% or more.
- the light transmittance can be measured for light having a wavelength of 300 to 800 nm using, for example, a spectrophotometer (trade name “V-530”, manufactured by JASCO Corporation).
- the conductive film preferably has a total light transmittance of 20% or more.
- the total light transmittance is 20% or more, for example, it can be suitably used for a display device such as electronic paper. More preferably, it is 40% or more as a total light transmittance, More preferably, it is 60% or more, Most preferably, it is 75% or more.
- the total light transmittance can be measured according to JIS K7361-1, for example, using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
- the area of the mesh line portion is preferably an area that can ensure sufficient conductivity.
- the preferred area of the mesh line portion varies depending on the film thickness and area of the conductive film, the metal material constituting the conductive film, and the like.
- the sheet resistance in the plane of the conductive film is 10 5 ⁇ / ⁇ or less. It is preferable to set the area of the mesh-like line portion so as to be.
- the sheet resistance of the conductive film is more preferably 10 3 ⁇ / ⁇ or less, further preferably 10 2 ⁇ / ⁇ or less, and particularly preferably 10 ⁇ / ⁇ or less.
- the sheet resistance can be measured, for example, by a four-terminal four-probe method using a resistivity meter Lorester-GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd., probe: ASP probe).
- the said electroconductive substance will not be specifically limited if it is a substance which has electroconductivity,
- a metal, the inorganic oxide which has electroconductivity, a carbonaceous material, a carbide type material etc. are mentioned.
- Various metals can be used as the metal, and any form such as a single metal, an alloy, and a solid solution may be used.
- the metal element is not particularly limited.
- platinum, gold, silver, copper, aluminum, chromium, cobalt, tungsten, or the like can be used, but a metal having high conductivity is preferable.
- the metal having high conductivity preferably contains at least one selected from the group consisting of platinum, gold, silver and copper.
- the metal is preferably a metal having high chemical stability.
- the metal preferably contains at least one selected from the group consisting of platinum, gold and silver.
- the metal used as the conductive material contains silver.
- the inorganic oxide having conductivity include indium oxides such as indium tin oxide, transparent conductive materials such as zinc oxide oxides, and non-transparent inorganic oxides having conductivity.
- the carbon-based material include carbon black.
- the mesh-like line portion may contain a nonconductive substance.
- fine particles eg, core “non-conductive substance”, shell “conductive substance” in which a non-conductive substance is surrounded by a conductive substance (metal, conductive inorganic oxide, carbon-based material, carbide-based material, etc.) It may be in a form formed by sintering a fine particle having a core-shell structure.
- the use of the conductive film is not particularly limited, and can be used for any application that requires conductivity.
- it can be used as an electromagnetic wave shielding film (EMI shield film) used for a plasma display or the like, and can also be used as an electrode used for a display device of electronic paper (digital paper) or a liquid crystal display device. It can also be used for touch panels and the like.
- EMI shield film electromagnetic wave shielding film
- the present invention is also a conductive film used for digital paper.
- a mesh-like conductive film can be produced easily and inexpensively, the mesh is fine, the light transmittance is excellent, and the in-plane uniformity is excellent. Can be manufactured. Further, such a conductive film can be suitably used for displays such as electronic paper because the mesh is fine. Further, since it is excellent in in-plane uniformity, when applied to a display or the like, moire or the like can be prevented.
- FIG. 1-1 is a conceptual diagram of a cross section of a coating film over time showing an example of a process of evaporating an organic solvent while condensing a coated organic solvent dispersion on the coating film surface.
- FIGS. 1-2 (a) to (e) are conceptual diagrams showing a process of evaporating the organic solvent while the applied organic solvent dispersion is condensed on the surface of the coating film.
- FIG. 2 is a schematic plan view of a mesh-like conductive film in which pores and mesh-like line portions are formed.
- FIG. 3 is a schematic cross-sectional view showing a method of using a Peltier device to cool a substrate and a coating film and to evaporate while blowing a humidified gas onto the coating film.
- FIG. 1-1 is a conceptual diagram of a cross section of a coating film over time showing an example of a process of evaporating an organic solvent while condensing a coated organic solvent dispersion on the coating film surface.
- FIG. 4 is an optical microscope observation image showing the form of the film before firing and after firing.
- A-1) is an observation of a film before firing at a magnification of 20 times
- a-2) is an observation at a magnification of 100 times.
- B-1) is obtained by observing a film fired at 200 ° C. for 1 hour at a magnification of 20 times
- B-2) is observed at a magnification of 100 times.
- C-1) is obtained by observing a film fired at 300 ° C. for 30 minutes at a magnification of 20 times
- C-2) is observed at a magnification of 100 times.
- D-1) is obtained by observing a film fired at 400 ° C.
- FIG. 5 is an electron microscope observation image showing the form of the film before firing and after firing.
- FIG. 5A shows a film before firing
- FIG. 5B shows a film fired at 200 ° C. for 1 hour
- FIG. 5C shows a film fired at 300 ° C. for 30 minutes
- FIG. 5D shows a film that is baked at 400 ° C. for 30 minutes.
- FIG. 6 is an electron microscope observation image when a film fired at 200 ° C. for 1 hour is observed at a reduced magnification.
- FIG. 7 is an original image as a result of observing a film fired at 200 ° C. for 1 hour.
- FIG. 5A shows a film before firing
- FIG. 5B shows a film fired at 200 ° C. for 1 hour
- FIG. 5C shows a film fired at 300 ° C. for 30 minutes
- FIG. 5D shows a film that is baked at 400 ° C. for 30 minutes.
- FIG. 6 is an electron microscope observation image when a film fired at 200
- FIG. 8 is a binarized image of a film that has been baked at 200 ° C. for 1 hour.
- FIG. 9 is a thinned image of a film that has been baked at 200 ° C. for 1 hour.
- FIG. 10 is an extracted image of a film that has been baked at 200 ° C. for 1 hour. It is a schematic diagram which shows the measuring method of a surface shape image and an electric current image by AFM. It is the surface shape image (a) and current image (b) of the film
- FIG. 15 is an optical microscope observation image showing the form of the fired film prepared in Reference Example 1. It was observed at a magnification of 3000 times.
- FIG. 16 is an image diagram of a state when a voltage is applied to the digital paper of the eighth embodiment.
- FIG. 17 is an image diagram of a state when a voltage is applied to the digital paper of Comparative Example 2.
- ⁇ Method for preparing conductive fine particle dispersion (x-1)> A 1 L beaker containing 148.1 g of octylamine (manufactured by Wako Pure Chemical Industries, Ltd.) is placed in a constant temperature bath at 40 ° C. Next, 18.6 g of silver acetate (manufactured by Wako Pure Chemical Industries, Ltd.) is added and thoroughly stirred and mixed for 20 minutes to prepare a uniform mixed solution. Subsequently, a reduction treatment was performed by gradually adding 20 g of a 20 wt% sodium borohydride aqueous solution.
- a conductive fine particle dispersion (x-2) was obtained in the same manner as in the conductive fine particle dispersion (x-1) except that benzene was used instead of toluene.
- This solution was a solution containing 20 wt% of silver fine particles, 9 wt% of octylamine, and 71 wt% of benzene. When this solution was observed by FE-SEM, it was confirmed to be a nanoparticle dispersion having a particle size distribution with an average particle size of 4 nm and a coefficient of variation of 14%.
- a conductive fine particle dispersion solution (x-3) was prepared in the same manner as in the conductive fine particle dispersion solution (x-1) except that cyclohexane was used instead of toluene.
