WO2017195500A1 - 導電性素子、入力装置および電子機器 - Google Patents
導電性素子、入力装置および電子機器 Download PDFInfo
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- WO2017195500A1 WO2017195500A1 PCT/JP2017/013958 JP2017013958W WO2017195500A1 WO 2017195500 A1 WO2017195500 A1 WO 2017195500A1 JP 2017013958 W JP2017013958 W JP 2017013958W WO 2017195500 A1 WO2017195500 A1 WO 2017195500A1
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- wiring
- conductive element
- fluorine
- element according
- contact angle
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/0412—Digitisers structurally integrated in a display
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/0416—Control or interface arrangements specially adapted for digitisers
- G06F3/04164—Connections between sensors and controllers, e.g. routing lines between electrodes and connection pads
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0448—Details of the electrode shape, e.g. for enhancing the detection of touches, for generating specific electric field shapes, for enhancing display quality
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/047—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using sets of wires, e.g. crossed wires
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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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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04111—Cross over in capacitive digitiser, i.e. details of structures for connecting electrodes of the sensing pattern where the connections cross each other, e.g. bridge structures comprising an insulating layer, or vias through substrate
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04112—Electrode mesh in capacitive digitiser: electrode for touch sensing is formed of a mesh of very fine, normally metallic, interconnected lines that are almost invisible to see. This provides a quite large but transparent electrode surface, without need for ITO or similar transparent conductive material
Definitions
- the present technology relates to a conductive element, an input device including the same, and an electronic device. Specifically, the present invention relates to a conductive element provided with a wiring.
- Patent Document 1 proposes a technique in which a lead-out wire connecting a transparent electrode and an external circuit in a touch panel is formed by performing a drying process or a baking process after printing a conductive paste.
- An object of the present technology is to provide a conductive element in which wiring is thinned, an input device including the same, and an electronic device.
- the 1st art is provided with the substrate which has the surface containing fluorine, and the wiring provided in the surface, and the detection intensity of the fluorine in the surface is a conductive element whose intensity is 96,834 cps or more. It is.
- the second technology is a conductive element including a substrate having a surface containing fluorine and a wiring provided on the surface, and the contact angle of water on the surface is 100 degrees or more.
- the third technology is an input device provided with the conductive element of the first or second technology.
- a fourth technology is an electronic device provided with the conductive element of the first or second technology.
- FIG. 1 is a perspective view showing an example of the appearance of an electronic device according to an embodiment of the present technology.
- FIG. 2A is a cross-sectional view showing an example of the configuration of a touch panel type display device.
- FIG. 2B is an exploded perspective view showing an example of the configuration of the input device.
- FIG. 3 is a plan view showing an example of the configuration of the first transparent conductive element.
- FIG. 3B is a plan view showing an example of the configuration of the second transparent conductive element.
- FIG. 4 is a graph showing the relationship between the amount of fluorine in the process gas and the line width.
- FIG. 5 is a graph showing an enlarged F1s peak.
- FIG. 6A is a graph showing the C1s peak in an enlarged manner.
- FIG. 6B is a graph showing the O1s peak in an enlarged manner.
- FIG. 7A is a graph showing the relationship between the amount of fluorine in the process gas and the contact angle.
- FIG. 7B is a graph showing the relationship between the amount of fluorine in the process gas and the line width.
- FIG. 8A is a graph showing the relationship between the amount of fluorine in the process gas and the wiring thickness.
- FIG. 8B is a graph showing the relationship between the amount of fluorine in the process gas and the resistance value.
- FIG. 9 is a graph showing the relationship between the amount of fluorine in the process gas and the adhesion.
- FIG. 10A is a plan view showing a microscopic observation image of the wiring film of Example 2-1.
- FIG. 10B is a perspective view showing a microscopic observation image of the wiring film of Example 2-1.
- FIG. 10C is a cross-sectional view taken along line XC-XC of FIG. 10B.
- FIG. 11A is a plan view showing a microscopic observation image of the wiring film of Example 2-3.
- FIG. 11B is a perspective view showing a microscopic observation image of the wiring film of Example 2-3.
- FIG. 11C is a cross-sectional view along the line XIC-XIC of FIG. 11B.
- FIG. 12A is a plan view showing a microscopic observation image of the wiring film of Comparative Example 2-1.
- FIG. 12B is a perspective view showing a microscopic observation image of the wiring film of Comparative Example 2-1.
- FIG. 12C is a cross-sectional view along the line XIIC-XIIC of FIG. 12B.
- FIG. 13A is a graph showing the measurement results of the adhesion of the wiring film of Example 2-3.
- FIG. 13B is a graph showing the measurement results of the adhesion of the wiring film of Comparative Example 2-1.
- an electronic device 10 As illustrated in FIG. 1, an electronic device 10 according to an embodiment of the present technology is a so-called smartphone, and includes a housing 11 and a touch panel display device 12 housed in the housing 11.
- the touch panel display device 12 includes a display element 20 and an input device 30 provided on the display surface of the display element 20, as shown in FIG. 2A.
- the display element 20 and the input device 30 are pasted together via the pasting layer 21 which consists of adhesives etc., for example.
- Display element As the display element 20, for example, various display elements such as a liquid crystal display element and an organic ELC luminescence (hereinafter referred to as "EL") element can be used.
- EL organic ELC luminescence
- the input device 30 is a so-called projected capacitive touch panel. As shown to FIG. 2A and FIG. 2B, the input device 30 is equipped with the 1st transparent conductive element 30a and the 2nd transparent conductive element 30b provided on the 1st transparent conductive element 30a. The 1st transparent conductive element 30a and the 2nd transparent conductive element 30b are bonded together through the bonding layer which is not shown in figure.
