WO2013161996A2 - 透明導電性インク及び透明導電パターン形成方法 - Google Patents
透明導電性インク及び透明導電パターン形成方法 Download PDFInfo
- Publication number
- WO2013161996A2 WO2013161996A2 PCT/JP2013/062387 JP2013062387W WO2013161996A2 WO 2013161996 A2 WO2013161996 A2 WO 2013161996A2 JP 2013062387 W JP2013062387 W JP 2013062387W WO 2013161996 A2 WO2013161996 A2 WO 2013161996A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- transparent conductive
- conductive ink
- pattern
- metal
- viscosity
- Prior art date
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/003—Apparatus or processes specially adapted for manufacturing conductors or cables using irradiation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0036—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0108—Transparent
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/026—Nanotubes or nanowires
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
- H05K2203/107—Using laser light
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
Definitions
- the present invention relates to a transparent conductive ink and a transparent conductive pattern forming method.
- Transparent conductive films include liquid crystal displays (LCDs), plasma display panels (PDPs), organic electroluminescence (OLEDs), transparent electrodes for solar cells (PVs) and touch panels (TPs), antistatic (ESD) films, and electromagnetic shielding (EMI). ) It is used in various fields such as film, and (1) low surface resistance, (2) high light transmittance, and (3) high reliability are required.
- LCDs liquid crystal displays
- PDPs plasma display panels
- OLEDs organic electroluminescence
- PVs transparent electrodes for solar cells
- TPs touch panels
- ESD antistatic
- EMI electromagnetic shielding
- the surface resistance is in the range of 10 to 300 ⁇ / ⁇ , and the light transmittance is 85% or more in the visible light region. More preferable ranges are a surface resistance of 20 to 100 ⁇ / ⁇ and a light transmittance of 90% or more.
- the surface resistance is in the range of 10 to 100 ⁇ / ⁇ , and the light transmittance is 80% or more in the visible light region. More preferable ranges are a surface resistance of 10 to 50 ⁇ / ⁇ and a light transmittance of 85% or more.
- the PV transparent electrode has a surface resistance in the range of 5 to 100 ⁇ / ⁇ and a light transmittance of 65% or more in the visible light region.
- More preferable ranges are a surface resistance of 5 to 20 ⁇ / ⁇ and a light transmittance of 70% or more.
- the surface resistance is in the range of 100 to 1000 ⁇ / ⁇ , and the light transmittance is 85% or more in the visible light region. More preferably, the surface resistance is in the range of 150 to 500 ⁇ / ⁇ , and the light transmittance is 90% or more in the visible light region.
- the surface resistance is in the range of 500 to 10,000 ⁇ / ⁇ , and the light transmittance is 90% or more in the visible light region. More preferably, the surface resistance is in the range of 1000 to 5000 ⁇ / ⁇ , and the light transmittance is 95% or more in the visible light region.
- ITO indium tin oxide
- ITO film formation a vacuum manufacturing apparatus is required, which requires a long manufacturing time and a high cost.
- ITO is difficult to be applied to a substrate provided with flexibility because cracks are generated due to physical stress such as bending and are easily broken. Therefore, search for an ITO alternative material that has solved these problems has been underway.
- poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfone) can be used as a coating film forming material that does not require the use of a vacuum manufacturing apparatus.
- Acid) PEDOT: PSS
- conductive materials containing metal nanowires for example, see Patent Document 2 and Non-Patent Document 1
- carbon A conductive material containing a nanostructured conductive component such as a conductive material containing nanotubes (see, for example, Patent Document 3) has been reported.
- the conductive material containing the metal nanowire (ii) has been reported to exhibit low surface resistance and high light transmittance (for example, see Patent Document 2 and Non-Patent Document 1), and further has flexibility. Therefore, it is suitable as an “ITO substitute material”.
- the transparent conductive film since the transparent conductive film is used as a transparent electrode, it requires pattern formation according to the application.
- a photolithography method using a resist material is generally used for the ITO pattern formation.
- Non-Patent Document 1 describes the following steps. (1) A step of applying a conductive ink containing metal nanowires to a substrate. (2) A step of firing to form a transparent conductive layer. (3) A step of forming a photosensitive resist on the transparent conductive layer. (4) A step of applying light energy to the resist through an appropriate light shielding mask corresponding to a fine pattern. (5) A step of developing the obtained latent image of the resist by elution with an appropriate developing solution. (6) A step of removing the exposed film to be patterned (transparent conductive layer) using an appropriate etching method. (7) A step of removing the remaining resist using an appropriate method.
- Patent Document 2 describes the following steps. (1) A step of applying a conductive ink containing silver nanowires dispersed in water to a substrate. (2) A step of firing to form a silver nanowire network layer. (3) A step of forming a photocurable matrix material containing a prepolymer on the silver nanowire network layer. (4) A step of applying light energy to the matrix material through an appropriate light shielding mask corresponding to a fine pattern. (5) A step of removing the non-cured region by washing with a solvent (ethanol). Or the process of physically removing a non-hardened area
- ethanol solvent
- Patent Document 4 describes the following steps. (1) A step of applying a conductive ink containing silver nanowires dispersed in a solution containing a photosensitive resin to a substrate. (2) A step of applying light energy to the photosensitive resin through an appropriate light shielding mask corresponding to a fine pattern. (3) The process which develops a non-hardened area
- Patent Document 5 describes the following steps. (1) The process of apply
- Non-Patent Document 1 a step of forming a photosensitive layer for pattern formation on the layer containing metal nanowires is required.
- the development process of the photosensitive layer and the removal process of the layer including the exposed metal nanowires are necessary, so that the silver nanowires in the removal region are wasted and the waste solution treatment of the developer is necessary.
- a step of removing the photosensitive layer may be necessary.
- Patent Document 4 also requires a development step, so that silver nanowires are wasted due to development, and a waste solution problem of the developer also occurs.
- Patent Document 5 is also plasma treatment or corona treatment, and it is very difficult to make the silver nanowires completely insulating, and the base material is deteriorated by the plasma treatment or corona treatment. There was a problem that the sex would deteriorate.
- Example by silver nanowire is not disclosed, the following method is disclosed by patent document 6 as a method of printing a conductive ink as a conductive layer patterned on the board
- a pattern is formed on a substrate by a printing method using a liquid-repellent transparent insulating ink containing a resin and a silicone-based or fluorine-based surfactant, (2) A conductive ink having repellency is applied to the entire surface of the dry film of the liquid repellent transparent insulating ink, and the conductive ink is repelled by the dry film of the liquid repellent transparent insulating ink.
- a conductive ink layer is formed on the substrate where the dry film of the liquid repellent transparent insulating ink is not formed.
- This method requires the design of both a water-repellent transparent ink and a hydrophilic conductive ink.
- the pattern accuracy is not only printing accuracy but also the repellent property between water-repellent and hydrophilic resin.
- a pattern directly on the silver nanowires by a printing method such as ink jet printing, screen printing, gravure printing, or flexographic printing.
- a binder resin is required to perform printing, and in order to ensure transparency, it is necessary to reduce the amount of silver nanowires used. Therefore, the binder resin used covers the surface of the silver nanowires and becomes conductive. There was a problem of disappearing.
- the binder resin is not used, there is a problem that the pattern is broken when the solvent is dried, even if the pattern cannot be secured at the time of printing or the pattern can be barely secured immediately after printing.
- an organic conductive polymer is used as a binder resin to form a pattern (transparent electrode) in the next step.
- Patent Document 8 discloses a method of forming a pattern in the following steps using a water-soluble polymer such as a cellulose derivative having a Tg in the range of 0 to 250 ° C. as a binder resin.
- a water-soluble polymer such as a cellulose derivative having a Tg in the range of 0 to 250 ° C. as a binder resin.
- (1) A step of printing on a substrate a conductive ink in which silver nanowires are dispersed in a solution containing a water-soluble polymer such as a cellulose derivative having a Tg in the range of 0 to 250 ° C. as a binder resin.
- An object of the present invention is to provide a transparent conductive ink capable of forming a coating film having both conductivity and light transmittance, using metal nanowires and / or metal nanotubes as a conductive component, and a simple method using the same.
- An object of the present invention is to provide a transparent conductive pattern forming method capable of forming a transparent conductive pattern by a manufacturing process and suppressing manufacturing cost and environmental load.