- This solution was a solution containing 20 wt% of silver fine particles, 9 wt% of octylamine, and 71 wt% of cyclohexane. When this solution was observed by FE-SEM, it was confirmed to be a nanoparticle dispersion having a particle size distribution with an average particle size of 4 nm and a coefficient of variation of 14%.
- the maximum thickness of the conductive film at this time is 1.60 ⁇ m for the film before firing, 1.07 ⁇ m for the film fired at 200 ° C. for 1 hour, and 1.07 ⁇ m for the film fired for 1 hour at 300 ° C. And 0.55 ⁇ m for the film fired at 400 ° C. for 1 hour.
- the maximum film thickness was observed with a laser microscope (VK-9700, manufactured by Keyence Corporation) at a magnification of 50 times. The maximum level difference of the coating film was measured at 10 locations from the observed image, and the average value was taken as the maximum film thickness of the conductive film.
- FIG. 4 is an optical microscope observation image showing the form of the film before firing and after firing.
- FIG. 4 (a-1) shows the film before firing observed at a magnification of 20 times, and (a-2) shows the film observed at a magnification of 100 times.
- FIG. 4 (b-1) shows a film fired at 200 ° C. for 1 hour, which was observed at a magnification of 20 times, and (b-2) was observed at a magnification of 100 times.
- FIG. 4 (c-1) shows a film fired at 300 ° C. for 30 minutes, which was observed at a magnification of 20 times, and (c-2) was observed at a magnification of 100 times.
- FIG. 4 (d-1) shows a film fired at 400 ° C.
- FIG. 5 is an electron microscope observation image showing the form of the film before firing and after firing.
- FIG. 5A shows a film before firing
- FIG. 5B shows a film fired at 200 ° C. for 1 hour
- FIG. 5C shows a film fired at 300 ° C. for 30 minutes
- FIG. 5D shows a film that is baked at 400 ° C. for 30 minutes.
- FIG. 6 is an electron microscope observation image when a film that has been baked at 200 ° C. for 1 hour is observed at a reduced magnification.
- both the film before firing and the film after firing are conductive films in which a mesh line portion and a void portion are formed.
- hole part were calculated
- the aperture ratio was 80%
- the line width was 1.1 ⁇ m
- the average area of the holes was 60.4 ⁇ m 2
- FIG. 7 is an original image as a result of observing a film fired at 200 ° C. for 1 hour.
- the binarization threshold value the peak values of white and black are obtained from the tone histogram, and set to the intermediate value.
- FIG. 8 is a binarized image of a film that has been baked at 200 ° C. for 1 hour. At this time, the area ratio of the black portion with respect to the entire area was determined and used as the aperture ratio.
- FIG. 9 is a thinned image of a film that has been baked at 200 ° C. for 1 hour.
- the area of the white part of the thinned image was obtained, and this was defined as the length (L) of the conductive part.
- FIG. 10 is an extracted image of a film that has been baked at 200 ° C. for 1 hour.
- the gray part is the extracted hole part (hole part counted for averaging), and the black part is the hole part not counted.
- the numbers in FIG. 10 are numbers when the number of extracted holes is counted.
- voids on the boundary were excluded.
- pores having an area of 1 ⁇ m 2 or less were also excluded.
- the area of each element and the maximum ferret diameter of each hole portion were measured and averaged to obtain the average area of the hole portion and the average maximum ferret diameter of the hole portion, respectively.
- FIG. 11 shows a schematic diagram of an AFM measuring apparatus. As shown in FIG.
- FIG. 12 shows a surface shape image (a) and a current image (b) for a film baked at 200 ° C. for 1 hour by AFM measurement.
- FIG. 13 shows a surface shape image (a) and a current image (b) of a film baked at 400 ° C. for 30 minutes by AFM measurement.
- the transmittance was evaluated for the conductive film before firing and after firing.
- the transmittance was measured for light having a wavelength of 300 to 800 nm using a spectrophotometer (trade name “V-530”, manufactured by JASCO Corporation).
- V-530 trade name “V-530”, manufactured by JASCO Corporation.
- FIG. 13 is a graph in which the vertical axis represents the transmittance and the horizontal axis represents the wavelength of light. In the film fired at 200 ° C. for 1 hour, the transmittance was about 20 to 70% for light having a wavelength of 300 to 700 nm.
- the conductive film in all wavelength ranges.
- a transmittance equal to or higher than the aperture ratio can be obtained. Further, the light transmittance was 40 to 90% in the film fired at 300 ° C. for 30 minutes and the film fired at 400 ° C. for 30 minutes.
- the maximum film thickness of the conductive film at this time was 0.2 ⁇ m
- the sheet resistance of the conductive film was 8.0 ⁇ 10 2 ⁇ / ⁇
- the total light transmittance was 77%.
- the aperture ratio, the line width, the average area of the pores, and the average maximum ferret diameter of the pores of the conductive film were obtained.
- the sheet resistance and total light transmittance of the conductive film were measured as follows.
- ⁇ Drying conditions> It was dried (air-dried) at room temperature and normal pressure.
- ⁇ Baking conditions> The dried film was heated at 10 ° C./min in an electric furnace at normal pressure and air atmosphere, and baked at 300 ° C. for 15 minutes. After firing, it was allowed to cool naturally and cooled to room temperature. At this time, the maximum film thickness of the conductive film was 0.4 ⁇ m, the sheet resistance of the conductive film was 46 ⁇ / ⁇ , and the total light transmittance was 63%. Further, the aperture ratio, the line width, the average area of the pores, and the average maximum ferret diameter of the pores of the conductive film were obtained.
- the organic solvent was evaporated by spraying to form a dry film.
- ⁇ Drying conditions> It was dried (air-dried) at room temperature and normal pressure.
- ⁇ Baking conditions> The dried film was heated in an electric furnace at normal pressure and an air atmosphere at 10 ° C./min, and baked at 200 ° C. for 1 hour and 150 ° C. for 1 hour. After firing, it was allowed to cool naturally and cooled to room temperature.
- the maximum film thickness of the conductive film was 0.5 ⁇ m
- the sheet resistance of the conductive film was 20 ⁇ / ⁇
- the total light transmittance was 28%.
- the aperture ratio, the line width, the average area of the pores, and the average maximum ferret diameter of the pores of the conductive film were obtained.
- the maximum film thickness of the conductive film was 0.8 ⁇ m
- the sheet resistance of the conductive film was 3.5 ⁇ 10 2 ⁇ / ⁇
- the total light transmittance was 30%.
- the aperture ratio, the line width, the average area of the pores, and the average maximum ferret diameter of the pores of the conductive film were obtained.
- a / ml cyclohexane solution was prepared.
- the organic solvent was evaporated by spraying to form a dry film.
- ⁇ Drying conditions> It was dried (air-dried) at room temperature and normal pressure.
- ⁇ Baking conditions> The dried film was heated at 10 ° C./min in an electric furnace at normal pressure and air atmosphere, and baked at 180 ° C. for 15 minutes. After firing, it was allowed to cool naturally and cooled to room temperature. At this time, the maximum film thickness of the conductive film was 0.9 ⁇ m, the sheet resistance of the conductive film was 42 ⁇ / ⁇ , and the total light transmittance was 43%. Further, the aperture ratio, the line width, the average area of the pores, and the average maximum ferret diameter of the pores of the conductive film were obtained.
- ⁇ Drying conditions> It was dried (air-dried) at room temperature and normal pressure.