- a protective layer may be provided on the surface on the input surface side of the second transparent conductive element 30b, if necessary, on the surface of the first transparent conductive element 30a on the display element 20 side.
- a shield layer may be provided if necessary.
- two directions having a relationship of orthogonal intersection in the plane of the input surface of the input device 30 are defined as an X-axis direction (first direction) and a Y-axis direction (second direction).
- a direction perpendicular to the input surface of the input device 30 is defined as a Z-axis direction (third direction).
- the first transparent conductive element 30a includes a base 31a, a plurality of transparent electrodes 32a and a plurality of wirings 33a provided on one surface of the base 31a, and the like. And an insulating layer 34a provided on one surface of the base 31 so as to cover the transparent electrode 32a and the wiring 33a.
- the second transparent conductive element 30b includes a base 31b, a plurality of transparent electrodes 32b provided on one surface of the base 31b, a plurality of wirings 33b, and the like.
- an insulating layer b provided on one surface of the base 31b so as to cover the transparent electrode 32b and the wiring 33b.
- the insulating layers 34a and 34b are not shown.
- a flexible printed circuit (FPC) 35 is provided on the periphery of the first transparent conductive element 30a and the second transparent conductive element 30b bonded together.
- the substrates 31a and 31b contain fluorine on at least one surface.
- the detection intensity of fluorine on one surface of the base materials 31a and 31b is not less than 96834 cps, preferably not less than 96834 cps and not more than 200,000 cps, more preferably not less than 149381 cps and not more than 200,000 cps. Since the contact angle of water (specifically, the contact angle of the solvent contained in the conductive ink) can be sufficiently increased when the detection strength of fluorine is at least 96834 cps, the wirings 33a and 33b can be thinned. On the other hand, the fall of the contact power of wiring 33a and 33b to substrate 31a and 31b can be controlled as the detection intensity of fluorine is 200,000 cps or less.
- the detected intensity of fluorine on one surface of the substrate 31a is measured as follows. First, depth direction analysis (depth profile measurement) of the first transparent conductive element 30a by X-ray photoelectron spectroscopy (XPS) is performed while ion milling from the insulating layer 34a side of the first transparent conductive element 30a. . Then, the position where the detection intensity of fluorine is maximum is regarded as the surface of the base 31a, and the detection intensity of fluorine at this position is taken as "the detection intensity of fluorine on one surface of the base 31a".
- depth direction analysis depth profile measurement
- XPS X-ray photoelectron spectroscopy
- the detection intensity of fluorine on one surface of the substrate 31b is also measured in the same manner as the detection intensity of fluorine on one surface of the substrate 31a.
- the contact angle of water on one surface of the substrates 31a and 31b is 100 degrees or more, preferably 100 degrees or more and 120 degrees or less, and more preferably 110 degrees or more and 120 degrees or less.
- the contact angle is 100 degrees or more
- the contact angle of water specifically, the contact angle of the solvent contained in the conductive ink
- the fall of the contact power of wiring 33a and 33b to substrate 31a and 31b can be controlled as a contact angle is 120 degrees or less.
- the fluorine is preferably deposited on one surface of the substrates 31a and 31b. This is because the contact angle of water (specifically, the contact angle of the solvent contained in the conductive ink) can be sufficiently increased, so that the degree of thinning of the wirings 33a and 33b can be further improved.
- the fluorine deposited on one surface of the substrates 31a and 31b may constitute a thin film.
- Arithmetic mean roughness Ra on one surface of the substrates 31a and 31b is, for example, 2 nm or less.
- the substrates 31a and 31b are preferably films having flexibility. This is because the first and second transparent conductive elements 30a and 30b can be manufactured by roll to roll, so that the production efficiency can be improved. It is preferable that the surface of one of the substrates 31a and 31b is subjected to an easy adhesion treatment. This is because the adhesion of the wires 33a and 33b can be improved.
- Examples of the material of the substrates 31a and 31b include polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polycarbonate (PC), polyimide (PI), triacetate (TAC), polyethylene naphthalate (PEN), Polymer of one or more of aramid, acrylic resin, polyester (TPEE), polyamide (PA), cycloolefin polymer (COP), cycloolefin copolymer (COC), epoxy resin, urea resin, urethane resin, melamine resin and the like Resin is mentioned. From the viewpoint of heat resistance, among these resins, at least one of polypropylene, polyimide, polyethylene naphthalate and aramid is preferable, and polyimide is most preferable.
- the thickness of the substrates 31a and 31b is preferably 3 ⁇ m to 500 ⁇ m from the viewpoint of productivity, but is not particularly limited to this range.
- the base 31a may have a single-layer structure, or may have a layer structure of two or more layers.
- a base material 31 which has a layer structure of two or more layers a thing provided with a base material layer and a surface layer provided in at least one side of a base material layer is mentioned, for example.
- materials of the base layer and the surface layer those exemplified above as the materials of the bases 31a and 31b can be used.
- the transparent electrodes 32 a are X electrodes extended in the X-axis direction, and are arrayed at predetermined intervals in the Y-axis direction.
- the transparent electrodes 32b are Y electrodes extended in the Y-axis direction, and are arrayed in the X-axis direction at predetermined intervals.
- the transparent electrodes 32a connect a plurality of pad portions (unit electrode bodies) 36a provided at predetermined intervals in the X-axis direction and a plurality of pad portions 36a adjacent in the X-axis direction. And a unit 37a.
