WO2021187573A1 - 透明導電性フィルム、および透明導電性フィルムの製造方法 - Google Patents

透明導電性フィルム、および透明導電性フィルムの製造方法 Download PDF

Info

Publication number
WO2021187573A1
WO2021187573A1 PCT/JP2021/011148 JP2021011148W WO2021187573A1 WO 2021187573 A1 WO2021187573 A1 WO 2021187573A1 JP 2021011148 W JP2021011148 W JP 2021011148W WO 2021187573 A1 WO2021187573 A1 WO 2021187573A1
Authority
WO
WIPO (PCT)
Prior art keywords
transparent conductive
film
conductive layer
conductive film
transparent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/011148
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
泰介 鴉田
望 藤野
鷹尾　寛行
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to CN202180022424.6A priority Critical patent/CN115298764A/zh
Priority to JP2021545721A priority patent/JP7308960B2/ja
Priority to KR1020227030820A priority patent/KR20220156824A/ko
Publication of WO2021187573A1 publication Critical patent/WO2021187573A1/ja
Priority to JP2022093446A priority patent/JP2022133292A/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • 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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B32B7/028—Heat-shrinkability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
    • H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/52—Means for reducing coupling between antennas; Means for reducing coupling between an antenna and another structure
    • 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
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes

Definitions

  • the present invention relates to a transparent conductive film and a method for producing a transparent conductive film.
  • a transparent conductive film in which a transparent base film made of resin and a transparent conductive layer are provided in order in the thickness direction is known.
  • the transparent conductive layer is used as a conductor film for forming a pattern of transparent electrodes in various devices such as liquid crystal displays, touch panels, and optical sensors.
  • an amorphous film of the transparent conductive material is formed on the base film by a sputtering method (film formation step).
  • film formation step a sputtering method
  • the amorphous transparent conductive layer on the base film is crystallized by heating (crystallization step).
  • a technique relating to such a transparent conductive film is described in, for example, Patent Document 1 below.
  • the transparent conductive layer of the transparent conductive film is required to have low resistance. Especially in transparent electrode applications, the demand is strong.
  • the present invention provides a transparent conductive film suitable for obtaining a transparent conductive film provided with a low-resistance crystalline transparent conductive layer in which the occurrence of cracks is suppressed, and a method for producing the transparent conductive film.
  • the present invention [1] is a transparent conductive film in which a transparent resin base material and a transparent conductive layer are provided in this order in the thickness direction, and the transparent resin base material is provided in a plane direction orthogonal to the thickness direction.
  • the heat shrinkage in the direction orthogonal to the direction in which the heat shrinkage after heat treatment at 165 ° C. for 60 minutes is maximum is 0.00% or more, and the transparent conductive layer is rare in that the atomic number is larger than that of argon.
  • the heat shrinkage of the transparent conductive film in the direction orthogonal to the direction in which the heat shrinkage rate after heat treatment at 165 ° C. for 60 minutes is maximum.
  • the transparent conductive film according to the above [1] which has a ratio of 0.03% or more.
  • the present invention [3] is a transparent conductive film in which a transparent resin base material and a transparent conductive layer are provided in this order in the thickness direction, and the transparent conductive film is provided in a plane direction orthogonal to the thickness direction.
  • the heat shrinkage in the direction orthogonal to the direction in which the heat shrinkage after heat treatment at 165 ° C. for 60 minutes is maximum is 0.03% or more, and the transparent conductive layer is rare in that the atomic number is larger than that of argon.
  • the present invention [4] includes the transparent conductive film according to any one of the above [1] to [3], wherein the noble gas atom is krypton.
  • the present invention [5] includes the transparent conductive film according to any one of the above [1] to [4], wherein the transparent conductive layer is amorphous.
  • the present invention [6] includes a step of preparing the transparent conductive film according to any one of the above [1] to [5] and a step of heating and crystallizing the transparent conductive layer. Includes a method for producing a conductive film.