- one embodiment of the present invention is a transparent conductive ink, comprising at least one of metal nanowires and metal nanotubes, and an organic compound having a molecular weight in the range of 150 to 500, and at 25 ° C. And a dispersion medium having a shape-retaining material having a viscosity of 1.0 ⁇ 10 3 to 2.0 ⁇ 10 6 mPa ⁇ s.
- the organic compound contained in the shape retaining material is preferably a monosaccharide, a polyol, a quaternary alkyl group or an alkyl group having a bridged ring skeleton, and a compound having a hydroxyl group, particularly diglycerin, 2,2,4-trimethyl-1.3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1.3-pentanediol diisobutyrate, xylulose, ribulose, bornylcyclohexanol, bornylphenol, It may be either isobornylcyclohexanol or isobornylphenol.
- the dispersion medium may further contain a viscosity adjusting solvent for adjusting the viscosity of the shape maintaining material.
- the viscosity adjusting solvent is preferably any one of water, alcohol, ketone, ester, ether, hydrocarbon solvent and aromatic solvent, and terpineol is preferable.
- the amount of metal nanowires and / or metal nanotubes is 0.01 to 10% by mass with respect to the total mass of the transparent conductive ink, and the content of the shape-retaining material is 10 to 90% by mass with respect to the total mass of the dispersion medium. % Should be good.
- Another embodiment of the present invention is a transparent conductive pattern forming method, wherein a pattern of an arbitrary shape is printed on a substrate with any of the transparent conductive inks described above, and the pattern is heated and dried. And irradiating the dried pattern with pulsed light.
- the present invention it is possible to provide a transparent conductive ink that can form a coating film having both conductivity and light transmittance by using metal nanowires and / or metal nanotubes as a conductive component. Moreover, the transparent conductive pattern formation method which can form a transparent conductive pattern by a simple manufacturing process using this transparent conductive ink, and can suppress manufacturing cost and environmental impact can be provided.
- the transparent conductive ink according to the embodiment can favorably disperse metal nanowires and / or metal nanotubes by using a dispersion medium containing the following shape-retaining material. If this transparent conductive ink is used, pattern formation by printing can be performed satisfactorily, and a coating film having both conductivity and light transmittance can be formed by distilling off the dispersion medium.
- the shape-retaining material contains an organic compound having a molecular weight range of 150 to 500 and has a viscosity at 25 ° C. of 1.0 ⁇ 10 3 to 2.0 ⁇ 10 6 mPa ⁇ s.
- the shape-retaining material can be composed only of the organic compound.
- an appropriate solvent a solvent capable of dissolving an organic compound, such as a viscosity adjusting solvent described later.
- the viscosity of the shape-retaining material is lower than the above range, the shape of the printed pattern cannot be maintained, and if it is higher than the above range, adverse effects such as stringiness during printing will occur.
- the viscosity at 25 ° C. of the shape-retaining material is more preferably in the range of 5.0 ⁇ 10 4 to 1.0 ⁇ 10 6 mPa ⁇ s.
- the viscosity is a value measured using a conical plate type rotational viscometer (cone plate type).
- the molecular weight of the organic compound contained in the shape-retaining material used is large, the shape-retaining material cannot be removed efficiently during sintering and the resistance does not decrease. Therefore, the molecular weight is 500 or less, preferably 400 or less, more preferably 300 or less.
- a compound containing a hydroxyl group is preferable, for example, a monosaccharide, a polyol, a quaternary alkyl group and / or an alkyl group having a bridged ring skeleton and a hydroxyl group-containing compound are preferable, such as diglycerin, 2 , 2,4-trimethyl-1.3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1.3-pentanediol diisobutyrate, xylulose, ribulose, bornylcyclohexanol, bornylphenol, iso Examples include bornylcyclohexanol and isobornylphenol.
- those having an isobornyl group and a hydroxyl group are particularly preferred. This is because, in addition to the complicated three-dimensional structure of the isobornyl group, the ink is imparted with appropriate tackiness by the hydrogen bond of the hydroxyl group.
- the compound having an isobornyl group and a hydroxyl group has a high viscosity even though the volatilization temperature is not so high, so that it is possible to realize a high viscosity of the ink.
- Examples of the compound having an isobornyl group and a hydroxyl group include either or both of isobornyl cyclohexanol and isobornyl phenol.
- the content of the shape-retaining material in the ink is preferably 10 to 90% by mass and more preferably 30 to 80% by mass with respect to the total mass of the dispersion medium.
- the content of the shape-retaining material is less than 10% by mass, the ink cannot have an appropriate viscosity and cannot be printed.
- the content of the shape-retaining material exceeds 90% by mass, the ink viscosity becomes too high, and the stringiness at the time of printing becomes worse, and printing may not be possible.
- a transparent conductive ink may be prepared by preparing a dispersion medium and dispersing metal nanowires and / or metal nanotubes as a conductive component in the dispersion medium.
- viscosity adjusting solvent examples include water, alcohol, ketone, ester, ether, aliphatic hydrocarbon solvent, and aromatic hydrocarbon solvent.
- the metal nanowire and the metal nanotube are metals having a diameter of a nanometer order size
- the metal nanowire is a conductive material having a wire shape
- the metal nanotube is a porous or non-porous tube shape.
- both “wire shape” and “tube shape” are linear, but the former is intended to have a hollow center, and the latter is intended to have a hollow center.
- the property may be flexible or rigid. Either the metal nanowire or the metal nanotube may be used, or a mixture of both may be used.
- the type of metal at least one selected from the group consisting of gold, silver, platinum, copper, nickel, iron, cobalt, zinc, ruthenium, rhodium, palladium, cadmium, osmium, iridium and an alloy combining these metals Etc.
- An optimal embodiment includes silver nanowires.
- the diameter of the metal nanowire and / or the metal nanotube in the transparent conductive ink, the length of the major axis, and the aspect ratio have a constant distribution. This distribution is selected so that the coating film obtained from the transparent conductive ink of the present embodiment has a high total light transmittance and a low surface resistance.
- the average diameter of the metal nanowire and the metal nanotube is preferably 1 to 500 nm, more preferably 5 to 200 nm, still more preferably 5 to 100 nm, and particularly preferably 10 to 100 nm.
- the average length of the major axis of the metal nanowire and / or metal nanotube is preferably 1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, further preferably 2 to 50 ⁇ m, and particularly preferably 5 to 30 ⁇ m.
- the average diameter and the average length of the major axis satisfy the above ranges, and the average aspect ratio is preferably greater than 5, more preferably 10 or more. 100 or more is more preferable, and 200 or more is particularly preferable.
- the aspect ratio is a value obtained by a / b when the average diameter of the metal nanowire and / or the metal nanotube is approximated to b and the average length of the major axis is approximated to a.
- a and b can be measured using a scanning electron microscope.
- metal nanowires and / or metal nanotubes As a method for producing metal nanowires and / or metal nanotubes, known production methods can be used. For example, silver nanowires can be synthesized by reducing silver nitrate in the presence of polyvinylpyrrolidone using the Poly-ol method (see Chem. Mater., 2002, 14, 4736). Similarly, gold nanowires can be synthesized by reducing chloroauric acid hydrate in the presence of polyvinylpyrrolidone (see J. Am. Chem. Soc., 2007, 129, 1733). There are detailed descriptions of techniques for large-scale synthesis and purification of silver nanowires and gold nanowires in International Publication Nos. WO2008 / 073143 and International Publication No. 2008/046058.
- Gold nanotubes having a porous structure can be synthesized by reducing a chloroauric acid solution using silver nanowires as a template.
- the silver nanowire used as the template is dissolved into the solution by a redox reaction with chloroauric acid, and as a result, a gold nanotube having a porous structure is formed.
- the content of metal nanowires and / or metal nanotubes in the transparent conductive ink according to the present embodiment is good dispersibility and good pattern formation property of the coating film obtained from the transparent conductive ink, high conductivity and good
- the amount of metal nanowires and / or metal nanotubes is 0.01 to 10% by mass, and more preferably 0.05 to 2% by mass, based on the total mass of the transparent conductive ink. . If the metal nanowires and / or metal nanotubes are less than 0.01% by mass, it is necessary to print the transparent conductive layer very thick in order to ensure the desired conductivity, and the difficulty of printing increases. It becomes difficult to maintain the pattern when drying. On the other hand, if it exceeds 10% by mass, it is necessary to print very thinly to ensure the desired transparency, and this system also becomes difficult to print.