- the pad portion 36a and the connecting portion 37a are integrally formed.
- the transparent electrode 32b connects a plurality of pad portions (unit electrode bodies) 36b provided at predetermined intervals in the Y-axis direction and a plurality of connection portions connecting the pad portions 36b adjacent in the Y-axis direction.
- a unit 37b The pad portion 36 b and the connecting portion 37 b are integrally formed.
- connection portions 37a and 37b are orthogonally crossed so that the connection portions 37a and 37b overlap, and the pad portions 36a and 36b are spread in the XY plane.
- the shape of the pad portions 36a and 36b may be, for example, a polygon such as a rhombus (diamond shape) or a rectangle, a star shape, a cross shape, a mesh shape, or the like, but is not limited to these shapes. .
- FIG. 2B, FIG. 3A, and FIG. 3B the case where the shape of pad part 36a, 36b is a rhombus is illustrated.
- the shape of the transparent electrodes 32a and 32b may be linear. In this case, the plurality of transparent electrodes 32a and 32b have stripe shapes orthogonally crossing each other in plan view in the Z-axis direction.
- a material of the transparent electrodes 32a and 32b for example, one or more selected from the group consisting of a metal oxide material having electrical conductivity, a metal material, a carbon material, a conductive polymer, and the like can be used.
- metal oxide materials include indium tin oxide (ITO), zinc oxide, indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, silicon-doped zinc oxide, zinc oxide And tin oxide type, indium oxide-tin oxide type, zinc oxide-indium oxide-magnesium oxide type, and the like.
- particles such as a metal nanoparticle and a metal wire
- materials constituting those particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, Examples thereof include metals such as bismuth, antimony and lead, and alloys thereof.
- the carbon material include carbon black, carbon fiber, fullerene, graphene, carbon nanotube, carbon micro coil, nano horn and the like.
- the conductive polymer for example, substituted or unsubstituted polyaniline, polypyrrole, polythiophene, and (co) polymer consisting of one or two or more selected from these can be used.
- the wiring 33a is a lead wiring that electrically connects the transparent electrode 32a and the FPC 35, is drawn out from one end of the transparent electrode 32a, is drawn around the peripheral portion of the base 31a, and is connected to the FPC 35.
- the wiring 33 b is a lead wiring that electrically connects the transparent electrode 32 b and the FPC 35, is drawn out from one end of the transparent electrode 32 b, is drawn around the peripheral portion of the base 31 b, and is connected to the FPC 35.
- the wiring 33a contains a powder of metal particles.
- the wiring 33a may further include at least one of a binder such as a thermoplastic resin and an additive, as required.
- the metal particles are, for example, gold (Au), silver (Ag), copper (Cu), titanium (Ti), tungsten (W), molybdenum (Mo), indium (In), aluminum (Al) and nickel (Ni) Contains at least one of the Examples of the shape of the metal particles include, for example, spheres, ellipsoids, needles, plates, scales, wires, rods (rods), and irregular shapes, but are not particularly limited thereto. .
- the width w of the wirings 33a and 33b is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and still more preferably 100 ⁇ m or less.
- the wirings 33a and 33b can be sufficiently narrowed (densified), so that the frame 13 of the electronic device 10 can be sufficiently narrowed.
- the width w of the wires 33a and 33b is 200 ⁇ m or less, the non-visibility of the wires 33a and 33b (that is, the transparency of the region in which the wires 33a and 33b are provided) can be improved.
- the thickness t of the wirings 33a and 33b is preferably 1.9 ⁇ m or more, more preferably 1.9 ⁇ m to 10.0 ⁇ m, and still more preferably 3.5 ⁇ m to 9.0 ⁇ m.
- the thickness t of the wirings 33a and 33b is 1.9 ⁇ m or more, the resistance of the wirings 33a and 33b can be reduced.
- the thickness t of the interconnections 33a and 33b varies in the width direction
- the thickness of the interconnections 33a and 33b means the thickness of the interconnections 33a and 33b which becomes maximum in the width direction.
- the aspect ratio (thickness t / width w) of the wirings 33a and 33b is preferably 0.03 or more, more preferably 0.03 or more and 0.10 or less, and still more preferably 0.06 or more and 0.10 or less.
- the aspect ratio is 0.03 or more, the wirings 33a and 33b can be narrowed while holding the wirings 33a and 33b at low resistance.
- the resistance value of the wires 33a and 33b is preferably 1.0 ⁇ / mm or less.
- the wirings 33 a and 33 b can be used for various electronic devices including the input device 30.
- any of an inorganic material and an organic material may be used.
- the inorganic materials for example, be SiO 2, SiNx, SiON, Al 2 O 3, Ta 2 O 5, Y 2 O 3, HfO 2, HfAlO, and ZrO 2, TiO 2 is used.
- the organic material for example, polyacrylate such as polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polystyrene (PS), transparent polyimide, polyester, epoxy, polyvinyl phenol, polyvinyl alcohol or the like can be used.
- the plasma water-repellent treatment refers to a treatment for imparting water repellency to one surface of the substrate 31 a by subjecting one surface of the substrate 31 a to plasma treatment.
- a plasma processing apparatus for performing plasma water repellent treatment one capable of performing plasma treatment under atmospheric pressure is preferable.
- the process gas one containing fluorine is used.
- a pulse power supply can be used as the power supply.
- the plasma water repellency treatment is adjusted so that the detection intensity of fluorine on one surface of the base material 31a is 96834 cps or more, preferably 96834 cps or more and 2000000 cps or less, more preferably 149381 cps or more and 200000 cps or less. Further, plasma water repellent treatment may be performed only on the region where the wiring 33a is to be formed.