  • the transparent conductive layer of the transparent conductive film of the present invention contains a rare gas atom having an atomic number larger than that of argon. Such a configuration is suitable for reducing the resistance of the transparent conductive layer. Further, the structure in which the transparent conductive layer contains a rare gas atom having an atomic number larger than that of argon is also suitable for heat-shrinking the transparent conductive layer by heat treatment.
  • the heat shrinkage rate in a predetermined direction after the heat treatment of the transparent resin base material is 0.00% or more, or the heat treatment of the transparent conductive film itself. The heat shrinkage rate in the subsequent predetermined direction is 0.03% or more.
  • Such a configuration is suitable for suppressing the generation of excessive internal stress in the heat-shrinked transparent conductive layer after, for example, heat treatment for crystallization of the transparent conductive layer.
  • the transparent conductive film as described above is suitable for obtaining a transparent conductive film provided with a low-resistance crystalline transparent conductive layer in which the occurrence of cracks is suppressed.
  • the method for producing a transparent conductive film of the present invention is suitable for obtaining a transparent conductive film provided with a low-resistance crystalline transparent conductive layer in which the occurrence of cracks is suppressed from such a transparent conductive film.
  • FIG. 2A shows a case where the transparent conductive layer includes the first region and the second region in order from the transparent resin base material side
  • FIG. 2B shows the case where the transparent conductive layer includes the second region and the first region in the transparent resin base material. Indicates the case of including in order from the side.
  • the method for producing the transparent conductive film shown in FIG. 1 is shown.
  • FIG. 3A shows a step of preparing a resin film
  • FIG. 3B shows a step of forming a functional layer on the resin film
  • FIG. 3C shows a step of forming a transparent conductive layer on the functional layer.
  • the transparent conductive film shown in FIG. 1 the case where the transparent conductive layer is patterned is shown.
  • the transparent conductive film shown in FIG. 1 the case where the amorphous transparent conductive layer is converted into the crystalline transparent conductive layer is shown. It is a graph which shows the relationship between the amount of oxygen introduced at the time of forming a transparent conductive layer by a sputtering method, and the specific resistance of the formed transparent conductive layer.
  • FIG. 1 is a schematic cross-sectional view of the transparent conductive film X, which is an embodiment of the transparent conductive film of the present invention.
  • the transparent conductive film X includes a transparent resin base material 10 and a transparent conductive layer 20 in this order toward one side in the thickness direction H.
  • the transparent conductive film X, the transparent resin base material 10, and the transparent conductive layer 20 each have a shape that spreads in a direction (plane direction) orthogonal to the thickness direction H.
  • the transmissive conductive film X is an element provided in a touch sensor, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shield member, a heater member, a lighting device, an image display device, and the like.
  • the transparent resin base material 10 includes a resin film 11 and a functional layer 12 in this order toward one side in the thickness direction H.
  • the resin film 11 is a transparent resin film having flexibility.
  • the material of the resin film 11 include polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyether sulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, and polystyrene resin.
  • the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate.
  • PET polyethylene terephthalate
  • Polyolefin resins include, for example, polyethylene, polypropylene, and cycloolefin polymers (COPs).
  • the acrylic resin include polymethacrylate.
  • At least one selected from the group consisting of polyester resin and polyolefin resin is preferably used from the viewpoint of transparency and strength, and more preferably selected from the group consisting of COP and PET. At least one of them is used, and more preferably PET is used.
  • the resin film 11 may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film.
  • the surface of the resin film 11 on the functional layer 12 side may be surface-modified.
  • Examples of the surface modification treatment include corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.
  • the thickness of the resin film 11 is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 30 ⁇ m or more.
  • the thickness of the resin film 11 is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 150 ⁇ m or less, and particularly preferably 100 ⁇ m or less.
  • the functional layer 12 is located on one surface of the resin film 11 in the thickness direction H.
  • the functional layer 12 include a hard coat layer, an adhesion improving layer, and a refractive index adjusting layer (index-matching layer).
  • the functional layer 12 as the hard coat layer makes it difficult for scratches to be formed on the exposed surface (upper surface in FIG. 1) of the transparent conductive layer 20.