- ⁇ Baking conditions> The dried film was heated at 10 ° C./min in an electric furnace at normal pressure and air atmosphere, and baked at 180 ° C. for 15 minutes. After firing, it was allowed to cool naturally and cooled to room temperature. At this time, the maximum film thickness of the conductive film was 0.8 ⁇ m, the sheet resistance of the conductive film was 6 ⁇ / ⁇ , and the total light transmittance was 42%. Further, the aperture ratio, the line width, the average area of the pores, and the average maximum ferret diameter of the pores of the conductive film were obtained.
- ⁇ Porous membrane preparation conditions As the conductive fine particles, a silver fine particle dispersion solution (chloroform solution) manufactured by Samsung Belts was used, and a chloroform solution having a silver weight concentration of 2.75 mg / ml was prepared. In an atmosphere of 23 ° C. and a relative humidity of 70%, 2.0 ml of the solution was applied onto a 5 cm square glass substrate, and humidified air (relative humidity 70%) was blown at a flow rate of 1.6 m / min for 10 minutes. And the organic solvent was evaporated to form a dry film.
- FIG. 15 is an optical microscope observation image showing the form of the fired film prepared in Reference Example 1. Optical microscope observation was performed at a magnification of 3000 times using a digital microscope VHX-100 (manufactured by Keyence Corporation). As a result of observation, the surface was uneven, but no pattern was formed. In FIG. 15, it can be observed that the white portion is a convex portion, the black portion is a concave portion, and the unevenness of the silver film covers the entire surface. In such a case, it can be said that there is no transparency and transparency.
- ⁇ Baking conditions> The dried film was heated at 10 ° C./min in an electric furnace at normal pressure and air atmosphere, and baked at 300 ° C. for 15 minutes. After firing, it was allowed to cool naturally and cooled to room temperature. When the form of the prepared film after baking was observed with a digital microscope as in Reference Example 1, the pattern structure could not be observed, and a silver thin film was formed on the entire surface.
- the organic solvent was evaporated to form a dry film.
- ⁇ Drying conditions> It was dried (air-dried) at room temperature and normal pressure.
- ⁇ Baking conditions> The dried film was heated at 10 ° C./min in an electric furnace at normal pressure and air atmosphere, and baked at 180 ° C. for 15 minutes. After firing, it was allowed to cool naturally and cooled to room temperature.
- ⁇ Result> The pattern was not made, and silver nanoparticles were applied to the entire surface.
- Example 8 With reference to a comparative example in Japanese Patent Laid-Open No. 2005-338189, a digital paper was produced as follows. ⁇ TiO 2 > A 300 mL four-necked flask was charged with 100 g of titanium oxide (product name: Taipei CR-97, manufactured by Ishihara Sangyo Co., Ltd.), 100 g of n-hexane and 4 g of octadecyltrichlorosilane (product name: LS6495, manufactured by Shin-Etsu Chemical Co., Ltd.), While stirring and mixing, the flask was placed in an ultrasonic bath at 55 ° C.
- titanium oxide product name: Taipei CR-97, manufactured by Ishihara Sangyo Co., Ltd.
- octadecyltrichlorosilane product name: LS6495, manufactured by Shin-Etsu Chemical Co., Ltd.
- ⁇ CB> A 200 mL beaker was charged with 5 g of carbon black (product name: MA100, manufactured by Mitsubishi Chemical Corporation) and 172.5 g of methyl methacrylate, and subjected to a dispersion treatment with an ultrasonic homogenizer (product name: BRANSON 5210, manufactured by Yamato Corporation). 3.5 g of azobisbutyronitrile was added and dissolved to obtain a monomer composition.
- the particle size (volume average particle size) of the black fine particles was measured by using a laser diffraction / scattering type particle size distribution analyzer (product name: LA-910, manufactured by Horiba, Ltd.) and found to be 0.8 ⁇ m.
- the dispersion was filtered, washed and dried to obtain black fine particles (p2).
- ⁇ Ink conversion> 85.6 g of Isopar M (Exxon Chemical Co., Ltd.) was charged with 3.1 g of black fine particles (p2) and 11.5 g of titanium oxide (p1), and subjected to a dispersion treatment for 2 hours in an ultrasonic bath. A liquid (i1) was obtained.
- the volume average particle diameter of the microcapsules (cm1) for electrophoretic display devices was 51.1 ⁇ m. This dispersion was classified by passing it through a mesh having an aperture of 80 ⁇ m and 30 ⁇ m to obtain a paste (solid content: 57 wt%) of an electrophoretic display device microcapsule (cm1) having a particle size of 30 to 80 ⁇ m.
- ⁇ Coating fluid> 2.1 g of an alkali-soluble acrylic resin emulsion (product name: WR503A, manufactured by Nippon Shokubai Co., Ltd., resin content: 30 wt%) was diluted with water to a solid content of 5 wt%, and 25 wt% ammonia was added thereto.
- Example 2 According to Example 10 of JP-T-2005-530005, a conductive film on which a silver pattern conductive film was formed was produced.
- the line width of the conductive film was 3.2 ⁇ m
- the average area of the holes was 5673 ⁇ m 2
- the average maximum ferret diameter of the holes was 84 ⁇ m.
- An electrophoretic display device (d2) having a counter electrode was prepared by laminating a conductive film on which a silver conductive film was formed on the coated surface of the electrophoretic display device sheet (s1). When a voltage of 3 V was applied to the device (d2), only the microcapsules on the silver pattern were electrophoresed, and the microcapsules not on the silver pattern were not electrophoresed.