- the plasma water repellent treatment is adjusted such that the contact angle of water on one surface of the substrate 31a is 100 degrees or more, preferably 100 degrees or more and 120 degrees or less, more preferably 110 degrees or more and 120 degrees or less.
- the transparent electrode 32a is formed on one surface of the base material 31a drawn out from the raw fabric.
- a method of forming the pattern of the transparent electrode 32a for example, a photolithography method or a printing method can be used.
- the transparent electrode 32a may be formed in advance on one surface of the substrate 31a before the plasma treatment. .
- the conductive ink is printed on one surface of the base 31a while the base 31a is being transported.
- the conductive ink contains the above-described powder of metal particles and a solvent.
- the conductive ink may optionally contain at least one of a binder and an additive such as a thermoplastic resin.
- a conductive paste may be used instead of the conductive ink.
- those capable of dispersing metal powder powder can be used, for example, water, alcohol (eg methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, etc.) At least one selected from tert-butanol etc.), anone (eg cyclohexanone, cyclopentanone), amide (eg N, N-dimethylformamide: DMF), sulfide (eg dimethyl sulfoxide: DMSO) etc. is used .
- alcohol eg methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, etc.
- At least one selected from tert-butanol etc. anone (eg cyclohexanone, cyclopentanone), amide (eg N, N-dimethyl
- a high boiling point solvent may be further added to the conductive ink to control the evaporation rate of the solvent from the conductive ink.
- a high boiling point solvent for example, butyl cellosolve, diacetone alcohol, butyl triglycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether , Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol isopropyl ether, trip Propylene glycol isopropyl ether, methyl glycol.
- a printing method for example, flexographic printing, screen printing, gravure printing, gravure offset printing, reverse offset printing, waterless flat plate printing, inkjet printing and the like can be used.
- the base materials 31a and 31b are transported to a heating furnace and passed through the heating furnace to volatilize the solvent contained in the printed conductive ink, thereby drying and baking the conductive ink.
- a heating furnace an infrared heating furnace, a heater heating furnace, a hot air circulation type heating furnace, etc. can be used, for example.
- An electronic device 10 includes first and second transparent conductive elements 30a and 30b.
- the first and second transparent conductive elements 30a and 30b respectively include substrates 31a and 31b having fluorine on one surface, and a plurality of wirings 33a and 33b provided on one surface of the substrates 31a and 31b. Equipped with The detection intensity of fluorine on one surface of the base materials 31a and 31b is 96,834 cps or more. For this reason, since the contact angle of water on one surface of the base materials 31a and 31b can be sufficiently increased, the wirings 33a and 33b can be thinned. Therefore, it is possible to narrow the frame 13 of the electronic device 10 and enlarge the display surface of the touch panel type display device 12.
- the conductive ink is printed on one surface of the substrates 31a and 31b subjected to plasma water repellent treatment, the conductive ink is the substrates 31a and 31b. It is possible to suppress the spread of wetting on one of the surfaces. Therefore, the wirings 33a and 33b can be thinned. In addition, since the thicknesses of the wirings 33a and 33b can be secured, low resistance wirings 33a and 33b can be obtained.
- the wiring and the conductive ink may contain carbon particles instead of or together with the metal particles.
- a carbon particle 1 or more types in fullerene, a graphene, a carbon nanotube, etc. can be used, for example.
- the substrate surface may be made water repellent by the
- the conductive element to which the present technology can be applied include transparent conductive elements such as resistive film type touch panels, IC cards, display elements (for example, liquid crystal display elements, organic EL elements, inorganic EL elements, electronic paper, etc.)
- a printed wiring board, a printed circuit board, etc. are mentioned.
- the term "printed wiring board” means one having no wiring but only wiring.
- printed circuit board means one provided with an electronic component along with a wiring to operate as an electronic circuit.
- the type of the board is not particularly limited, and any of a flexible board, a rigid board, and a rigid flexible board may be used.
- the above-mentioned embodiment explained the example which applied this art to frame wiring of an input device, this art is applicable also to wiring other than frame wiring.
- the present technology is also applicable to the formation of a pattern of electrodes having a matrix or the like. In this case, since the electrode can be thinned (narrowed), the non-visibility of the electrode can be improved.
- the input device includes a transparent conductive element in which transparent electrodes and wires are provided on both sides, instead of the first and second transparent conductive elements in which the transparent electrodes and wires are provided on one side. Good. In this case, the input device can be further thinned.
- Examples 1-1, 1-2, Comparative Examples 1-1 to 1-3 (Plasma treatment) First, a raw film of PET film (A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 250 ⁇ m subjected to double-sided easy adhesion treatment was attached to a roll-to-roll atmospheric pressure plasma processing apparatus. Next, plasma water repellent treatment was performed on one side of the PET film drawn from the raw fabric, and then it was wound up. As the process gas, a mixture of fluorine and nitrogen was used, and the mixture ratio was changed for each sample. A pulse power source was used as a power source.
- the conductive ink printed PET film was transported to a heating oven at 120 ° C., and the printed conductive ink was dried and fired by transporting it in the oven for 30 minutes, and then wound up.
- the target wiring film conductive element
- the wiring width of the wiring film obtained as described above was measured using a laser microscope (LEXT OLS4000 manufactured by Olympus Corporation).
- FIG. 4 shows the measurement results of the wiring widths of the wiring films of Examples 1-1 and 1-2 and Comparative Examples 1-1 to 1-3, and the approximate curve of the second-order polynomial obtained from the measurement results.