  • the functional layer 12 as the adhesion improving layer realizes high adhesion of the transparent conductive layer 20 to the transparent resin base material 10.
  • the functional layer 12 as the refractive index adjusting layer adjusts the reflectance of the surface (one side of the thickness direction H) of the transparent resin base material 10.
  • the refractive index adjusting layer makes it difficult to visually recognize the pattern shape of the transparent conductive layer 20 when the transparent conductive layer 20 on the transparent resin base material 10 is patterned.
  • the functional layer 12 may be a layer that also serves as two or more layers selected from the group consisting of a hard coat layer, an adhesion improving layer, and a refractive index adjusting layer.
  • the functional layer 12 is a cured product layer of a curable resin composition.
  • the composition of the curable resin composition is adjusted according to the function of the functional layer 12.
  • the curable resin composition contains a curable resin and, if necessary, fine particles. The fine particles are useful for adjusting the hardness, surface roughness, and refractive index of the functional layer 12.
  • the curable resin examples include acrylic resin, urethane resin, amide resin, silicone resin, epoxy resin, and melamine resin.
  • the curable resin may be used alone or in combination of two or more.
  • examples of the curable resin include an ultraviolet curable resin and a thermosetting resin.
  • An ultraviolet curable resin is preferable as the curable resin from the viewpoint of helping to improve the production efficiency of the transparent conductive film X because it can be cured without heating at a high temperature.
  • Examples of the fine particles include metal oxide particles, glass particles, and organic particles.
  • Materials for the metal oxide particles include, for example, silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide.
  • Materials for organic particles include, for example, polymethylmethacrylate, polystyrene, polyurethane, acrylic-styrene copolymers, benzoguanamine, melamine, and polycarbonate.
  • the scratch hardness (JIS K 5600-5-4) measured by the pencil method for the functional layer 12 is preferably hardness H or higher.
  • the thickness of the functional layer 12 as the hard coat layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, from the viewpoint of exhibiting sufficient scratch resistance in the transparent conductive layer 20.
  • the thickness of the functional layer 12 is preferably 10 ⁇ m or less, more preferably 3 ⁇ m or less, from the viewpoint of ensuring the transparency of the functional layer 12.
  • the functional layer 12 When the functional layer 12 is an adhesion improving layer, the functional layer 12 preferably contains nanosilica particles.
  • the average particle size of the nanosilica particles is preferably 1 nm or more, more preferably 5 nm or more, and preferably 100 nm or less, more preferably 30 nm or less.
  • the average particle size of the nanosilica particles is the median size (particle size at which the cumulative volume frequency reaches 50% from the small diameter side) in the volume-based particle size distribution, and is based on, for example, the particle size distribution obtained by the laser diffraction / scattering method. Desired.
  • the thickness of the functional layer 12 as the adhesion improving layer is preferably 10 nm or more, more preferably 20 nm or more, and preferably 100 nm or less, more preferably 50 nm or less.
  • the refractive index of the functional layer 12 is, for example, 1.40 or more, preferably 1.55 or more, and for example, 1.80 or less, preferably 1.70 or less. Is.
  • the refractive index can be measured, for example, by an Abbe refractive index meter.
  • the thickness of the functional layer 12 as the refractive index adjusting layer is, for example, 5 nm or more, preferably 10 nm or more, and for example, 100 nm or less, preferably 50 nm or less.
  • the functional layer 12 may be a composite layer in which a plurality of layers are connected in the thickness direction H.
  • the composite layer preferably includes two or more layers selected from the group consisting of a hard coat layer, an adhesion improving layer, and a refractive index adjusting layer. Such a configuration is suitable for complex expression of the above-mentioned functions of each selected layer in the functional layer 12.
  • the surface of the functional layer 12 on the transparent conductive layer 20 side may be surface-modified.
  • Examples of the surface modification treatment include corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.
  • a cured product layer of the curable resin composition may be arranged on the other surface of the resin film 11 in the thickness direction H.
  • the layer include the above-mentioned hard coat layer, adhesion improving layer, and refractive index adjusting layer.