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Abstract
Description
光透過性を有する導電性膜としては、現在では、酸化インジウム錫(ITO)が用いられることが一般的である。酸化インジウム錫により作成された導電性膜は、光透過性、導電性のバランスに優れており、通常の液晶ディスプレイ等だけではなく、例えば、タッチパネル用途等にも使用されている。しかしながら、インジウムのような希金属は高価であり、また、資源枯渇のおそれがあるため、より安価で、資源枯渇のおそれが少ない材料を用いた光透過性を有する導電性膜が求められているところであった。また、ITOの成膜には通常、スパッタリング法等が用いられているため、生産性が低い点でも改善の余地があった。
図2の焼成後に得られたもののSEM写真を見ると、確かに網目状構造の規則性は消失している。しかしながら、二次元ネットワークに関しては、それを形成していることは確認できず、表面の全面に渡り無秩序な凹凸が形成されているとしか見えない。そのような状態においては、開口部の面積が充分に確保されないものと考えられる。
また特許文献7(本件発明の基礎出願後に公開)に開示された透明電極及びその製造方法ついては、上記のように焼成後に網目状構造の規則性は消失していて、網目状の導電性膜の製造方法とはなっていない。また後述する参考例で示されているように、銀の膜が全面において凹凸を形成しているだけであり、表面全面を覆って開口率が無いということになり、透明性も認められないものである。従って、網目状の導電性膜を製造するということを開示する従来技術は見当たらず、このような課題を解決することができれば、導電性フィルム等の導電性材料を用いる技術分野において、液晶ディスプレイ、プラズマディスプレイ、電子ペーパー(デジタルペーパー)等に対して種々の用途展開を図ることができ、大きな技術的意義があるといえる。
上記のような従来の技術とは相違して、塗布された導電性微粒子を含む有機溶媒分散体を、塗膜表面で結露させながら有機溶媒を蒸発させる工程を含む導電性膜の製造方法とすることによって、簡易かつ安価に網目状の導電性膜を製造することができ、また、生産性を向上させることができることを見いだした。更に、上記方法で製造した導電性膜は、線幅が小さく、網目の細かいものとすることができることを見いだし、本発明に到達したものである。網目状の導電性膜とすることができれば、近年急速に需要、用途が拡大している導電性材料における新たな導電性付与手法となり、種々の用途展開が期待されるところである。
本発明はまた、導電性物質の網目状線部と空孔部とによって形成された網目状の導電性膜であって、該導電性膜は、空孔部の平均面積が400μm2以下であり、網目状線部の線幅が5μm以下である導電性膜でもある。
以下に本発明を詳述する。
なお、網目状の導電性膜における網目状線部と空孔部との配置形態としては、ランダム状であってもよいし、規則的に並んでいる状態であってもよい。その例としては、後述する図6~10等で示されるようなものである。これらの図においては、大きめの網目や小さめの網目が混在し、いくつか網目が切れているところもあるが、全体的に見れば、ミクロな技術分野において網目状の構造が認められると評価されるものである。すなわち、マイクロスコープで観察して、網目状の構造が確認できればよい。網目状の構造は、導電性膜全面に形成されていることが好ましいが、導電性膜が用いられる用途に応じて適宜設定されればよく、導電性膜としての機能が発揮され得る限り部分的であってもよい。その他の網目状の好ましい形態については後述する。
それに対して、特許文献7に開示された透明電極及びその製造方法においては、同文献の図2に示される通り、網目状構造は消失したと評価されることになる。これを確認したものが、後述する図15である。また、後述する参考例3のように、銀粒子が網目状の開口部の底の部分にも析出していることが認められ、基材が直接観察できる領域が無いと評価される場合も網目状の導電性膜とはならない。
上記のことから、本発明の導電性膜の製造方法は、塗布された有機溶媒を、塗膜表面で結露が生じる条件で蒸発させる工程を含むものということもできる。塗膜表面で結露が生じる条件とは、例えば、有機溶媒を蒸発させる雰囲気の露点を、塗膜表面の温度よりも高いものとする条件である。結露を生じさせる方法としては特に限定されるものではないが、例えば、塗膜表面の温度を、有機溶媒を蒸発させる雰囲気の露点以下に冷却する方法、上記有機溶媒を蒸発させる雰囲気を加湿雰囲気として、該雰囲気の露点を塗膜表面の温度より高くする方法等が好適である。これらの方法は、一つの方法で用いてもよいし、複数の方法を組み合わせて用いてもよい。複数の方法を組み合わせて行うことによって、有機溶媒を蒸発させる条件をより精密に制御することができ、導電性膜の形態を調整することができる。
また、図3に示すように、ペルチェ素子20を用いて、基板21及び塗膜22の冷却を行い、更に加湿気体を塗布された有機溶媒分散体に吹きつけることにより有機溶媒を蒸発させる方法は、本発明の導電性膜の製造方法の好適な形態の一つである。すなわち、上記製造方法は、基板及び塗膜の冷却を行い、かつ加湿気体を塗膜に吹きつけ、該塗膜表面で結露させながら有機溶媒を蒸発させる工程を含む製造方法が好ましい。
上記導電性微粒子の形状は、球状に限られず、例えば、楕円球状、立方体状、直方体状、ピラミッド状、針状、柱状、棒状、筒状、りん片状、板状(例えば、六角板状)等の薄片状、紐状等の形状でも好適に用いることができる。
上記有機溶媒としては、例えば、ベンゼン、トルエン、o-キシレン、m-キシレン、p-キシレン、混合キシレン、エチルベンゼン、ヘキシルベンゼン、ドデシルベンゼン、フェニルキシリルエタン等のベンゼン系炭化水素等の芳香族炭化水素類;n-ヘキサン、n-デカン等のパラフィン系炭化水素、アイソパー(Isopar、エクソン化学社製)等のイソパラフィン系炭化水素、1-オクテン、1-デセン等のオレフィン系炭化水素、シクロヘキサン、デカリン等のナフテン系炭化水素等の脂肪族炭化水素類;ケロシン、石油エーテル、石油ベンジン、リグロイン、工業ガソリン、コールタールナフサ、石油ナフサ、ソルベントナフサ等の石油や石炭由来の炭化水素混合物;ジクロロメタン、クロロホルム、四塩化炭素、1,2-ジクロロエタン、1,1,1-トリクロロエタン、1,1,2,2-テトラクロロエタン、トリクロロフルオロエタン、テトラブロモエタン、ジブロモテトラフルオロエタン、テトラフルオロジヨードエタン、1,2-ジクロロエチレン、トリクロロエチレン、テトラクロロエチレン、トリクロロフルオロエチレン、クロロブタン、クロロシクロヘキサン、クロロベンゼン、o-ジクロロベンゼン、ブロモベンゼン、ヨードメタン、ジヨードメタン、ヨードホルム等のハロゲン化炭化水素類;酢酸エチル、酢酸ブチル等のエステル類;アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類;メタノール、エタノール、イソプロパノール、オクタノール、メチルセロソルブ等のアルコール類;ジメチルシリコーンオイル、メチルフェニルシリコーンオイル等のシリコーンオイル類;ハイドロフルオロエーテル等のフッ素系溶剤;二硫化炭素等が好ましい。これらの有機溶媒は、単独で用いても2種以上を併用してもよい。
また、上記両親媒性高分子の数平均分子量は3000以上であることが好ましい。数平均分子量が3000以上の両親媒性高分子であると、溶媒蒸発時や焼成の際にパターン構造が崩れにくくなる。両親媒性高分子の数平均分子量としては、5000以上であることがより好ましく、10000以上であることが更に好ましく、20000以上であることが特に好ましい。
重量平均分子量及び数平均分子量は、例えば、測定装置として、ゲル浸透クロマトグラフィ(GPC)HLC-8120(東ソー社製)を使用し、カラムにTSK-GEL GMHXL-L(東ソー社製)を用いて、ポリスチレン換算の分子量として測定することができる。