- the wiring width can be made 200 ⁇ m or less by setting the detection intensity of fluorine on the surface of the PET film to 96834 [cps] or more. Further, the wiring width can be made 150 ⁇ m or less by setting the detection intensity of fluorine on the surface of the PET film to 149381 [cps] or more.
- Example 2-1 Example 1 using a mixture of fluorine and nitrogen at a volume ratio of 5:95 as a process gas, and using the detection strength of fluorine and the contact angle of water on one side of a PET film as follows: A wiring film was obtained in the same manner as -1. Detection strength of fluorine: 159645 cps Water contact angle: 100 degrees
- the detection intensity of fluorine was determined in the same manner as in Example 1-1.
- the contact angle was determined using a contact angle meter (Biolin Scientific, Theta T200 Basic).
- Embodiment 2-2 Example 1 using a mixture of fluorine and nitrogen at a volume ratio of 15: 85 as a process gas, and using the detection strength of fluorine and the contact angle of water on one side of a PET film as follows: A wiring film was obtained in the same manner as -1. Detection strength of fluorine: 174914 cps Water contact angle: 103 degrees
- Example 2-3 Using a mixture of fluorine and nitrogen at a volume ratio of 25:75 as the process gas, the detection strength of fluorine, the contact angle of water, and the arithmetic average roughness Ra on one side of the PET film were as follows: A wiring film was obtained in the same manner as in Example 1-1 except for the above. Detection strength of fluorine: 184946 cps Water contact angle: 106 degrees Arithmetic mean roughness Ra: 1.74 nm
- arithmetic mean roughness Ra was calculated
- AFM Atomic Force Microscope
- Comparative Example 2-1 A wiring film was obtained in the same manner as in Example 1-1 except that the wiring was printed with a conductive ink without subjecting one surface of the PET film to plasma water repellent treatment.
- the detection strength of fluorine, the contact angle of water, and the arithmetic mean roughness Ra on one side of the PET film not subjected to plasma water repellency treatment were the following values. Detection strength of fluorine: 11444 cps Water contact angle: 75 degrees Arithmetic mean roughness Ra: 2.26 nm
- the wiring width w and the wiring thickness t of the wiring film were measured using a laser microscope (LEXT OLS4000 manufactured by Olympus Corporation). Since the wiring thickness t fluctuates in the width direction of the wiring, the wiring thickness t that is the maximum in the width direction of the wiring is taken as the “wiring thickness t”. Next, the aspect ratio (t / w) was calculated using the measured wiring width w and wiring thickness t.
- the wiring resistance of the wiring film was measured using a tester (M-03, manufactured by Custom Co., Ltd.).
- Table 1 shows preparation conditions of the wiring films of Examples 2-1 to 2-3 and Comparative Example 2-1 and the results of measurement / calculation.
- FIG. 5, FIG. 6A, and FIG. 6B are graphs which expand and represent F1s, C1s, and O1s peaks, respectively.
- 7A, 7B, 8A, 8B, and 9 show the measurement results of the contact angle, the wire width, the wire thickness, the resistance value, and the adhesion, respectively.
- 10A, 10B and 10C show microscopically observed images of the wiring film of Example 2-1.
- 11A, 11B, and 11C show microscopic images of the wiring film of Example 2-3.
- 12A, 12B, and 12C show microscopically observed images of the wiring film of Comparative Example 2-1.
- FIG. 13A shows the measurement results of the adhesion of the wiring film of Example 2-3.
- FIG. 13B shows the measurement results of the adhesion of the wiring film of Comparative Example 2-1.
- the contact angle of water on one side of the PET film can be made 100 degrees or more (see FIG. 7A).
- the wiring width can be 200 ⁇ m or less and the wiring thickness can be 1.9 ⁇ m or more.
- the wiring film subjected to the plasma water repellent treatment has a resistance value similar to that of the wiring film not subjected to the plasma water repellent treatment (see FIG. 8B).
- the wiring film subjected to the plasma water repellent treatment has the same adhesion as the wiring film not subjected to the plasma water repellent treatment (see FIG. 9). Therefore, by setting the contact angle of water on one side of the PET film to 100 degrees or more, the wiring width can be 200 ⁇ m or less and the wiring thickness can be 1.9 ⁇ m or more. Further, in the wiring film subjected to the plasma water repellent treatment, it is possible to achieve both the thinning (narrowing) of the wiring and the reduction of the resistance without causing a significant decrease in the adhesion.
- the present technology may adopt the following configuration.
- the substrate comprises one or more of polyethylene terephthalate, polyethylene, propylene, polycarbonate, polyimide, triacetyl cellulose and polyethylene naphthalate.
- the substrate is a film.
- the conductive element according to any one of (1) to (8), wherein the ratio of the thickness of the wiring to the width of the wiring is 0.06 or more.
- An input device comprising the conductive element according to any one of (1) to (10).
- the electronic device provided with the electroconductive element in any one of (1) to (10).
- the substrate surface is subjected to plasma treatment so that the detection intensity of fluorine on the substrate surface is 96834 cps or more
- a method of manufacturing a conductive element comprising printing a conductive ink on the surface of the substrate that has been subjected to plasma treatment.
- the substrate surface is subjected to plasma treatment so that the contact angle of water on the substrate surface is 100 degrees or more.
- a method of manufacturing a conductive element comprising printing a conductive ink on the surface of the substrate that has been subjected to plasma treatment.