- the transparent conductive ink according to the present embodiment is an optional component other than the above components (shape holding material, viscosity adjusting solvent, metal nanowire, metal nanotube), for example, binder resin, corrosion inhibitor, An adhesion promoter, a surfactant and the like may be included.
- polyacryloyl compounds such as polymethyl methacrylate, polyacrylate, polyacrylonitrile; polyvinyl alcohol; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate; highly conjugated polymers such as novolac; polyimide, polyamideimide, poly Polyimides; Polysulfones; Polyphenylenes; Polyphenyl ethers; Polyurethanes; Epoxy; Aromatic polyolefins such as polystyrene, polyvinyltoluene, and polyvinylxylene; Aliphatic polyolefins such as polypropylene and polymethylpentane; Fats such as polynorbornene Polyolefins such as cyclic olefins and polyvinylpyrrolidone; acrylonitrile-butadiene-styrene Copolymer (ABS); celluloses such as hydroxypropylmethylcellulose (HPMC) and
- examples of the corrosion inhibitor include benzotriazole
- examples of the adhesion promoter include 2-hydroxymethylcellulose
- examples of the surfactant include trade name F-472SF (manufactured by DIC Corporation).
- the transparent conductive ink according to the present embodiment can be produced by appropriately selecting the above-described components by stirring, mixing, heating, cooling, dissolution, dispersion, or the like by a known method.
- the preferred viscosity of the transparent conductive ink according to the present embodiment varies depending on the printing method, but in the case of screen printing, the viscosity at 25 ° C. is preferably 100 to 2 ⁇ 10 5 mPa ⁇ s, more preferably 10 3 to 5 ⁇ 10 4 mPa ⁇ s.
- the viscosity is a value measured using a conical plate type rotational viscometer (cone plate type).
- pattern printing is performed by gravure printing, screen printing, ink jet printing, flexographic printing, or the like.
- the substrate on which pattern printing is performed may be rigid (rigid) or bend easily (flexibility). Moreover, it may be colored.
- the substrate include materials such as glass, polyimide, polycarbonate, polyethersulfone, acrylic resin, polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyolefin, polyvinyl chloride, and the like. These preferably have a high light transmittance and a low haze value.
- a circuit such as a TFT element may be formed on the substrate, and a functional material such as a color filter may be formed. A large number of substrates may be stacked.
- the amount of the transparent conductive ink applied to the substrate is determined in consideration of the film thickness of the transparent conductive pattern required by the application.
- the film thickness is selected based on the application.
- the desired film thickness can be obtained by adjusting the application amount of the transparent conductive ink and the conditions of the application method.
- the film thickness is preferably as thick as possible from the viewpoint of low surface resistance and as thin as possible from the viewpoint of suppressing the occurrence of display defects due to steps, so that when considering these in total, a film thickness of 5 to 500 nm is preferable.
- a film thickness of 5 to 200 nm is more preferable, and a film thickness of 5 to 100 nm is more preferable.
- the printed (coated) transparent conductive ink is dried by heating the coated material as necessary.
- the heating temperature varies depending on the liquid component constituting the dispersion medium, but if the drying temperature is too high, the formed pattern may not be retained. Therefore, the drying temperature is at most 120 ° C., more preferably 100 ° C. or less. Since the initial drying temperature is particularly important, it is particularly preferable to start the drying from about 40 to 80 ° C. and raise the temperature stepwise within a range not exceeding 120 ° C. as necessary.
- a viscous liquid shape-retaining material generally has a high boiling point, and when a viscosity-adjusting solvent having a lower boiling point than the shape-retaining material coexists in the dispersion medium, the low-boiling viscosity adjusting solvent is preferentially distilled off. Therefore, the viscosity of the dispersion medium increases by drying, and the collapse of the print pattern during drying is suppressed.
- the surface resistance and the total light transmittance of the obtained transparent conductive pattern are adjusted by adjusting the film thickness, that is, the coating amount of the composition and the conditions of the coating method, and the metal nanowire or metal nanotube in the transparent conductive ink according to this embodiment.
- the film thickness that is, the coating amount of the composition and the conditions of the coating method, and the metal nanowire or metal nanotube in the transparent conductive ink according to this embodiment.
- the thicker the film the lower the surface resistance and the total light transmittance.
- the higher the concentration of metal nanowires or metal nanotubes in the transparent conductive ink the lower the surface resistance and the total light transmittance.
- the coating film obtained as described above preferably has a surface resistance value of 5 to 1000 ⁇ / ⁇ , a total light transmittance of 80% or more, and a surface resistance value of 10 to 200 ⁇ / ⁇ . More preferably, the total light transmittance is 90% or more.
- the surface resistance of the transparent conductive ink according to the present embodiment is lowered to some extent even if it is dried, but it is preferable to irradiate with pulsed light in order to lower the efficiency more efficiently.
- pulse light means light having a short light irradiation period (irradiation time).
- the second light irradiation period (on) means light irradiation having a period (irradiation interval (off)) in which light is not irradiated.
- FIG. 1 shows that the light intensity of the pulsed light is constant, the light intensity may change within one light irradiation period (on).
- the pulsed light is emitted from a light source including a flash lamp such as a xenon flash lamp.
- the metal nanowires or metal nanotubes deposited on the substrate are irradiated with pulsed light.
- irradiation is repeated n times, one cycle (on + off) in FIG. 1 is repeated n times.
- an electromagnetic wave having a wavelength range of 1 pm to 1 m can be used, preferably an electromagnetic wave having a wavelength range of 10 nm to 1000 ⁇ m (from far ultraviolet to far infrared), more preferably 100 nm to 2000 nm.
- Electromagnetic waves in the wavelength range can be used. Examples of such electromagnetic waves include gamma rays, X-rays, ultraviolet rays, visible light, infrared rays, microwaves, radio waves on the longer wavelength side than microwaves, and the like. In consideration of conversion to thermal energy, if the wavelength is too short, damage to the shape-retaining material, the resin base material on which pattern printing is performed, etc. is not preferable.
- the wavelength range is preferably the ultraviolet to infrared range, more preferably the wavelength range of 100 to 2000 nm, among the wavelengths described above.
- the irradiation time (on) of pulsed light is preferably in the range of 20 microseconds to 50 milliseconds, although it depends on the light intensity. If it is shorter than 20 microseconds, the sintering of the metal nanowire or the metal nanotube does not proceed, and the effect of improving the performance of the conductive film is lowered. On the other hand, if it is longer than 50 milliseconds, the base material may be adversely affected by light deterioration and heat deterioration, and the metal nanowire or the metal nanotube is likely to be blown off. More preferably, it is 40 microseconds to 10 milliseconds. For this reason, pulse light is used instead of continuous light in this embodiment.
- the irradiation interval (off) is preferably in the range of 20 microseconds to 5 seconds, more preferably 2 milliseconds to 2 seconds in consideration of productivity. If it is shorter than 20 microseconds, it becomes close to continuous light and is irradiated without being allowed to cool after a single irradiation, so that the substrate may be heated to increase the temperature and deteriorate. . Further, if it is longer than 5 seconds, the process time becomes longer, which is not preferable.
- a pattern of any shape is printed on a suitable substrate using the transparent conductive ink according to the present embodiment, and after heat treatment and drying, This pattern is irradiated with pulsed light having a pulse width (on) of 20 microseconds to 50 milliseconds, more preferably 40 microseconds to 10 milliseconds, using a xenon-type pulse irradiation lamp or the like. Join the intersections of metal nanotubes.
- bonding means that the nanowire or nanotube material (metal) absorbs the pulsed light at the intersection of the metal nanowires or metal nanotubes, and the internal heat is generated more efficiently at the intersection, so that the part is welded. It is to be done.
- connection area between the nanowires or nanotubes at the intersections can be increased and the surface resistance can be lowered.
- a conductive layer in which the metal nanowires or metal nanotubes are network-like is formed. Therefore, the conductivity of the transparent conductive pattern can be improved, and the surface resistance value is 10 to 800 ⁇ / ⁇ .
- the network formed by the metal nanowires or the metal nanotubes is not preferable in a dense state without a gap. This is because the light transmittance decreases if the interval is not provided.
- the conductive film after the pulse light irradiation, it is preferable to protect the conductive film by attaching a protective film on the transparent conductive pattern.
- the press mentioned here refers to applying pressure to the base material, and any form may be used.
- a method in which the base material is pressed between two flat plates or a cylindrical roll is used.
- a method of applying pressure to the material is preferable, and a method using the latter roll is particularly preferable because the pressure is applied uniformly.