式中、mに対するnの比率(n/m)としては、1~15が好ましく、より好ましくは、2~12であり、更に好ましくは、3~10である。
疎水性(メタ)アクリレート及び親水性(メタ)アクリレートはそれぞれ単独で用いてもよいし、2種以上を併用してもよい。また、異なる成分を含んでいてもよい。
上記有機溶媒分散体を塗布する基板は、基板表面に親水化処理を行われたものであることが好ましい。これによれば、上述のように、有機溶媒分散体中に取り込まれた水滴を好適な形状で保持することができる。また、基板表面の親水性を制御することによって、導電性膜の形状を更に制御することができる。親水化処理の方法としては、特に限定されるものではないが、例えば、アルカリ性溶液に浸漬させる方法が好ましい。アルカリ性溶液としては、特に限定されるものではないが、水酸化カリウム溶液、水酸化ナトリウム溶液等を好ましく用いることができる。具体的には、飽和水酸化カリウムエタノール溶液等を好ましく用いることができる。また、親水化処理の方法としては、コロナ放電処理、プラズマ処理、UV-オゾン処理を行う方法等が挙げられる。このような方法は、基板の種類、有機溶媒分散体の種類等によって適宜好ましい方法を選択することが好ましい。また、親水化による基板の接触角は、上述した好ましい接触角の値を用いることができる。
上記導電性膜の形態としては、空孔部の平均面積が400μm2以下であり、網目状線部の線幅が5μm以下であることが好ましい。空孔部の平均面積が小さく、網目状線部の線幅が細いことによって、光の透過性が高く、均一性の高い網目状の導電性膜を形成することができる。また、上記製造方法により製造される導電性膜のより好ましい形態としては、後述する網目状の導電性膜の好ましい形態と同様である。すなわち、空孔部の平均面積としてより好ましくは、300μm2以下であり、更に好ましくは、200μm2以下であり、特に好ましくは、100μm2以下である。また、上記空孔部は、平均最大フェレ径が20μm以下であることが好ましく、10μm以下であることがより好ましい。空孔部による開口率としては、60%以上であることが好ましく、これにより光透過率を高めた導電性膜とすることができる。空孔部による開口率は65%以上であることがより好ましく、更に好ましくは、70%以上であり、特に好ましくは、80%以上であり、最も好ましくは、90%以上である。上記網目状線部の線幅としてより好ましくは、2μm以下であり、更に好ましくは、1μm以下である。なお、最大フェレ径とは、各空孔部の輪郭に接するように引いた2本の平行線間の最大のものを最大フェレ径といい、平均最大フェレ径とは、計測した各空孔部の最大フェレ径の平均をとったものを平均最大フェレ径という。
開口率、線幅、空孔部の平均面積及び平均最大フェレ径については、以下の方法により求めることができる。
導電性膜の表面を超高分解能電界放出形走査電子顕微鏡(日立ハイテクノロジーズ社製、S-4800)にて倍率1000倍で観察し、観察した画像を画像処理ソフト(Image-Pro Plus ver.4.0、米国Media Cybernetics社製)を用いて、以下の方法で処理し、導電膜の開口率、線幅、空孔部の平均面積、フェレ径を求める。
導電部の線幅=S/L (1)
なお、上記全光線透過率は、例えば、ヘイズメーター NDH5000(日本電色工業社製)を用いて、JIS K7361-1に準拠して測定することができる。
なお、上記シート抵抗は、例えば、抵抗率計 ロレスター-GP(三菱化学アナリテック社製、プローブ:ASPプローブ)を用いて、四端子四探針法により測定することができる。
このように、本発明はまた、デジタルペーパーに用いられる導電性膜でもある。
オクチルアミン(和光純薬工業株式会社製)148.1gをいれた1Lビーカーを40℃の恒温槽に入れる。次に酢酸銀(和光純薬工業株式会社製)18.6gを添加し20分間充分に攪拌混合し、均一な混合溶液を調整する。続いて、20wt%水素化ホウ素ナトリウム水溶液20gを徐々に添加することにより還元処理を実施した。
還元処理後、アセトンを200g添加し、しばらく放置後、ろ過により銀及び有機物からなる沈殿物を分離回収する。回収物にトルエンを添加し、再溶解後、10℃以下まで冷却させた後、再度ろ過し、不純物を低減させたトルエン分散溶液を調整した。次に、エバボレーターによりトルエンを留去し、銀微粒子を20wt%含有する導電性微粒子分散溶液(x-1)を調整した。この溶液は、銀微粒子の他にオクチルアミン9wt%、トルエン71wt%を含有する溶液であった。この溶液をFE-SEMで観察したところ、平均粒子径4nm、変動係数が14%の粒子径分布をもつナノ粒子分散体であることが確認された。
トルエンの代わりにベンゼンを用いた以外は、導電性微粒子分散溶液(x-1)と同様に調整し、導電性微粒子分散溶液(x-2)を得た。この溶液は、銀微粒子を20wt%、オクチルアミンを9wt%、ベンゼンを71wt%含有する溶液であった。この溶液をFE-SEMで観察したところ、平均粒子径4nm、変動係数が14%の粒子径分布をもつナノ粒子分散体であることが確認された。
トルエンの代わりにシクロヘキサンを用いた以外は、導電性微粒子分散溶液(x-1)と同様に調整し、導電性微粒子分散溶液(x-3)を得た。この溶液は、銀微粒子を20wt%、オクチルアミンを9wt%、シクロヘキサンを71wt%含有する溶液であった。この溶液をFE-SEMで観察したところ、平均粒子径4nm、変動係数が14%の粒子径分布をもつナノ粒子分散体であることが確認された。
<多孔質膜作製条件>
導電性微粒子分散溶液(x-1)を用いて、銀の重量濃度として2.5mg/ml、CAP(n:m=4:1、Mn=99000、Mw=280000)1.0mg/mlのトルエン溶液を調整した。スライドカラスを飽和水酸化カリウムエタノール溶液に2時間浸漬後、エタノール、水で超音波洗浄を行うことにより、親水化処理を行った。このときの基板の接触角は、測定できないほど低く、ほぼ0°であった。0.5ml程度の溶液を上記基板上に塗布し、ペルチェ素子で基板を8℃に冷却して加湿空気(相対湿度50%以上)を0.8m/minの流速で、20分間吹きつけて有機溶媒を蒸発させて、乾燥製膜した。
<乾燥条件>
室温、常圧下で乾燥(風乾)した。
<焼成条件>
乾燥を行った後の膜を、電気炉で常圧、空気雰囲気下で10℃/分で昇温した。3つの試料を用いて行い、それぞれ、200℃で1時間、300℃で30分、400℃で30分の焼成を行った。焼成後、自然放冷し、室温まで冷却した。このときの導電性膜の最大膜厚としては、焼成前の膜では1.60μm、200℃で1時間の焼成を行った膜では1.07μm、300℃で1時間の焼成を行った膜ではで0.51μm、400℃で1時間の焼成を行った膜では0.35μmであった。
なお、最大膜厚は、レーザー顕微鏡(VK-9700、キーエンス社製)で倍率50倍で塗膜を観測した。観察した画像から塗膜の最大の段差を10箇所で計測し、平均した値を導電性膜の最大膜厚とした。
図5は、焼成前、焼成後の膜の形態を示す電子顕微鏡観察像である。図5(a)は、焼成前の膜、図5(b)は、200℃で1時間の焼成を行った膜、図5(c)は、300℃で30分間の焼成を行った膜、図5(d)は、400℃で30分間の焼成を行った膜である。また、図6は、200℃で1時間の焼成を行った膜を倍率を下げて観察したときの電子顕微鏡観察像である。
導電性膜の表面を超高分解能電界放出形走査電子顕微鏡(S-4800、日立ハイテクノロジーズ社製)にて倍率1000倍で観察し、観察した画像を画像処理ソフト(Image-Pro Plus ver.4.0、米国Media Cybernetics社製)を用いて、以下の方法で処理し、導電膜の開口率、線幅、空孔部の平均面積、フェレ径を求めた。
導電部の線幅=S/L (1)
測定条件