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Abstract
Description
1 電子機器の構成
2 導電性素子の製造方法
3 効果
4 変形例
図1に示すように、本技術の一実施形態に係る電子機器10は、いわゆるスマートフォンであり、筐体11と、この筐体11に収容されたタッチパネル式の表示装置12とを備える。タッチパネル式の表示装置12は、図2Aに示すように、表示素子20と、表示素子20の表示面に設けられた入力装置30を備える。表示素子20と入力装置30とは、例えば粘着剤などからなる貼合層21を介して貼り合わされている。
表示素子20としては、例えば、液晶表示素子、有機エルクトロルミネッセンス(以下「EL」という。)素子などの各種表示素子を用いることができる。
入力装置30は、いわゆる投影型静電容量方式タッチパネルである。図2A、図2Bに示すように、入力装置30は、第1の透明導電性素子30aと、第1の透明導電性素子30a上に設けられた第2の透明導電性素子30bとを備える。第1の透明導電性素子30aと第2の透明導電性素子30bとは、図示しない貼合層を介して貼り合わされている。また、第2の透明導電性素子30bの入力面側の表面には、必要に応じて保護層が設けられていてもよいし、第1の透明導電性素子30aの表示素子20側の表面には、必要に応じてシールド層が設けられていてもよい。ここでは、入力装置30の入力面の面内において直交交差の関係にある2方向をX軸方向(第1方向)およびY軸方向(第2方向)と定義する。また、入力装置30の入力面に対して垂直な方向をZ軸方向(第3方向)と定義する。
第1の透明導電性素子30aは、図2A、図2Bに示すように、基材31aと、基材31aの一方の表面に設けられた複数の透明電極32aおよび複数の配線33aと、それらの透明電極32aおよび配線33aを覆うように基材31の一方の表面に設けられた絶縁層34aとを備える。第2の透明導電性素子30bは、図2A、図2Bに示すように、基材31bと、基材31bの一方の面に設けられた複数の透明電極32bおよび複数の配線33bと、それらの透明電極32bおよび配線33bを覆うように基材31bの一方の面に設けられた絶縁層34bとを備える。なお、図2Bでは、絶縁層34a、34bの図示を省略している。貼り合わされた第1の透明導電性素子30aおよび第2の透明導電性素子30bの周縁部には、フレキシブルプリント配線基板(Flexible Printed Circuit:FPC)35が設けられている。
基材31a、31bは、少なくとも一方の表面にフッ素を含んでいる。基材31a、31bの一方の表面におけるフッ素の検出強度が、96834cps以上、好ましくは96834cps以上200000cps以下、より好ましくは149381cps以上200000cps以下である。フッ素の検出強度が96834cps以上であると、水の接触角(具体的には導電インクに含まれる溶剤の接触角)を十分に大きくできるため、配線33a、33bを細線化できる。一方、フッ素の検出強度が200000cps以下であると、基材31a、31bに対する配線33a、33bの密着力の低下を抑制することができる。
透明電極32aは、X軸方向に延在されたX電極であり、Y軸方向に所定間隔離して配列されている。一方、透明電極32bは、Y軸方向に延在されたY電極であり、X軸方向に所定間隔離して配列されている。
配線33aは、透明電極32aとFPC35とを電気的に接続する引き回し配線であって、透明電極32aの一端から引き出され、基材31aの周縁部に引き回れてFPC35に接続されている。配線33bは、透明電極32bとFPC35とを電気的に接続する引き回し配線であって、透明電極32bの一端から引き出され、基材31bの周縁部に引き回れてFPC35に接続されている。
絶縁層34a、34bの材料としては、無機材料および有機材料のいずれを用いてもよい。無機材料としては、例えば、SiO2、SiNx、SiON、Al2O3、Ta2O5、Y2O3、HfO2、HfAlO、ZrO2、TiO2などを用いることができる。有機材料としては、例えば、ポリメチルメタクリレート(PMMA)などのポリアクリレート、ポリビニルアルコール(PVA)、ポリスチレン(PS)、透明性ポリイミド、ポリエステル、エポキシ、ポリビニルフェノール、ポリビニルアルコールなどを用いることができる。
次に、第1の透明導電性素子30aの製造方法について説明する。なお、第2の透明導電性素子30bの製造方法は第1の透明導電性素子30aの製造方法と同様であるため、ここでは、第1の透明導電性素子30aの製造方法についてのみ説明する。
まず、基材31aを搬送しながら基材31aの一方の面にプラズマ撥水処理を施す。ここで、プラズマ撥水処理とは、基材31aの一方の面にプラズマ処理を施すことにより、基材31aの一方の面に撥水性を付与する処理のことをいう。プラズマ撥水処理を施すためのプラズマ処理装置としては、生産性の観点からすると、大気圧下でプラズマ処理を施すことが可能なものが好ましい。プロセスガスとしては、フッ素を含むものが用いられる。電源としては、パルス電源を用いることができる。
次に、原反から繰り出された基材31aの一方の面に透明電極32aを形成する。透明電極32aのパターンの形成方法としては、例えばフォトリソグラフィ法または印刷法を用いることができる。ここでは、プラズマ処理後に基材31aの一方の面に透明電極32aを形成する場合について説明するが、プラズマ処理前に基材31aの一方の面に透明電極32aを予め形成しておいてもよい。
次に、基材31aを搬送しながら、基材31aの一方の面に導電インクを印刷する。導電インクは、上述の金属粒子の粉末および溶剤を含んでいる。導電インクが、必要に応じて熱可塑性樹脂などのバインダおよび添加剤のうちの少なくとも1種を含んでいてもよい。なお、導電インクに代えて導電ペーストを用いてもよい。
次に、基材31a、31bを加熱炉に搬送し加熱炉を通過させることにより、印刷された導電インクに含まれる溶剤を揮発させ、導電インクを乾燥焼成させる。加熱炉としては、例えば赤外線加熱炉、ヒータ加熱炉、熱風循環式加熱炉などを用いることができる。