- the linear pressure is preferably 0.1 kgf / cm (98 Pa ⁇ m) or more and 1000 kgf / cm (980 kPa ⁇ m) or less, preferably 1 kgf / cm (980 Pa ⁇ m) or more and 100 kgf / cm ( 98 kPa ⁇ m) or less is more preferable.
- the feed rate (line speed) of the substrate can also be appropriately selected within a practical range, but is generally preferably 10 mm / min to 10000 mm / min, more preferably 10 mm / min to 100 m / min. If it is too early, sufficient pressurization time cannot be obtained, and it is difficult to apply pressure accurately and uniformly.
- the pressure is not as uniform as the pressure roll, so the pressure is preferably 0.1 MPa to 200 MPa, more preferably 1 MPa to 100 MPa.
- heating may be performed during pressurization.
- pressure By applying pressure, not only the volume resistivity is lowered, but also mechanical properties such as bending strength can be improved.
- the pressure the higher the pressure, the more effective it is to reduce the volume resistivity and improve the mechanical strength.
- the pressure is too high, the cost of the pressurizing device will be very high.
- the upper limit is a desirable value.
- the light irradiation and pressing may be carried out either alone or in combination.
- Example 1 ⁇ Production of silver nanowires> Polyvinylpyrrolidone K-90 (manufactured by Nippon Shokubai Co., Ltd.) (0.049 g), AgNO 3 (0.052 g), and FeCl 3 (0.04 mg) were dissolved in ethylene glycol (12.5 ml) at 150 ° C. The resulting precipitate was isolated by centrifugation, and the precipitate was dried to obtain the intended silver nanowire, as shown in FIGS.
- the SEM used is FE-SEM S-5200 manufactured by Hitachi High-Tech Co., Ltd.
- the silver nanowires are rod-shaped, the diameter of the rod-shaped wire is about 70 nm, the length is 10 to 20 ⁇ m, and the ones growing in a rod shape are the whole. About 95% or more. The remainder was granular.
- the ethylene glycol, AgNO 3 and FeCl 3 are manufactured by Wako Pure Chemical Industries, Ltd.
- the length and diameter of the silver nanowires were measured with SEM and TEM.
- the TEM used was a TEM manufactured by JEOL Ltd .; JEOL, JEM-2100 transmission electron microscope.
- thermogravimetric analyzer is a differential ultra-high temperature thermobalance TG-DTA galaxy (S) manufactured by Bruker Ax Co., Ltd.
- the solvent was calculated from the ratio of the shape-retaining material used and the viscosity adjusting solvent, but the dibutyl ether brought in from the silver nanowires was calculated as 4 times the amount of silver nanowires.
- Examples 2 and 3 A transparent conductive ink prepared in the same manner as in Example 1 except that dibutyl ether, tersolve MTPH, the type of viscosity adjusting solvent, and the amount added were changed to the amounts shown in Table 1 to the concentrations shown in Table 1.
- Examples 4-7, 9-13 Instead of using the synthesized product as a silver nanowire, a commercially available product SLV-NW-35 (isopropanol dispersion by bluenano, concentration 10 mg / ml, silver nanowire diameter 35 nm, length of about 15 ⁇ m (catalog value)) A small amount of terpineol (manufactured by Nippon Terpene Chemical Co., Ltd.) was added to the silver nanowire dispersion and dispersed well, and then isopropanol was distilled off to perform solvent substitution.
- SLV-NW-35 isopropanol dispersion by bluenano, concentration 10 mg / ml, silver nanowire diameter 35 nm, length of about 15 ⁇ m (catalog value)
- terpineol manufactured by Nippon Terpene Chemical Co., Ltd.
- Tersolve MTPH manufactured by Nippon Terpene Chemical Co., Ltd., isobornylcyclohexanol
- terpineol were added so that the dispersion medium concentration finally became the blending ratio (mass ratio) described in Tables 1 to 3.
- a well-dispersed dispersion was obtained using ARV-310 manufactured by Shinky Corporation. The amount of the small amount of terpineol added first was determined in advance so that the concentration of the finally obtained dispersion became the concentrations shown in Tables 1 to 3.
- NW means nanowire.
- Comparative Example 1 An ink added to the synthetic silver nanowire used in Example 1 was prepared using the mixture shown in Table 1 with a mixture of polyvinylpyrrolidone (K-90 (manufactured by Nippon Shokubai Co., Ltd.)) and diethylene glycol as a dispersion medium.
- K-90 polyvinylpyrrolidone
- diethylene glycol diethylene glycol
- Comparative Example 2 As shown in Table 1, inks added to the synthetic silver nanowires used in Example 1 were prepared without using Telsolve MTPH and using only dibutyl ether and L- ⁇ -terpineol as dispersion media.
- Example 8 A copper nanowire (an isopropanol dispersion manufactured by NANOFORGE, concentration of about 1 g / 900 ml) was used as the nanowire to produce an ink.
- polyvinylpyrrolidone is attached to the wire surface for the purpose of preventing aggregation of copper nanowires, and therefore, a purification operation described later was performed before ink preparation.
- terpineol manufactured by Nippon Terpene Chemical Co., Ltd.
- isopropanol was distilled off to perform solvent substitution.
- tersolve MTPH manufactured by Nippon Terpene Chemical Co., Ltd., isobornylcyclohexanol
- a well-dispersed dispersion was obtained using ARV-310 manufactured by Sinky Corporation. The amount of the small amount of terpineol added first was determined in advance so that the concentration of the finally obtained dispersion was 1% by mass shown in Table 1.
- the base material used was a biaxially stretched polyester film manufactured by Toyobo Co., Ltd .: Cosmo Shine (registered trademark) A4300 (thickness 125 ⁇ m).
- Examples 4 to 13 Using each of the transparent conductive inks of Examples 4 to 13, a 2.5 cm square solid film was printed with a screen printer MT-320TVZ (manufactured by Microtech Co., Ltd.) (clearance: 1.0 mm, squeegee tack angle: 70 °, squeegee speed: 6 mm / sec, squeegee pressure: 0.2 MPa, scraper pressure: 0.15 MPa, back pressure: 0.1 MPa). Moreover, PET film (125U98 easy-adhesion grade thickness 125micrometer made by Toray Industries, Inc.) was used for the base material.
- the solid film did not need to maintain the pattern, and was dried with a hot air circulating dryer at 120 ° C. for 1 hour.
- ⁇ Viscosity measurement> The viscosity of the shape-retaining material and the transparent conductive ink was measured at 25 ° C. using Brookfield Model DV-II + Pro. Incidentally, the rotor number 52 if the viscosity exceeds 1.0 ⁇ 10 4 mPa ⁇ s, in the following cases 1.0 ⁇ 10 4 mPa ⁇ s rotor No. 40, were measured using, respectively.
- Examples 9, 10 For the deposited layer of silver nanowires after irradiation with the pulsed light shown in Table 2, the surface resistance value was measured using a LOCESTA-GP MCP-T610 4-probe method surface resistivity and volume resistivity measuring device manufactured by Mitsubishi Chemical Corporation. Was measured.
- Example 4 a roll press was performed under the conditions shown in Table 3 using a 10-t hydraulic roll press (manufactured by Sank Metal Co., Ltd.) instead of the pulsed light irradiation. At that time, a PET film (Lumilar 125T60 surface untreated grade thickness 125 ⁇ m manufactured by Toray Industries, Inc., thickness 125 ⁇ m) was laminated on the silver nanowire deposition layer for the purpose of protecting the coating film, and therefore the gap was 250 ⁇ m, which was the sum of the uniform base material thickness. About the deposited layer of the silver nanowire after pressing, the surface resistance value was measured using a LORESTA-GP MCP-T610 4-probe method surface resistivity and volume resistivity measuring device manufactured by Mitsubishi Chemical Corporation.
- LORESTA-GP MCP-T610 4-probe method surface resistivity and volume resistivity measuring device manufactured by Mitsubishi Chemical Corporation.
- Comparative Example 1 Although there was no problem in printability and pattern maintainability during heating, conductivity was not exhibited even when light irradiation was performed or heating at 200 ° C.
- Comparative Example 2 A pattern was printed in the same manner as in the example, and an attempt was made to evaluate it, but the viscosity was too low to print.