導電測定AFMホルダ(セイコーインスツル社製)を用いて測定した。焼成後のサンプルを約1cm角に切り出し、端部をドータイト銀ペーストで固定した。金コートした探針を用い、探針と基板の間にバイアス電圧1~5Vを印加して表面形状像と電流像の同時測定を行った。スキャン範囲は50μm四方である。図11に、AFM測定装置の模式図を示す。図11に示すように、ピエゾステージ31上に試料ステージ32を乗せ、その上に基板上に導電性膜を形成した試料33を設置する。そして、金コート探針34により試料33の表面を走査しながら、試料の表面形状を観察した。また、銀ペースト35により試料表面の導電性膜と試料ステージとを連結することにより、金コート探針34と銀ペースト35との間に1~5Vのバイアスを印加することによって、電流像を観察した。図12に、AFM測定によって、200℃で1時間焼成を行った膜について、表面形状像(a)、電流像(b)を示す。また、図13に、AFM測定によって、400℃で30分間焼成を行った膜について、表面形状像(a)、電流像(b)を示す。
400℃で30分間の焼成を行った膜においては、図13(a)の表面形状像から空孔部と網目状線部とが形成された膜であることを確認したが、導電性物質の凝集等によって好適な状態で導電性のネットワークが形成されておらず、図13(b)の電流像からは、電流が流れていることを確認することができなかった。
<多孔質膜作製条件>
導電性微粒子分散溶液(x-2)を用いて、銀の重量濃度として1.0mg/ml、CAP(n:m=4:1、Mn=99000、Mw=280000)1.0mg/mlのベンゼン溶液を調整した。25℃、相対湿度50%の雰囲気下で、2.0mlの溶液を5cm角のスライドガラス基板上に塗布し、加湿空気(相対湿度90%以上)を0.6m/minの流速で、10分間吹きつけて有機溶媒を蒸発させて、乾燥製膜した。
<乾燥条件>
室温、常圧下で乾燥(風乾)した。
<焼成条件>
乾燥を行った後の膜を、電気炉で常圧、空気雰囲気下で10℃/分で昇温し、300℃で30分間焼成を行った。焼成後、自然放冷し、室温まで冷却した。このときの導電性膜の最大膜厚は、0.2μmであり、導電性膜のシート抵抗は、8.0×102Ω/□、全光線透過率は、77%であった。また、導電性膜の開口率、線幅、空孔部の平均面積、空孔部の平均最大フェレ径を求めた結果、表1の通りであった。
なお、導電性膜のシート抵抗、全光線透過率は、以下のようにして測定された。
導電性膜のシート抵抗は、抵抗率計 ロレスター-GP(三菱化学アナリテック社製、プローブ:ASPプローブ)を用いて、四端子四探針法により測定した。
<全光線透過率>
導電性膜の全光線透過率は、ヘイズメーター NDH5000(日本電色工業社製)を用いて、JIS K7361-1に準拠して測定した。
<多孔質膜作製条件>
導電性微粒子分散溶液(x-3)を用いて、銀の重量濃度として1.0mg/ml、CAP(n:m=7.6:1、Mn=25000、Mw=95000)1.0mg/mlのシクロヘキサン溶液を調整した。25℃、相対湿度50%の雰囲気下で、2.0mlの溶液を5cm角のスライドガラス基板上に塗布し、加湿空気(相対湿度90%以上)を0.6m/minの流速で、10分間吹きつけて有機溶媒を蒸発させて、乾燥製膜した。
<乾燥条件>
室温、常圧下で乾燥(風乾)した。
<焼成条件>
乾燥を行った後の膜を、電気炉で常圧、空気雰囲気下で10℃/分で昇温し、300℃で15分間焼成を行った。焼成後、自然放冷し、室温まで冷却した。このときの導電性膜の最大膜厚は、0.4μmであり、導電性膜のシート抵抗は、46Ω/□、全光線透過率は、63%であった。また、導電性膜の開口率、線幅、空孔部の平均面積、空孔部の平均最大フェレ径を求めた結果、表1の通りであった。
<多孔質膜作製条件>
導電性微粒子分散溶液(x-3)を用いて、銀の重量濃度として1.0mg/ml、エポミンRP20(オクタデシルイソシアネート変性ポリエチレンイミン、日本触媒社製、Mn=6500、Mw=13700)1.0mg/mlのシクロヘキサン溶液を調整した。23℃、相対湿度70%の雰囲気下で、2.0mlの溶液を5cm角のスライドガラス基板上に塗布し、加湿空気(相対湿度70%以上)を1.5m/minの流速で、10分間吹きつけて有機溶媒を蒸発させて、乾燥製膜した。
<乾燥条件>
室温、常圧下で乾燥(風乾)した。
<焼成条件>
乾燥を行った後の膜を、電気炉で常圧、空気雰囲気下で10℃/分で昇温し、200℃で1時間、150℃で1時間焼成を行った。焼成後、自然放冷し、室温まで冷却した。このときの導電性膜の最大膜厚は、0.5μmであり、導電性膜のシート抵抗は、20Ω/□、全光線透過率は、28%であった。また、導電性膜の開口率、線幅、空孔部の平均面積、空孔部の平均最大フェレ径を求めた結果、表1の通りであった。
<多孔質膜作製条件>
導電性微粒子分散溶液(x-3)を用いて、銀の重量濃度として3.7mg/ml、シクロへキシルメタクリレート-プラクセルFM-1(カプロラクトン変性メタクリレート)共重合体(シクロへキシルメタクリレート:プラクセルFM-1のモル比9:1、Mn=25000、Mw=93000)0.11mg/mlのシクロヘキサン溶液を調整した。23℃、相対湿度70%の雰囲気下で、2.0mlの溶液を5cm角のスライドガラス基板上に塗布し、加湿空気(相対湿度70%以上)を1.6m/minの流速で、10分間吹きつけて有機溶媒を蒸発させて、乾燥製膜した。
<乾燥条件>
室温、常圧下で乾燥(風乾)した。
<焼成条件>
乾燥を行った後の膜を、電気炉で常圧、空気雰囲気下で10℃/分で昇温し、180℃で15分間焼成を行った。焼成後、自然放冷し、室温まで冷却した。このときの導電性膜の最大膜厚は、0.8μmであり、導電性膜のシート抵抗は、3.5×102Ω/□、全光線透過率は、30%であった。また、導電性膜の開口率、線幅、空孔部の平均面積、空孔部の平均最大フェレ径を求めた結果、表1の通りであった。
<多孔質膜作製条件>
導電性微粒子分散溶液(x-3)を用いて、銀の重量濃度として3.7mg/ml、エポミンRP20(オクタデシルイソシアネート変性ポリエチレンイミン、日本触媒社製、Mn=6500、Mw=13700)0.11mg/mlのシクロヘキサン溶液を調整した。23℃、相対湿度70%の雰囲気下で、2.0mlの溶液を5cm角のスライドガラス基板上に塗布し、加湿空気(相対湿度70%以上)を1.6m/minの流速で、10分間吹きつけて有機溶媒を蒸発させて、乾燥製膜した。
<乾燥条件>
室温、常圧下で乾燥(風乾)した。
<焼成条件>
乾燥を行った後の膜を、電気炉で常圧、空気雰囲気下で10℃/分で昇温し、180℃で15分間焼成を行った。焼成後、自然放冷し、室温まで冷却した。このときの導電性膜の最大膜厚は、0.9μmであり、導電性膜のシート抵抗は、42Ω/□、全光線透過率は、43%であった。また、導電性膜の開口率、線幅、空孔部の平均面積、空孔部の平均最大フェレ径を求めた結果、表1の通りであった。
<多孔質膜作製条件>
導電性微粒子分散溶液(x-3)を用いて、銀の重量濃度として3.7mg/ml、CAP(n:m=7.6:1、Mn=25000、Mw=95000)0.11mg/mlのシクロヘキサン溶液を調整した。23℃、相対湿度70%の雰囲気下で、2.0mlの溶液を5cm角のスライドガラス基板上に塗布し、加湿空気(相対湿度70%以上)を1.6m/minの流速で、10分間吹きつけて有機溶媒を蒸発させて、乾燥製膜した。
<乾燥条件>
室温、常圧下で乾燥(風乾)した。
<焼成条件>
乾燥を行った後の膜を、電気炉で常圧、空気雰囲気下で10℃/分で昇温し、180℃で15分間焼成を行った。焼成後、自然放冷し、室温まで冷却した。このときの導電性膜の最大膜厚は、0.8μmであり、導電性膜のシート抵抗は、6Ω/□、全光線透過率は、42%であった。また、導電性膜の開口率、線幅、空孔部の平均面積、空孔部の平均最大フェレ径を求めた結果、表1の通りであった。
<多孔質膜作製条件>
導電性微粒子として、三ッ星ベルト製の銀微粒子分散溶液(クロロホルム溶液)を用いて、銀の重量濃度として2.75mg/mlのクロロホルム溶液を調整した。23℃、相対湿度70%の雰囲気下で、2.0mlの溶液を5cm角のスライドガラス基板上に塗布し、加湿空気(相対湿度70%)を1.6m/minの流速で、10分間吹きつけて有機溶媒を蒸発させて、乾燥製膜した。