  • the thickness of the transparent resin base material 10 is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 15 ⁇ m or more, and particularly preferably 30 ⁇ m or more.
  • the thickness of the transparent resin base material 10 is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and further preferably 150 ⁇ m or less.
  • the total light transmittance (JIS K 7375-2008) of the transparent resin base material 10 is preferably 60% or more, more preferably 80% or more, still more preferably 85% or more. Such a configuration is obtained when the transparent conductive film X is provided in a touch sensor, a dimming element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shield member, a heater member, a lighting device, an image display device, or the like. It is suitable for ensuring the transparency required for the transparent conductive film X.
  • the total light transmittance of the transparent resin base material 10 is, for example, 100% or less.
  • the first direction is the direction in which the transparent resin base material 10 shrinks most in the plane direction when it undergoes heat treatment under heating conditions of 165 ° C. and 60 minutes.
  • the heat shrinkage rate of the transparent resin base material 10 in the first direction after heat treatment at 165 ° C. for 60 minutes is from the viewpoint of both suppressing the warp of the transparent resin base material 10 and suppressing cracks in the transparent conductive layer 20. Therefore, it is preferably 1.2% or less, more preferably 1% or less, and further preferably 0.8% or less.
  • the heat shrinkage rate is, for example, 0% or more.
  • the direction orthogonal to the first direction in the plane direction is defined as the second direction.
  • the heat shrinkage rate of the transparent resin base material 10 in the second direction after heat treatment at 165 ° C. for 60 minutes is the transparent resin base material 10 and the transparent conductive film X. From the viewpoint of suppressing warpage, it is 0.00% or more, preferably 0.03% or more, more preferably 0.1% or more, still more preferably 0.2% or more, and particularly preferably 0.3% or more. Is. From the viewpoint of suppressing warpage of the transparent conductive film X and suppressing cracks in the transparent conductive layer 20, the heat shrinkage rate in the second direction is preferably 1.2% or less, more preferably 1% or less. , More preferably 0.8% or less.
  • the transparent resin base material 10 is subjected to heat treatment and standing at room temperature for, for example, 30 minutes in sequence, and then the dimensional change of the transparent resin base material 10 before and after the heat treatment is measured. (The heat shrinkage of the transparent conductive film X, which will be described later, is also obtained). Further, in the first direction in which the heat shrinkage rate of the transparent resin base material 10 is maximum, for example, the axis extending in an arbitrary direction in the transparent resin base material 10 is set as a reference axis (0 °) in 15 ° increments from the reference axis. It is obtained by measuring the dimensional change rate before and after the heat treatment in the axial direction of.
  • the first direction is, for example, the MD direction for the transparent resin base material 10 (that is, the film running direction in the manufacturing process described later in the roll-to-roll method).
  • the second direction is the TD direction orthogonal to each of the MD direction and the thickness direction H.
  • Examples of the method for adjusting the heat shrinkage of the transparent resin base material 10 include adjusting the draw ratio of the resin film 11, adjusting the thickness of the resin film 11, and adjusting the composition and thickness of the functional layer 12 on the surface of the resin film 11. Adjustment can be mentioned. Examples of the method for adjusting the heat shrinkage of the transparent resin base material 10 include adjusting the temperature and time when the transparent resin base material 10 is annealed before the transparent conductive layer 20 is formed.
  • the transparent conductive layer 20 is located on one surface of the transparent resin base material 10 in the thickness direction H.
  • the transparent conductive layer 20 is an amorphous film having both light transmission and conductivity.
  • the amorphous transparent conductive layer 20 is converted into a crystalline transparent conductive layer (transparent conductive layer 20'described later) by heating, and the specific resistance is lowered.
  • the transparent conductive layer 20 is a layer formed of a light-transmitting conductive material.
  • the light-transmitting conductive material contains, for example, a conductive oxide as a main component.
  • the conductive oxide for example, at least one kind of metal selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd and W.
  • a metal oxide containing a semi-metal can be mentioned.