- Example 8 Conductivity was exhibited by irradiation at 600 V and 100 ⁇ sec (exposure amount 2.89 J / cm 2 ). It should be noted that conductivity was not exhibited by pulsed light irradiation under the same conditions as in Examples 1-7. It is presumed that copper is hard to sinter for reasons such as higher melting point than silver or easy oxidation of the surface.
- Examples 7, 9, and 10 are the results of studying the influence of light irradiation conditions (exposure amount). It was confirmed that by increasing the irradiation energy of the pulsed light, it was reduced to 50 ⁇ / ⁇ and high transmittance could be maintained.
- the transparent conductive ink was irradiated with light after pattern printing.
- the printed pattern was pressed instead of light irradiation. It was confirmed that the conductive ink of the present invention can exhibit conductivity even by pressing. It was also confirmed that the conductivity was improved with increasing press pressure.
- the solvent was dried at 80 ° C. for 30 minutes after drying with a hot air dryer at 50 ° C. for 30 minutes. At this point, the printed pattern is tack-free, but the resistance value can be measured. Resistance did not drop.
- Pulse light irradiation was performed 5 times at 600 V-50 ⁇ sec using PulseForge 3300 manufactured by NovaCentrix.
- the irradiation interval (off time) was set to about 30 seconds without considering productivity.
- the resistance value between Ia and Ib in FIG. 3 was measured with a digital multimeter PC500a manufactured by Sanwa Denki Keiki. As a result, the resistance value was 5 k ⁇ to 6 k ⁇ . Range.
- the resistance value is not measurable (high resistance exceeding the measurement limit) and short-circuited. I knew it was n’t there.
Abstract
Description
(1)金属ナノワイヤを含有する導電性インクを基板に塗布する工程。
(2)焼成を行い、透明導電層を形成する工程。
(3)感光性を有するレジストを上記透明導電層上に形成する工程。
(4)微細パターンに相当する適当な遮光マスクを通じてレジストに光エネルギーを付与する工程。
(5)得られたレジストの潜像を、適当な現像用溶液による溶出によって現像する工程。
(6)適当なエッチング方法を用いて露出した被パターニング膜(透明導電層)を除去する工程。
(7)残存したレジストを適当な方法を用いて除去する工程。
(1)水に分散した銀ナノワイヤを含有する導電性インクを基板に塗布する工程。
(2)焼成を行い、銀ナノワイヤ網層を形成する工程。
(3)プレポリマーを含有する光硬化型のマトリクス材を前記銀ナノワイヤ網層上に形成する工程。
(4)微細パターンに相当する適当な遮光マスクを通じてマトリクス材に光エネルギーを付与する工程。
(5)非硬化領域を溶媒(エタノール)で洗浄することによって除去する工程。または、粘着テープや粘着性ロールを用いて非硬化領域を物理的に除去する工程。
(1)感光性樹脂を含む溶液に分散した銀ナノワイヤを含有する導電性インクを基板に塗布する工程。
(2)微細パターンに相当する適当な遮光マスクを通じて感光性樹脂に光エネルギーを付与する工程。
(3)非硬化領域を現像液によって現像する工程。
(1)透明基材の表面に金属ナノフィラーを含む樹脂溶液を塗布する工程。
(2)この透明導電膜の表面に、パターン状の開口部が形成されたマスクを配置する工程。
(3)このマスクの透明導電膜と反対側からプラズマ処理またはコロナ処理を行なって、マスクの開口部に対応する部分の透明導電膜中の金属ナノフィラーを強制酸化することによって、酸化された金属ナノフィラーで非導通部を形成すると共に酸化されていない金属ナノフィラーで導通部を形成する工程。
(1)樹脂、及び、シリコーン系又はフッ素系の界面活性剤を含有する撥液性透明絶縁インキを用いて、印刷法によりパターンを基板上に形成し、
(2)前記撥液性透明絶縁インキの乾燥皮膜に対して、はじき性を有する導電インクを全面に塗布し、該導電インクが、該撥液性透明絶縁インキの乾燥皮膜に、はじかれることにより、基板上の、該撥液性透明絶縁インキの乾燥皮膜が形成されていない部分に導電インキ層を形成する。
(1)バインダーとして有機導電性高分子を含む溶液に分散した銀ナノワイヤを含有する導電性インクを使用し、グラビア印刷法により導電層パターンを形成する工程。
(2)前工程で形成した該導電層パターンを第二の基板上に転写して透明電極を形成する工程。
(1)バインダー樹脂としてTgが0~250℃の範囲のセルロース誘導体のような水溶性高分子含む溶液に銀ナノワイヤが分散された導電性インクを基板に印刷する工程。
(2)導体パターンを加圧条件下で加熱加湿処理して水溶性高分子を溶出させる工程。
<銀ナノワイヤの作製>
ポリビニルピロリドンK-90((株)日本触媒社製)(0.049g)、AgNO3(0.052g)およびFeCl3(0.04mg)を、エチレングリコール(12.5mlに溶解し、150℃で1時間加熱反応した。得られた析出物を遠心分離により単離し、析出物を乾燥して目的の銀ナノワイヤを得た。図2(a)、(b)に、得られた銀ナノワイヤのSEM像を示す。使用したSEMは、日立ハイテク株式会社製 FE-SEM S-5200である。
上記150℃で1時間加熱反応した銀ナノワイヤの反応液に、6倍容量のジブチルエーテルを添加して攪拌後、静置してナノワイヤを沈降させた。ナノワイヤの沈降後、デカンテーションにより上澄み液を分離することにより、溶媒置換を行い、銀ナノワイヤを約20質量%含んだジブチルエーテルに分散した銀ナノワイヤの懸濁液を得た。
実施例1においてジブチルエーテル、テルソルブ MTPH、粘度調整溶媒の種類、添加量を表1に示した量に変更した以外は実施例1同様に表1に記載の濃度となるよう調製し透明導電性インクを得た。
銀ナノワイヤとして前記合成品を使用する代わりに市販品SLV-NW-35(bluenano社製 イソプロパノール分散液、濃度10mg/ml、銀ナノワイヤの径35nm、長さ約15μm(カタログ値))を用い、その銀ナノワイヤ分散液に対して、テルピネオール(日本テルペン化学(株)製)を少量加え、良く分散させた後、イソプロパノールを留去し溶媒置換を行った。その後テルソルブ MTPH(日本テルペン化学(株)製、イソボルニルシクロヘキサノール)およびテルピネオールを最終的に分散媒の濃度が表1~3に記載の配合比(質量比)となるように加え、(株)シンキー社製のARV-310を用いてよく分散させた分散液を得た。なお、最終的に得られる分散液の濃度が表1~3記載の濃度になるよう、最初に加える少量のテルピネオールの量はそれぞれ予め計算して決定しておいた。
表1に示した配合でポリビニルピロリドン(K-90((株)日本触媒社製)とジエチレングリコールの混合物を分散媒として、実施例1において用いた合成銀ナノワイヤに対して添加したインクを調製した。
表1に示したようにテルソルブ MTPHを使用せず、ジブチルエーテルとL-α-テルピネオールのみを分散媒として、実施例1において用いた合成銀ナノワイヤに対して添加したインクを調製した。
ナノワイヤとして銅ナノワイヤ(NANOFORGE社製 イソプロパノール分散液、濃度約1g/900ml)を用い、インクを作製した。本分散液には銅ナノワイヤの凝集を防ぐ目的でワイヤ表面にポリビニルピロリドンがワイヤを付着させているので、インク作製の前に、後述する精製操作を行った。
実施例1~3、比較例1、2
実施例1~3の各透明導電性インクを用いて3cm角のベタ膜と図3に示すパターンをスクリーン印刷機MT-320TVZ(マイクロテック(株)製)により印刷(クリアランス:1.0~1.5mm、スキージアタック角度:70°、スキージスピード:6mm/sec、スキージ圧:0.2MPa、スクレッパ圧:0.15MPa、背圧:0.1MPa)した。また、基材には東洋紡(株)社製二軸延伸ポリエステルフィルム:コスモシャイン(登録商標)A4300(厚み125μm)を用いた。
実施例4~13の各透明導電性インクを用いて2.5cm角のベタ膜をスクリーン印刷機MT-320TVZ(マイクロテック(株)製)により印刷(クリアランス:1.0mm、スキージアタック角度:70°、スキージスピード:6mm/sec、スキージ圧:0.2MPa、スクレッパ圧:0.15MPa、背圧:0.1MPa)した。また、基材にはPETフィルム(東レ株式会社製125U98易接着グレード 厚み125μm)を用いた。
ブルックフィールド社製型DV-II+Proを用いて形状保持材および透明導電性インクの粘度を25℃にて測定した。なお、粘度が1.0×104mPa・sを超える場合はロータ番号52を、1.0×104mPa・s以下の場合はロータ番号40を、各々用いて測定した。
実施例1~8、比較例1
表1に記載している600V、50μsec(露光量1.14J/cm2)のパルス光を照射した後の銀ナノワイヤの堆積層について、三菱化学株式会社製LORESTA-GP MCP-T610 4探針法表面抵抗率、体積抵抗率測定装置を使用して表面抵抗値を測定した。