<乾燥条件>
室温、常圧下で乾燥(風乾)した。
<焼成条件>
乾燥を行った後の膜を、電気炉で常圧、空気雰囲気下で10℃/分で昇温し、300℃で15分間焼成を行った。焼成後、自然放冷し、室温まで冷却した。
なお、図15において、白く見える部分が凸部、黒く見える部分が凹部であり、銀膜の凹凸が表面全面を覆っていることが観察される。このような場合、透明性、透過性は無いといえる。
<多孔質膜作製条件>
導電性微粒子分散溶液(x-3)を用いて、銀の重量濃度として0.2mg/mlのシクロヘキサン溶液を調整した。25℃、相対湿度80%の雰囲気下で、2.0mlの溶液を5cm角のスライドガラス基板上に塗布し、加湿空気(相対湿度80%)を0.6m/minの流速で、10分間吹きつけて有機溶媒を蒸発させて、乾燥製膜した。
<乾燥条件>
室温、常圧下で乾燥(風乾)した。
<焼成条件>
乾燥を行った後の膜を、電気炉で常圧、空気雰囲気下で10℃/分で昇温し、300℃で15分間焼成を行った。焼成後、自然放冷し、室温まで冷却した。
作成した焼成後の膜の形態を参考例1と同様に、デジタルマイクロスコープで観察したところ、パターン構造を観察することが出来ず、全面に銀の薄膜が形成された。
<多孔質膜作製条件>
導電性微粒子分散溶液(x-3)を用いて、銀の重量濃度として0.1mg/ml、ポリスチレン(アルドリッチ(Aldrich)社製、Mw=280000)0.2mg/mlのシクロヘキサン溶液を調整した。5cm角のスライドガラスを飽和水酸化カリウムエタノール溶液に2時間浸漬後、エタノール、水で超音波洗浄を行うことにより、親水化処理を行った。このときの基板の接触角は、測定できないほど低く、ほぼ0°であった。25℃、相対湿度80%の雰囲気下で、2.0mlの溶液を5cm角のスライドガラス基板上に塗布し、加湿空気(相対湿度80%)を0.6m/minの流速で、10分間吹きつけて有機溶媒を蒸発させて、乾燥製膜した。
<乾燥条件>
室温、常圧下で乾燥(風乾)した。
<焼成条件>
乾燥を行った後の膜を、電気炉で常圧、空気雰囲気下で10℃/分で昇温し、300℃で15分間焼成を行った。焼成後、自然放冷し、室温まで冷却した。
作成した焼成後の膜の形態を参考例1と同様に、デジタルマイクロスコープで観察したところ、部分的にしかパターン構造が出来ておらず、また、パターン構造が観察された部分も、銀粒子が開口部の底にも析出しており、基材が直接観察出来る領域がなかった。
<多孔質膜作製条件>
導電性微粒子分散溶液(x-3)を用いて、銀の重量濃度として3.7mg/ml、エポミンRP20(オクタデシルイソシアネート変性ポリエチレンイミン、日本触媒社製、Mn=6500、Mw=13700)0.11mg/mlのシクロヘキサン溶液を調整した。23℃、相対湿度40%の雰囲気下で、2.0mlの溶液を5cm角のスライドガラス基板上に塗布し、空気(相対湿度40%)を1.6m/minの流速で、10分間吹き付けて有機溶媒を蒸発させて、乾燥製膜した。
<乾燥条件>
室温、常圧下で乾燥(風乾)した。
<焼成条件>
乾燥を行った後の膜を、電気炉で常圧、空気雰囲気下で10℃/分で昇温し、180℃で15分間焼成を行った。焼成後、自然放冷し、室温まで冷却した。
<結果>
パターンが出来ず、全面に銀ナノ粒子が塗布されていた。
透過率:12%
導電性:ロレスターで測定できず。
パターンが出来ないため、透過率が低く、また、パターンが出来たときと比較し、全面に塗布されて膜厚が薄くなるため、導電性が出なくなっていた。
特開2005-338189号公報の比較例を参考に、以下のようにしてデジタルペーパーを作製した。
<TiO2>
300mLの4つ口フラスコに、酸化チタン(製品名:タイペークCR-97、石原産業社製)100g、n-ヘキサン100gおよびオクタデシルトリクロロシラン(製品名:LS6495、信越化学工業社製)4gを仕込み、攪拌混合をしながら、上記フラスコを55℃の超音波浴槽(超音波ホモジナイザー(製品名:BRANSON5210、ヤマト社製)により超音波を発生させた浴槽)に入れ、超音波分散を行いながらカップリング剤処理を2時間行った。
この分散液を遠心分離用沈降管に移し、遠心分離機(製品名:高速冷却遠心機GRX-220、トミー社製)により10000Gで15分間沈降操作を行い、その後、沈降管の上澄み液を除去して、表面処理された酸化チタン(p1)を得た。
<CB>
200mLのビーカーに、カーボンブラック(製品名:MA100、三菱化学社製)5gおよびメチルメタアクリレート172.5gを仕込み、超音波ホモジナイザー(製品名:BRANSON5210、ヤマト社製)で分散処理を行った後、アゾビスブチロニトリル3.5gを加えて溶解させ、モノマー組成物を得た。
アニオン性界面活性剤(製品名:ハイテノールNO8)2.5gを水750gに溶解させた水溶液を予め調製しておき、これに上記モノマー組成物を全量添加し、高速攪拌乳化機(製品名:クリアミックスCLM-0.8S、エム・テクニック社製)により分散処理して、上記モノマー組成物の懸濁液を得た。
この懸演液を75℃に昇温させ5時間保持することにより重合反応を行い、黒色微粒子の分散体を得た。この黒色微粒子の粒子経(体積平均粒子経)を、レーザー回折/散乱式粒度分布測定装置(製品名:LA-910、堀場製作所社製)を用いて測定したところ、0.8μmであった。上記分散体について、ろ過、洗浄および乾燥を施すことにより、黒色微粒子(p2)を得た。
<インキ化>
アイソパーM(エクソン化学社製)85.6gに、黒色微粒子(p2)3.1gおよび酸化チタン(p1)11.5gを仕込み、超音波浴槽で2時間分散処理を行い、電気泳動表示装置用分散液(i1)を得た。
<カプセル化>
500mLの平底セパラブルフラスコに、水60g、アラビアゴム6gおよびゼラチン6gを仕込み、溶解させた。
この溶液を43℃に保持しながら、ディスパー(製品名:ROBOMICS、特殊機化工業社製)による攪拌下で、50℃に加温した電気泳動表示装置用分散液(i1)95gを添加し、その後、攪拌速度を徐々に上げ、1200rpmで30分間攪拌して懸濁液を得た。この懸濁液に43℃の温水300mLを添加しながら攪拌速度を徐々に下げた。
櫂型攪拌羽根により懸濁液全体を均一状態に保持し得る攪拌下で、10wt%酢酸水溶液約11mLを22分かけて定量添加し、pH4.0とした後、10℃に冷却した。
冷却した状態で懸濁液を2時間保持した後、37wt%ホルマリン水溶液3mLを添加し、さらに10wt%Na2CO3水溶液22mLを25分かけて定量添加した。
さらに、懸濁液の温度を常温に戻し、20時間保持して熟成させ、電気泳動表示装置用マイクロカプセル(cm1)の分散液を得た。電気泳動表示装置用マイクロカプセル(cm1)の体積平均粒子径は51.1μmであった。
この分散液を目開き孔径80μmと30μmのメッシュに通して分級し、粒子径30~80μmの電気泳動表示装置用マイクロカプセル(cm1)のペースト(固形分:57wt%)を得た。
<塗工液>
次に、アルカリ可溶型アクリル樹脂エマルション(製品名:WR503A、日本触媒社製、樹脂含量:30wt%)2.1gを固形分が5wt%となるように水で希釈し、これに25wt%アンモニア水0.2gを添加して、上記アルカリ可溶型アクリル樹脂の溶液を調製した。この樹脂溶液12.8gを、上記ペースト12.8gに添加して、混合機(製品名:あわとり練太郎AR-100、シンキー社製)で10分間混合し、塗工液を得た。
<塗布、ラミネート>
上記塗工液を、ITO付きPETフィルムにアプリケーターで塗布した後、90℃で10分乾燥して、電気泳動表示装置用シート(s1)を得た。
電気泳動表示装置用シート(s1)の塗工面に、本発明の銀導電性膜付きガラスをラミネートし、対向電極を有する電気泳動表示装置(d1)を作製した。