本技術の一実施形態に係る電子機器10は、第1、第2の透明導電性素子30a、30bを備える。第1、第2の透明導電性素子30a、30bはそれぞれ、一方の表面にフッ素を含む基材31a、31bと、基材31a、31bの一方の面に設けられた複数の配線33a、33bとを備える。基材31a、31bの一方の表面におけるフッ素の検出強度が、96834cps以上である。このため、基材31a、31bの一方の表面における水の接触角を十分に大きくできるため、配線33a、33bを細線化できる。したがって、電子機器10の額縁13を狭額縁化して、タッチパネル式の表示装置12の表示面を大きくすることが可能となる。
配線および導電インクが、金属粒子に代えて、または金属粒子とともに、炭素粒子を含むようにしてもよい。炭素粒子としては、例えば、フラーレン、グラフェンおよびカーボンナノチューブなどのうちの1種以上を用いることができる。
(プラズマ処理)
まず、両面易接着処理が施された厚さ250μmのPETフィルム(東洋紡株式会社製、A4300)の原反を、Roll to Roll方式の大気圧プラズマ処理装置に取り付けた。次に、原反から繰り出されたPETフィルムの一方の面にプラズマ撥水処理を施した後、巻き取った。プロセスガスとしては、フッ素と窒素とを混合したものを用い、その混合比をサンプル毎に変化させた。電源としては、パルス電源を用いた。
X線源:マグネシウム
X線高圧値:8kV
エミッション電流値:20mA
分析範囲:φ6mm
次に、PETフィルムの一方の面にプラズマ撥水処理を施した原反をフレキソ印刷装置に取り付けた後、原反から繰り出されたPETフィルムの一方の面に導電インクで配線を印刷した。導電インクとしては、藤倉化成株式会社製のXA-3609(低粘度7700mpa・s)を用いた。フレキソ版(凸版)としては、線幅25μm(コムラテック製)のものを用いた。
次に、導電インクが印刷されたPETフィルムを120℃の加熱オーブンに搬送し、オーブン内を30分間かけて搬送することにより、印刷された導電インクを乾燥焼成させた後、巻き取った。以上により、目的とする配線フィルム(導電性素子)を得た。
上述のようにして得られた配線フィルムの配線幅をレーザー顕微鏡(オリンパス株式会社製、LEXT OLS4000)を用いて測定した。
図4に、実施例1-1、1-2、比較例1-1~1-3の配線フィルムの配線幅の測定結果、およびそれらの測定結果から求めた2次多項式の近似曲線を示す。図4から以下のことがわかる。PETフィルム表面におけるフッ素の検出強度を96834[cps]以上にすることで、配線幅を200μm以下にできる。また、PETフィルム表面におけるフッ素の検出強度を149381[cps]以上にすることで配線幅を150μm以下にできる。
プロセスガスとしてフッ素と窒素とを5:95との体積比で混合したものを用い、PETフィルムの一方の面におけるフッ素の検出強度および水の接触角を以下のようにしたこと以外は実施例1-1と同様にして配線フィルムを得た。
フッ素の検出強度:159645cps
水の接触角:100度
プロセスガスとしてフッ素と窒素とを15:85との体積比で混合したものを用い、PETフィルムの一方の面におけるフッ素の検出強度および水の接触角を以下のようにしたこと以外は実施例1-1と同様にして配線フィルムを得た。
フッ素の検出強度:174914cps
水の接触角:103度
プロセスガスとしてフッ素と窒素とを25:75との体積比で混合したものを用い、PETフィルムの一方の面におけるフッ素の検出強度、水の接触角および算術平均粗さRaを以下のようにしたこと以外は実施例1-1と同様にして配線フィルムを得た。
フッ素の検出強度:184946cps
水の接触角:106度
算術平均粗さRa:1.74nm
プラズマ撥水処理をPETフィルムの一方の面に施さずに、導電インクで配線を印刷したこと以外は実施例1-1と同様にして配線フィルムを得た。なお、プラズマ撥水処理をしていないPETフィルムの一方の面におけるフッ素の検出強度、水の接触角および算術平均粗さRaは、以下の値であった。
フッ素の検出強度:11444cps
水の接触角:75度
算術平均粗さRa:2.26nm
まず、配線フィルムの配線幅wおよび配線厚みtをレーザー顕微鏡(オリンパス株式会社製、LEXT OLS4000)を用いて測定した。なお、配線厚みtは配線の幅方向に変動していたため、配線の幅方向において最大となる配線厚みtを“配線厚みt”とした。次に、測定した配線幅wおよび配線厚みtを用いて、アスペクト比(t/w)を算出した。
配線フィルムの配線抵抗をテスター(株式会社カスタム製、M-03)を用いて測定した。
配線フィルムの密着力をスクラッチテスタを用いて測定した。
プロセスガス中におけるフッ素の体積比を5vol%以上にすることで、PETフィルムの一方の面における水の接触角を100度以上にできる(図7A参照)。
プロセスガス中におけるフッ素の体積比を5vol%以上にすることで、配線幅を200μm以下、配線厚さを1.9μm以上にできる。(図7B、図8A参照)
プラズマ撥水化処理を施した配線フィルムは、プラズマ撥水化処理をしていない配線フィルムと同程度の抵抗値を有している(図8B参照)。
プラズマ撥水化処理を施した配線フィルムは、プラズマ撥水化処理をしていない配線フィルムと同程度の密着力を有している(図9参照)。
したがって、PETフィルムの一方の面における水の接触角を100度以上とすることで、配線幅を200μm以下、配線厚さを1.9μm以上にできる。また、プラズマ撥水化処理を施した配線フィルムは、密着力の大幅な低下を招くことなく、配線の細線化(挟幅化)と低抵抗化とを両立することができる。
(1)
フッ素を含む表面を有する基材と、
前記表面に設けられた配線と
を備え、
前記表面におけるフッ素の検出強度が、96834cps以上である導電性素子。
(2)
前記配線の幅が、200μm以下である(1)に記載の導電性素子。
(3)
前記表面におけるフッ素の検出強度が、149381cps以上である(1)に導電性素子。