表2に記載のパルス光を照射した後の銀ナノワイヤの堆積層について、三菱化学株式会社製LORESTA-GP MCP-T610 4探針法表面抵抗率、体積抵抗率測定装置を使用して表面抵抗値を測定した。
実施例4においてパルス光照射の代わりに10t油圧式ロールプレス(サンクメタル(株)製)を用い、表3に示す条件でロールプレスを行った。その際、塗膜保護の目的でPETフィルム(東レ株式会社製ルミラー125T60表面未処理グレード 厚み125μm)を銀ナノワイヤの堆積層上に積層したため、ギャップは一律基材厚みを足し合わせた250μmとした。プレス後の銀ナノワイヤの堆積層について、三菱化学株式会社製LORESTA-GP MCP-T610 4探針法表面抵抗率、体積抵抗率測定装置を使用して表面抵抗値を測定した。
実施例1~3、比較例1
日本電色工業(株)製濁度計NDH2000を用いて、全光線透過率を測定した。カッコ内の値は日本分光株式会社製の紫外可視近赤外分光光度計 Jasco V-570を用いて測定した可視光域(400~800nm)の光線透過率の参考値である。
日本電色工業(株)製濁度計NDH2000を用いて、全光線透過率を測定した。
印刷性や加熱時のパターン維持性は問題がなかったが、光照射を行っても、200℃で加熱しても導電性は発現しなかった。
実施例同様にパターンを印刷し評価を行おうとしたが、粘度が低すぎて印刷が出来なかった。
600V、100μsec(露光量2.89J/cm2)を照射することにより導電性が発現した。なお、実施例1~7と同条件のパルス光照射では導電性が発現しなかった。銀に比べて銅の方が融点が高い、あるいは表面が酸化しやすい等の理由で焼結し難いと推定される。
図3に示すパターンを持ったスクリーン版を用い、実施例1の組成を有するインクをスクリーン印刷機MT-320TVZ(マイクロテック(株)製)により印刷した。なお、基材にはコスモシャイン(登録商標)A4300(厚み125μm)を用いた。また、図3において、菱形パターンPの対角線長さは2.6mmとし、各菱形パターンPの角同士の間隔dは、図の横方向及び縦方向(上下左右方向)とも0.4mmとした。また、菱形パターンPを図の横方向(左右方向)を接続する接続部Cの線幅は0.3mmとした。
Claims (8)
- 金属ナノワイヤと金属ナノチューブの少なくとも一方と、分子量の範囲が150~500である有機化合物を含みかつ25℃における粘度が1.0×103~2.0×106mPa・sである形状保持材を有する分散媒と、を含むことを特徴とする透明導電性インク。
- 前記形状保持材に含まれる有機化合物は、単糖類、ポリオール、4級アルキル基または橋かけ環骨格を有するアルキル基、および水酸基を有する化合物のいずれかであることを特徴とする請求項1に記載の透明導電性インク。
- 前記形状保持材に含まれる有機化合物が、ジグリセリン、2,2,4-トリメチル-1.3-ペンタンジオールモノイソブチレート、2,2,4-トリメチル-1.3-ペンタンジオールジイソブチレート、キシルロース、リブロース、ボルニルシクロヘキサノール又はボルニルフェノール、イソボルニルシクロヘキサノール、イソボルニルフェノールのいずれかであることを特徴とする請求項2に記載の透明導電性インク。
- 前記分散媒は、形状保持材の粘度を調製する粘度調整溶媒をさらに含むことを特徴とする請求項1から請求項3のいずれか一項に記載の透明導電性インク。
- 前記粘度調整溶媒が、水、アルコール、ケトン、エーテル、炭化水素系溶剤および芳香族系溶剤のいずれかであることを特徴とする請求項4に記載の透明導電性インク。
- 前記粘度調整溶媒が、テルピネオールである請求項5に記載の透明導電性インク。
- 透明導電性インク総質量に対して、金属ナノワイヤまたは金属ナノチューブが0.01~10質量%の量であり、形状保持材の含有量が分散媒総質量に対して10~90質量%である請求項1から請求項6のいずれか一項に記載の透明導電性インク。
- 請求項1から請求項7のいずれか一項に記載の透明導電性インクにより、基板上に任意の形状のパターンを印刷する工程と、
前記パターンを加熱処理して乾燥させる工程と、
前記乾燥後のパターンにパルス光を照射する工程またはプレス工程と、
を有することを特徴とする透明導電パターン形成方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020147029936A KR101570398B1 (ko) | 2012-04-26 | 2013-04-26 | 투명 도전성 잉크 및 투명 도전 패턴형성방법 |
EP13782608.7A EP2843667B1 (en) | 2012-04-26 | 2013-04-26 | Transparent conductive ink, and method for producing transparent conductive pattern |
US14/396,853 US9236162B2 (en) | 2012-04-26 | 2013-04-26 | Transparent conductive ink and transparent conductive pattern forming method |
JP2014512709A JP5706998B2 (ja) | 2012-04-26 | 2013-04-26 | 透明導電性インク及び透明導電パターン形成方法 |
CN201380021843.3A CN104303238B (zh) | 2012-04-26 | 2013-04-26 | 透明导电性墨以及透明导电图案形成方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012101049 | 2012-04-26 | ||
JP2012-101049 | 2012-04-26 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2013161996A2 true WO2013161996A2 (ja) | 2013-10-31 |
WO2013161996A3 WO2013161996A3 (ja) | 2013-12-19 |
Family
ID=49483993
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/062387 WO2013161996A2 (ja) | 2012-04-26 | 2013-04-26 | 透明導電性インク及び透明導電パターン形成方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9236162B2 (ja) |
EP (1) | EP2843667B1 (ja) |
JP (1) | JP5706998B2 (ja) |
KR (1) | KR101570398B1 (ja) |
CN (1) | CN104303238B (ja) |
TW (1) | TWI499647B (ja) |
WO (1) | WO2013161996A2 (ja) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015153680A (ja) * | 2014-02-18 | 2015-08-24 | 大倉工業株式会社 | 透明導電フィルムの製造方法 |
JP2016087877A (ja) * | 2014-10-31 | 2016-05-23 | 国立大学法人大阪大学 | シートの製造方法 |
JP2016121241A (ja) * | 2014-12-24 | 2016-07-07 | 昭和電工株式会社 | 薄膜印刷用導電性組成物及び薄膜導電パターン形成方法 |
JP2017509108A (ja) * | 2014-01-22 | 2017-03-30 | ヌォーヴォ フィルム インコーポレイテッドNuovo Film Inc. | 溶融した金属ナノワイヤを含む透明導電電極、及び、これを含む表示装置 |
CN107112093A (zh) * | 2014-08-11 | 2017-08-29 | 天津奈博科技有限公司 | 利用多级光照射的透明导电性膜的制造方法 |
WO2017208925A1 (ja) * | 2016-05-31 | 2017-12-07 | 昭和電工株式会社 | 透明導電パターンの形成方法 |
WO2017208924A1 (ja) * | 2016-05-31 | 2017-12-07 | 昭和電工株式会社 | 透明導電パターンの形成方法 |
WO2019073833A1 (ja) * | 2017-10-13 | 2019-04-18 | ユニチカ株式会社 | ニッケルナノワイヤーを含有するペースト |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6366577B2 (ja) * | 2013-04-26 | 2018-08-01 | 昭和電工株式会社 | 導電パターンの製造方法及び導電パターン形成基板 |
DE102013104577B3 (de) * | 2013-05-03 | 2014-07-24 | Heraeus Noblelight Gmbh | Vorrichtung zum Trocknen und Sintern metallhaltiger Tinte auf einem Substrat |
EP3064556B1 (en) * | 2013-10-31 | 2019-10-02 | Showa Denko K.K. | Electrically conductive composition for thin film printing, and method for forming thin film conductive pattern |
US11090858B2 (en) | 2014-03-25 | 2021-08-17 | Stratasys Ltd. | Method and system for fabricating cross-layer pattern |
WO2016068602A1 (ko) * | 2014-10-28 | 2016-05-06 | 주식회사 엔앤비 | 투명 전도체 및 이의 제조방법 |
US20160164171A1 (en) * | 2014-12-04 | 2016-06-09 | Chung-Ping Lai | Wireless antenna made from binder-free conductive carbon inks |
US20180254549A1 (en) * | 2014-12-04 | 2018-09-06 | Chung-Ping Lai | Wireless antenna made from binder-free conductive carbon-based inks |
KR20170130515A (ko) * | 2015-03-25 | 2017-11-28 | 스트라타시스 엘티디. | 전도성 잉크의 인 시츄 소결을 위한 방법 및 시스템 |