装置(d1)に3Vの電圧を印加したところ、陰極側表面に白色が、陽極側表面に黒色が得られ、電圧の極性を逆にすると各々色が逆転し、本発明の導電性膜がデジタルペーパー用の透明電極として使用できることが確認出来た。なお、装置(d1)に電圧を印加した時の様子は、図16のように表すことができる。
特表2005-530005号公報の実施例10に従い、銀パターン導電性膜が形成された導電性フィルムを作製した。導電性膜の線幅は3.2μm、空孔部の平均面積は5673μm2、空孔部の平均最大フェレ径は84μmであった。前記、電気泳動表示装置用シート(s1)の塗工面に、銀導電性膜が形成された導電性フィルムをラミネートし、対向電極を有する電気泳動表示装置(d2)を作製した。
装置(d2)に3Vの電圧を印加したところ、銀のパターン上のマイクロカプセルのみが電気泳動し、銀のパターンにかからないマイクロカプセルは電気泳動しなかった。この様子を簡略化して表すと、図17のように表すことができる。このため、全面に渡って白色、黒色にならず、陰極側、陽極側共に、白黒が混じったまだらな模様が観察され、比較例2の導電性膜はデジタルペーパー用の透明電極として不適であった。
12、22:塗膜(塗布された有機溶媒分散体)
13:水滴
14:空孔部
15:網目状線部
20:ペルチェ素子
31:ピエゾステージ
32:試料ステージ
33:試料
34:金コート探針
35:銀ペースト
Claims (5)
- 導電性微粒子を含む有機溶媒分散体を基板に塗布して網目状の導電性膜を製造する方法であって、
該製造方法は、塗布された有機溶媒分散体を、塗膜表面で結露させながら有機溶媒を蒸発させる工程を含むことを特徴とする導電性膜の製造方法。 - 前記有機溶媒分散体は、水及び有機溶媒に対する両親媒性化合物を含有することを特徴とする請求項1記載の導電性膜の製造方法。
- 請求項1又は2のいずれかに記載の方法により製造されることを特徴とする導電性膜。
- 導電性物質の網目状線部と空孔部とによって形成された網目状の導電性膜であって、
該導電性膜は、空孔部の平均面積が400μm2以下であり、網目状線部の線幅が5μm以下であることを特徴とする導電性膜。 - デジタルペーパーに用いられることを特徴とする請求項3又は4記載の導電性膜。
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US12/737,350 US20110124252A1 (en) | 2008-07-02 | 2009-06-24 | Process for producing conductive film and conductive film |
CN2009801247846A CN102077302B (zh) | 2008-07-02 | 2009-06-24 | 导电性膜的制造方法以及导电性膜 |
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JP (1) | JP5515010B2 (ja) |
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JP5405374B2 (ja) * | 2010-03-26 | 2014-02-05 | 富士フイルム株式会社 | ハニカム構造フィルムの製造方法 |
KR101487342B1 (ko) * | 2010-07-30 | 2015-01-30 | 주식회사 잉크테크 | 투명 도전막의 제조방법 및 이에 의해 제조된 투명 도전막 |
WO2012053456A1 (ja) * | 2010-10-21 | 2012-04-26 | 旭硝子株式会社 | 水素化銅微粒子分散液の製造方法、導電インクおよび導体付き基材の製造方法 |
US8933906B2 (en) * | 2011-02-02 | 2015-01-13 | 3M Innovative Properties Company | Patterned substrates with non-linear conductor traces |
EP2671438A4 (en) | 2011-02-02 | 2017-06-14 | 3M Innovative Properties Company | Patterned substrates with darkened conductor traces |
TWI527062B (zh) * | 2011-09-27 | 2016-03-21 | Lg化學股份有限公司 | 透明導電基板及其製備方法 |
CN103959397B (zh) * | 2011-11-29 | 2016-09-07 | 东丽株式会社 | 导电层合体及使用该导电层合体而成的显示体 |
CN103325441A (zh) * | 2012-03-21 | 2013-09-25 | 宸鸿科技(厦门)有限公司 | 触控面板之导电薄膜及其制造方法 |
JPWO2014010270A1 (ja) * | 2012-07-10 | 2016-06-20 | 東レ株式会社 | 導電積層体、パターン化導電積層体、その製造方法、および、それらを用いてなるタッチパネル |
JP2014072147A (ja) * | 2012-10-01 | 2014-04-21 | Otsuka Chem Co Ltd | 導電膜、その製造方法及び製造装置 |
US9954526B2 (en) * | 2013-09-09 | 2018-04-24 | Atmel Corporation | Generic randomized mesh design |
DE102013114572A1 (de) * | 2013-12-19 | 2015-06-25 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Verfahren zur Herstellung strukturierter metallischer Beschichtungen |
JP6421077B2 (ja) * | 2015-05-19 | 2018-11-07 | 富士フイルム株式会社 | アンテナの製造方法およびタッチセンサ |
KR102541112B1 (ko) * | 2016-04-05 | 2023-06-09 | 미래나노텍(주) | 터치 센서 및 이를 이용한 터치스크린 패널 |
CN106288107A (zh) * | 2016-10-28 | 2017-01-04 | 佛山市南海科日超声电子有限公司 | 具有发光功能的雾化器 |
US9865527B1 (en) | 2016-12-22 | 2018-01-09 | Texas Instruments Incorporated | Packaged semiconductor device having nanoparticle adhesion layer patterned into zones of electrical conductance and insulation |
US9941194B1 (en) | 2017-02-21 | 2018-04-10 | Texas Instruments Incorporated | Packaged semiconductor device having patterned conductance dual-material nanoparticle adhesion layer |
KR20190111115A (ko) * | 2017-03-13 | 2019-10-01 | 후지필름 가부시키가이샤 | 전자파 실드 부재 |
US20230245797A1 (en) * | 2019-10-15 | 2023-08-03 | Kyoto University | Conductive film, dispersion, manufacturing methods for these, and device including conductive film |
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