(4)
前記配線の幅が、150μm以下である(3)に記載の導電性素子。
(5)
前記表面における水の接触角が、100度以上である(1)から(4)のいずれかに記載の導電性素子。
(6)
前記基材は、ポリエチレンテレフタレート、ポリエチレン、プロピレン、ポリカーボネート、ポリイミド、トリアセチルセルロースおよびポリエチレンナフタレートのうちの1種以上を含む(1)から(5)のいずれかに記載の導電性素子。
(7)
前記基材が、フィルムである(1)から(6)のいずれかに記載の導電性素子。
(8)
前記配線の幅に対する前記配線の厚みの比率が、0.06以上である(1)から(8)のいずれかに記載の導電性素子。
(9)
フッ素が前記表面に堆積している(1)から(9)のいずれかに記載の導電性素子。
(10)
フッ素を含む表面を有する基材と、
前記表面に設けられた配線と
を備え、
前記表面における水の接触角が、100度以上である導電性素子。
(11)
(1)から(10)のいずれかに記載の導電性素子を備える入力装置。
(12)
(1)から(10)のいずれかに記載の導電性素子を備える電子機器。
(13)
基材表面におけるフッ素の検出強度が96834cps以上となるように、前記基材表面にプラズマ処理を施し、
プラズマ処理を施した前記基材表面に導電インクを印刷する
ことを含む導電性素子の製造方法。
(13)
基材表面における水の接触角が100度以上となるように、前記基材表面にプラズマ処理を施し、
プラズマ処理を施した前記基材表面に導電インクを印刷する
ことを含む導電性素子の製造方法。
11 筐体
12 タッチパネル式の表示装置
20 表示素子
30 入力装置
30a 第1の透明導電性素子
30b 第2の透明導電性素子
31a、31b 基材
32a、32b 透明電極
33a、33b 配線
34a、34b 絶縁層
Claims (12)
- フッ素を含む表面を有する基材と、
前記表面に設けられた配線と
を備え、
前記表面におけるフッ素の検出強度が、96834cps以上である導電性素子。 - 前記配線の幅が、200μm以下である請求項1に記載の導電性素子。
- 前記表面におけるフッ素の検出強度が、149381cps以上である請求項1に導電性素子。
- 前記配線の幅が、150μm以下である請求項3に記載の導電性素子。
- 前記表面における水の接触角が、100度以上である請求項1に記載の導電性素子。
- 前記基材は、ポリエチレンテレフタレート、ポリエチレン、プロピレン、ポリカーボネート、ポリイミド、トリアセチルセルロースおよびポリエチレンナフタレートのうちの1種以上を含む請求項1に記載の導電性素子。
- 前記基材が、フィルムである請求項1に記載の導電性素子。
- 前記配線の幅に対する前記配線の厚みの比率が、0.06以上である請求項1に記載の導電性素子。
- フッ素が前記表面に堆積している請求項1に記載の導電性素子。
- フッ素を含む表面を有する基材と、
前記表面に設けられた配線と
を備え、
前記表面における水の接触角が、100度以上である導電性素子。 - 請求項1に記載の導電性素子を備える入力装置。
- 請求項1に記載の導電性素子を備える電子機器。
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US16/097,512 US10474309B2 (en) | 2016-05-10 | 2017-04-03 | Conductive element, input device, and electronic apparatus |
KR1020187031260A KR20190004272A (ko) | 2016-05-10 | 2017-04-03 | 도전성 소자, 입력 장치 및 전자 기기 |
EP17795861.8A EP3460638A4 (en) | 2016-05-10 | 2017-04-03 | CONDUCTIVE ELEMENT, INPUT DEVICE AND ELECTRONIC DEVICE |
CN201780027677.6A CN109154870A (zh) | 2016-05-10 | 2017-04-03 | 导电性元件、输入装置和电子设备 |
JP2018516893A JP6891881B2 (ja) | 2016-05-10 | 2017-04-03 | 導電性素子、入力装置および電子機器 |
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JP (1) | JP6891881B2 (ja) |
KR (1) | KR20190004272A (ja) |
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- 2017-04-03 US US16/097,512 patent/US10474309B2/en not_active Expired - Fee Related
- 2017-04-03 CN CN201780027677.6A patent/CN109154870A/zh active Pending
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KR20190004272A (ko) | 2019-01-11 |
TW201740524A (zh) | 2017-11-16 |
CN109154870A (zh) | 2019-01-04 |
EP3460638A4 (en) | 2019-05-08 |
JPWO2017195500A1 (ja) | 2019-03-22 |
JP6891881B2 (ja) | 2021-06-18 |
US20190129542A1 (en) | 2019-05-02 |
EP3460638A1 (en) | 2019-03-27 |
US10474309B2 (en) | 2019-11-12 |
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