  • the conductive oxide include an indium-containing conductive oxide and an antimony-containing conductive oxide.
  • the indium-containing conductive oxide include indium tin oxide composite oxide (ITO), indium zinc composite oxide (IZO), indium gallium composite oxide (IGO), and indium gallium zinc composite oxide (IGZO). Be done.
  • the antimony-containing conductive oxide include antimony tin composite oxide (ATO).
  • an indium-containing conductive oxide is preferably used as the conductive oxide, and ITO is more preferably used.
  • the ITO may contain a metal or a semimetal other than In and Sn in an amount less than the respective contents of In and Sn.
  • the ratio of the tin oxide content to the total content of indium (In 2 O 3 ) and tin oxide (SnO 2) in the ITO is preferably 0.1% by mass. As mentioned above, it is more preferably 1% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more.
  • the ratio of the number of tin atoms to the number of indium atoms in ITO is preferably 0.001 or more, more preferably 0.03 or more, still more preferably 0.05 or more, and particularly preferably 0.05 or more. It is 07 or more.
  • the ratio of the tin oxide content to the total content of indium oxide (In 2 O 3 ) and tin oxide (SnO 2 ) in ITO is preferably 15% by mass or less, more preferably 13% by mass or less, still more preferably. Is 12% by mass or less.
  • the ratio of the number of tin atoms to the number of indium atoms in ITO is preferably 0.16 or less, more preferably 0.14 or less, and further preferably 0.13 or less.
  • the ratio of the number of tin atoms to the number of indium atoms in ITO can be obtained, for example, by specifying the abundance ratio of indium atoms and tin atoms in the object to be measured by X-ray Photoelectron Spectroscopy.
  • the above-mentioned content ratio of tin oxide in ITO is obtained from, for example, the abundance ratio of the indium atom and the tin atom thus specified.
  • the above-mentioned content ratio of tin oxide in ITO may be judged from the tin oxide (SnO 2) content ratio of the ITO target used at the time of sputtering film formation.
  • the transparent conductive layer 20 contains a noble gas atom (atom E) having an atomic number larger than that of argon.
  • a noble gas atom include krypton (Kr) and xenon (Xe), and Kr is preferably used.
  • the transparent conductive layer 20 may contain argon (Ar).
  • the noble gas atom in the transparent conductive layer 20 is derived from a rare gas atom used as a sputtering gas in the sputtering method described later for forming the transparent conductive layer 20.
  • the transparent conductive layer 20 is a film (sputtered film) formed by a sputtering method.
  • the structure in which the transparent conductive layer 20 contains the atom E realizes good crystal growth when the amorphous transparent conductive layer 20 is crystallized by heating to form a crystalline transparent conductive layer 20'. It is suitable for forming large crystal grains, and therefore suitable for obtaining a transparent conductive layer 20'with low resistance (the larger the crystal grains in the transparent conductive layer 20', the lower the resistance of the transparent conductive layer 20').
  • the content ratio of atomic E such as Kr in the transparent conductive layer 20 is preferably 1 atomic% or less, more preferably 0.5 atomic% or less, still more preferably 0.3 atomic% or less, particularly in the entire thickness direction H. It is preferably 0.2 atomic% or less. With such a configuration, when the amorphous transparent conductive layer 20 is crystallized by heating to form a crystalline transparent conductive layer 20', good crystal growth is realized and large crystal grains are formed. Suitable, and therefore suitable for obtaining a low resistance transparent conductive layer 20'.
  • the atomic E content ratio in the transparent conductive layer 20 is preferably 0.0001 atomic% or more over the entire area in the thickness direction H.
  • the transparent conductive layer 20 may include a region in which the atomic E content is less than 0.0001 atomic% in at least a part of the thickness direction H (that is, in a part of the thickness direction H, the thickness direction H).
  • the abundance ratio of atoms E in the cross section in the plane direction orthogonal to is may be less than 0.0001 atomic%).
  • the content ratio of the noble gas atom in the transparent conductive layer 20 can be identified by, for example, fluorescent X-ray analysis.