KR102555869B1 (ko) * | 2015-08-06 | 2023-07-13 | 삼성전자주식회사 | 도전체 및 그 제조 방법 |
KR20170108612A (ko) * | 2016-03-18 | 2017-09-27 | 한국과학기술원 | 빛을 이용한 박막 제조방법 |
JP6889020B2 (ja) * | 2016-05-02 | 2021-06-18 | デクセリアルズ株式会社 | 異方性導電フィルムの製造方法、及び異方性導電フィルム |
WO2017191776A1 (ja) * | 2016-05-02 | 2017-11-09 | デクセリアルズ株式会社 | 異方性導電フィルムの製造方法、及び異方性導電フィルム |
WO2017205285A1 (en) | 2016-05-23 | 2017-11-30 | Konica Minolta Laboratory U.S.A., Inc. | Method of forming transparent correlated metal electrode |
WO2018101334A1 (ja) * | 2016-12-01 | 2018-06-07 | 昭和電工株式会社 | 透明導電基板及びその製造方法 |
CN110168047B (zh) * | 2016-12-13 | 2023-08-08 | 默克专利有限公司 | 有机功能材料的制剂 |
WO2018131702A1 (ja) * | 2017-01-16 | 2018-07-19 | 昭和電工株式会社 | 透明導電フィルム及び透明導電パターンの製造方法 |
EP3587020A4 (en) * | 2017-02-23 | 2020-01-01 | Osaka University | CONNECTING ELEMENT, METHOD FOR PRODUCING THE CONNECTING ELEMENT AND METHOD FOR PRODUCING THE CONNECTING STRUCTURE |
TWI691403B (zh) * | 2017-07-18 | 2020-04-21 | 日商旭化成股份有限公司 | 銅配線 |
TW202022063A (zh) * | 2018-09-13 | 2020-06-16 | 日商昭和電工股份有限公司 | 導電性墨及碳配線基板 |
CN110272663A (zh) * | 2019-06-24 | 2019-09-24 | 南昌和创优材电子科技有限公司 | 透明导电薄膜及其制备方法 |
CN110204963A (zh) * | 2019-06-24 | 2019-09-06 | 南昌和创优材电子科技有限公司 | 透明导电油墨、其制备方法及应用 |
CN111249765B (zh) * | 2020-02-25 | 2021-04-06 | 中国科学院化学研究所 | 一种去除碳材料中金属离子的加压流体提取系统和方法 |
CN111416058B (zh) * | 2020-04-03 | 2024-04-19 | 苏州星烁纳米科技有限公司 | 一种导电薄膜、显示装置和显示装置的制作方法 |
CN111446382B (zh) * | 2020-04-03 | 2023-05-09 | 苏州星烁纳米科技有限公司 | 一种电致发光器件及其制备方法、显示装置 |
KR102461794B1 (ko) * | 2020-08-13 | 2022-11-02 | 한국과학기술연구원 | 은 나노와이어 메쉬 전극 및 이의 제조방법 |
CN111883286A (zh) * | 2020-08-25 | 2020-11-03 | 深圳先进电子材料国际创新研究院 | 一种透明导电膜的制备方法及透明导电膜 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH077675B2 (ja) | 1986-10-27 | 1995-01-30 | 株式会社荏原製作所 | レドツクスフロ−形電池の水溶液に蓄熱し、該熱を熱源として使用する方法 |
JP2003100147A (ja) | 2001-09-25 | 2003-04-04 | Nagase & Co Ltd | カーボンナノチューブを含有する導電性材料およびその製造方法 |
WO2008046058A2 (en) | 2006-10-12 | 2008-04-17 | Cambrios Technologies Corporation | Nanowire-based transparent conductors and applications thereof |
WO2008073143A2 (en) | 2006-06-21 | 2008-06-19 | Cambrios Technologies Corporation | Methods of controlling nanostructure formations and shapes |
JP2009505358A (ja) | 2005-08-12 | 2009-02-05 | カンブリオス テクノロジーズ コーポレイション | ナノワイヤに基づく透明導電体 |
JP2010073322A (ja) | 2008-09-16 | 2010-04-02 | Konica Minolta Holdings Inc | 透明電極とその製造方法及びそれを用いた有機エレクトロルミネッセンス素子 |
JP2010165900A (ja) | 2009-01-16 | 2010-07-29 | Dic Corp | 透明電極の製造方法、透明電極及びそれに用いる導電インキ及び撥液性透明絶縁インキ |
JP2010287540A (ja) | 2009-06-15 | 2010-12-24 | Panasonic Electric Works Co Ltd | 透明導電パターンの製造方法及び透明導電パターン付き基材 |
JP2011070968A (ja) | 2009-09-25 | 2011-04-07 | Panasonic Electric Works Co Ltd | 導電性ペースト及び導体パターン |
JP2012009383A (ja) | 2010-06-28 | 2012-01-12 | Jnc Corp | 塗膜形成用組成物、該組成物から得られるパターニングされた透明導電膜を有する基板の製造方法および該製造物の用途 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06139814A (ja) * | 1992-10-26 | 1994-05-20 | Hitachi Ltd | 導体ペースト |
JP4077675B2 (ja) | 2002-07-26 | 2008-04-16 | ナガセケムテックス株式会社 | ポリ(3,4−ジアルコキシチオフェン)とポリ陰イオンとの複合体の水分散体およびその製造方法 |
US7303854B2 (en) * | 2003-02-14 | 2007-12-04 | E.I. Du Pont De Nemours And Company | Electrode-forming composition for field emission type of display device, and method using such a composition |
US7569165B2 (en) | 2005-03-09 | 2009-08-04 | E. I. Du Pont De Nemours And Company | Black conductive compositions, black electrodes, and methods of forming thereof |
CN1848303B (zh) | 2005-03-09 | 2011-05-04 | E.I.内穆尔杜邦公司 | 黑导电组合物、黑电极及利用它们的制品 |
KR101456838B1 (ko) * | 2007-04-20 | 2014-11-04 | 캄브리오스 테크놀로지즈 코포레이션 | 복합 투명 도전체 및 그 제조 방법 |
JP2009140788A (ja) * | 2007-12-07 | 2009-06-25 | Konica Minolta Holdings Inc | 導電材料、それを用いたインクジェットインク及び透明導電性フィルム |
CN101932666A (zh) | 2008-01-30 | 2010-12-29 | 陶氏康宁公司 | 玻璃状硅氧烷基硬涂层作为可印刷电子器件的剥离涂层的用途 |
KR101135337B1 (ko) * | 2008-08-07 | 2012-04-17 | 교토 에렉스 가부시키가이샤 | 태양전지소자의 전극형성용 도전성 페이스트, 태양전지소자 및 그 태양전지소자의 제조방법 |
KR20100109416A (ko) * | 2009-03-31 | 2010-10-08 | 디아이씨 가부시끼가이샤 | 도전성 페이스트 조성물 및 그 제조 방법 |
JP2011060752A (ja) | 2009-08-12 | 2011-03-24 | Nippon Kineki Kk | 導電性ペースト組成物 |
JP2011159670A (ja) * | 2010-01-29 | 2011-08-18 | Mitsubishi Electric Corp | セラミック多層回路基板の製造方法および該製造方法により製造されたセラミック多層回路基板 |
JP2012023088A (ja) * | 2010-07-12 | 2012-02-02 | Yokohama Rubber Co Ltd:The | 太陽電池電極用ペーストおよび太陽電池セル |
TWI481326B (zh) * | 2011-11-24 | 2015-04-11 | Showa Denko Kk | A conductive pattern forming method, and a conductive pattern forming composition by light irradiation or microwave heating |
TW201339279A (zh) * | 2011-11-24 | 2013-10-01 | Showa Denko Kk | 導電圖型形成方法及藉由光照射或微波加熱的導電圖型形成用組成物 |
TWI569700B (zh) * | 2011-11-25 | 2017-02-01 | 昭和電工股份有限公司 | 導電性圖案生成方法 |
JP5587522B2 (ja) * | 2012-03-09 | 2014-09-10 | 昭和電工株式会社 | 透明導電パターンの製造方法 |
JPWO2013161997A1 (ja) * | 2012-04-26 | 2015-12-24 | 国立大学法人大阪大学 | 透明導電基板の製造方法、透明導電基板及び静電容量式タッチパネル |
-
2013
- 2013-04-26 CN CN201380021843.3A patent/CN104303238B/zh active Active
- 2013-04-26 JP JP2014512709A patent/JP5706998B2/ja active Active
- 2013-04-26 KR KR1020147029936A patent/KR101570398B1/ko active IP Right Grant
- 2013-04-26 WO PCT/JP2013/062387 patent/WO2013161996A2/ja active Application Filing
- 2013-04-26 US US14/396,853 patent/US9236162B2/en active Active
- 2013-04-26 TW TW102115035A patent/TWI499647B/zh active
- 2013-04-26 EP EP13782608.7A patent/EP2843667B1/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH077675B2 (ja) | 1986-10-27 | 1995-01-30 | 株式会社荏原製作所 | レドツクスフロ−形電池の水溶液に蓄熱し、該熱を熱源として使用する方法 |
JP2003100147A (ja) | 2001-09-25 | 2003-04-04 | Nagase & Co Ltd | カーボンナノチューブを含有する導電性材料およびその製造方法 |
JP2009505358A (ja) | 2005-08-12 | 2009-02-05 | カンブリオス テクノロジーズ コーポレイション | ナノワイヤに基づく透明導電体 |
WO2008073143A2 (en) | 2006-06-21 | 2008-06-19 | Cambrios Technologies Corporation | Methods of controlling nanostructure formations and shapes |
WO2008046058A2 (en) | 2006-10-12 | 2008-04-17 | Cambrios Technologies Corporation | Nanowire-based transparent conductors and applications thereof |
JP2010073322A (ja) | 2008-09-16 | 2010-04-02 | Konica Minolta Holdings Inc | 透明電極とその製造方法及びそれを用いた有機エレクトロルミネッセンス素子 |
JP2010165900A (ja) | 2009-01-16 | 2010-07-29 | Dic Corp | 透明電極の製造方法、透明電極及びそれに用いる導電インキ及び撥液性透明絶縁インキ |
JP2010287540A (ja) | 2009-06-15 | 2010-12-24 | Panasonic Electric Works Co Ltd | 透明導電パターンの製造方法及び透明導電パターン付き基材 |
JP2011070968A (ja) | 2009-09-25 | 2011-04-07 | Panasonic Electric Works Co Ltd | 導電性ペースト及び導体パターン |
JP2012009383A (ja) | 2010-06-28 | 2012-01-12 | Jnc Corp | 塗膜形成用組成物、該組成物から得られるパターニングされた透明導電膜を有する基板の製造方法および該製造物の用途 |
Non-Patent Citations (5)
Title |
---|
CHEM. MATER., vol. 14, 2002, pages 4736 |
J. AM. CHEM. SOC., vol. 126, 2004, pages 3892 - 3901 |
J. AM. CHEM. SOC., vol. 129, 2007, pages 1733 |
See also references of EP2843667A4 |
SHIH-HSIANG LAI; CHUN-YAO OU; CHIA-HAO TSAI; BOR-CHUAN CHUANG; MING-YING MA; SHUO-WEI LIANG, SID SYMPOSIUM DIGEST OF TECHNICAL PAPERS, vol. 39, no. 1, 2008, pages 1200 - 1202 |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017509108A (ja) * | 2014-01-22 | 2017-03-30 | ヌォーヴォ フィルム インコーポレイテッドNuovo Film Inc. | 溶融した金属ナノワイヤを含む透明導電電極、及び、これを含む表示装置 |
JP2015153680A (ja) * | 2014-02-18 | 2015-08-24 | 大倉工業株式会社 | 透明導電フィルムの製造方法 |
US10270004B2 (en) * | 2014-08-11 | 2019-04-23 | N&B Co., Ltd. | Production method for transparent electrically-conductive film using multistage light irradiation |
CN107112093A (zh) * | 2014-08-11 | 2017-08-29 | 天津奈博科技有限公司 | 利用多级光照射的透明导电性膜的制造方法 |
CN107112093B (zh) * | 2014-08-11 | 2019-09-03 | 天津奈博科技有限公司 | 利用多级光照射的透明导电性膜的制造方法 |
JP2016087877A (ja) * | 2014-10-31 | 2016-05-23 | 国立大学法人大阪大学 | シートの製造方法 |
JP2016121241A (ja) * | 2014-12-24 | 2016-07-07 | 昭和電工株式会社 | 薄膜印刷用導電性組成物及び薄膜導電パターン形成方法 |
WO2017208924A1 (ja) * | 2016-05-31 | 2017-12-07 | 昭和電工株式会社 | 透明導電パターンの形成方法 |
KR20180121638A (ko) | 2016-05-31 | 2018-11-07 | 쇼와 덴코 가부시키가이샤 | 투명 도전 패턴의 형성 방법 |
KR20180121639A (ko) | 2016-05-31 | 2018-11-07 | 쇼와 덴코 가부시키가이샤 | 투명 도전 패턴의 형성 방법 |
WO2017208925A1 (ja) * | 2016-05-31 | 2017-12-07 | 昭和電工株式会社 | 透明導電パターンの形成方法 |
WO2019073833A1 (ja) * | 2017-10-13 | 2019-04-18 | ユニチカ株式会社 | ニッケルナノワイヤーを含有するペースト |
US10954396B2 (en) | 2017-10-13 | 2021-03-23 | Unitika Ltd. | Paste containing nickel nanowires |
Also Published As
Publication number | Publication date |
---|---|
US9236162B2 (en) | 2016-01-12 |
US20150056382A1 (en) | 2015-02-26 |
WO2013161996A3 (ja) | 2013-12-19 |
CN104303238A (zh) | 2015-01-21 |
TW201410801A (zh) | 2014-03-16 |
EP2843667A4 (en) | 2015-10-21 |
KR20150004355A (ko) | 2015-01-12 |
JPWO2013161996A1 (ja) | 2015-12-24 |
CN104303238B (zh) | 2016-11-09 |
TWI499647B (zh) | 2015-09-11 |
KR101570398B1 (ko) | 2015-11-19 |
EP2843667A2 (en) | 2015-03-04 |
EP2843667B1 (en) | 2017-09-06 |
JP5706998B2 (ja) | 2015-04-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5706998B2 (ja) | 透明導電性インク及び透明導電パターン形成方法 | |
TWI655090B (zh) | 透明電極及其製造方法 | |
CN106928773B (zh) | 一种可用于喷墨打印的石墨烯复合导电墨水及其制备方法 | |
TWI619060B (zh) | 透明導電基板之製造方法、透明導電基板及靜電電容式觸控面板 | |
EP2824676B1 (en) | Method for manufacturing transparent conductive pattern | |
KR20170066555A (ko) | 투명 코팅 및 투명 전도성 필름을 위한 특성 향상 충진제 | |
JPWO2015068654A1 (ja) | 導電パターン形成方法及びこれを使用したオンセル型タッチパネルの製造方法並びにこれに使用する転写用フィルム及びオンセル型タッチパネル | |
TWI671766B (zh) | 導電性薄膜及導電性薄膜之製造方法 | |
KR102228232B1 (ko) | 투명 도전 패턴의 형성 방법 | |
JP6356453B2 (ja) | 透明導電パターン形成用基板、透明導電パターン形成基板及び透明導電パターン形成基板の製造方法 | |
WO2017208925A1 (ja) | 透明導電パターンの形成方法 | |
JP2011070968A (ja) | 導電性ペースト及び導体パターン |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13782608 Country of ref document: EP Kind code of ref document: A2 |
|
ENP | Entry into the national phase |
Ref document number: 2014512709 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20147029936 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14396853 Country of ref document: US |
|
REEP | Request for entry into the european phase |
Ref document number: 2013782608 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013782608 Country of ref document: EP |