  • the content ratio of atoms E such as Kr in the transparent conductive layer 20 may be non-uniform in the thickness direction H.
  • the atomic E content may gradually increase or decrease as the distance from the transparent resin base material 10 increases.
  • the partial region where the atomic E content ratio gradually increases as the distance from the transparent resin base material 10 increases is located on the transparent resin base material 10 side, and the atomic E content ratio increases as the distance from the transparent resin base material 10 increases.
  • the partial region where is gradually reduced may be located on the opposite side of the transparent resin base material 10.
  • the partial region where the atomic E content ratio gradually decreases as the distance from the transparent resin base material 10 increases is located on the transparent resin base material 10 side, and the atomic E content ratio gradually decreases as the distance from the transparent resin base material 10 increases.
  • the partial region where is gradually increased may be located on the side opposite to the transparent resin base material 10.
  • the transparent conductive layer 20 may contain an atom E such as Kr in a part of the region in the thickness direction H.
  • FIG. 2A shows a case where the transparent conductive layer 20 includes the first region 21 and the second region 22 in this order from the transparent resin base material 10 side.
  • the first region 21 contains the atom E.
  • the second region 22 does not contain an atom E, and contains, for example, a noble gas atom other than the atom E.
  • Ar is preferably mentioned.
  • FIG. 2B shows a case where the transparent conductive layer 20 includes the second region 22 and the first region 21 in this order from the transparent resin base material 10 side.
  • the boundary between the first region 21 and the second region 22 is drawn by a virtual line.
  • the boundary between the first region 21 and the second region 22 is clearly defined. Cannot be determined.
  • the transparent conductive layer 20 has a first region 21 (atom E-containing region) and a second region 22 (atom E non-). (Containing region) is included in this order from the transparent resin base material 10 side.
  • the ratio of the thickness of the first region 21 to the total thickness of the first region 21 and the second region 22 is preferably 10% or more. It is more preferably 20% or more, further preferably 30% or more, and particularly preferably 40% or more. The same ratio is less than 100%.
  • the ratio of the thickness of the second region 22 to the total thickness of the first region 21 and the second region 22 is preferably 90% or less, more preferably 80% or less, still more preferably 70% or less, and particularly preferably. Is 60% or less.
  • the content ratio of the atom E in the first region 21 is preferably 1 atomic% or less, more preferably 0.5 atomic% or less, still more preferably 0.3 atomic% in the entire area of the thickness direction H of the first region 21. Hereinafter, it is particularly preferably 0.2 atomic% or less. Such a configuration is preferable from the viewpoint of reducing the resistance of the transparent conductive layer 20'obtained by crystallizing the transparent conductive layer 20. Further, the content ratio of the atom E in the first region 21 is, for example, 0.0001 atomic% or more in the entire area of the thickness direction H of the first region 21.
  • the content ratio of the atom E in the first region 21 may be non-uniform in the thickness direction H of the first region 21.
  • the atomic E content ratio may gradually increase or decrease as the distance from the transparent resin base material 10 increases.
  • a partial region in which the atomic E content ratio gradually increases as the distance from the transparent resin base material 10 increases is located on the transparent resin base material 10 side and moves away from the transparent resin base material 10.
  • the partial region where the atomic E content ratio gradually decreases may be located on the opposite side of the transparent resin base material 10.
  • a partial region in which the atomic E content ratio gradually decreases as the distance from the transparent resin base material 10 increases is located on the transparent resin base material 10 side and moves away from the transparent resin base material 10.
  • the partial region where the atomic E content ratio gradually increases may be located on the opposite side of the transparent resin base material 10.
  • the thickness of the transparent conductive layer 20 is preferably 10 nm or more, more preferably 20 nm or more, and further preferably 25 nm or more. Such a configuration is preferable from the viewpoint of reducing the resistance of the transparent conductive layer 20'obtained by crystallizing the transparent conductive layer 20.
  • the thickness of the transparent conductive layer 20 is preferably 1000 nm or less, more preferably less than 300 nm, further preferably 250 nm or less, still more preferably 200 nm or less, particularly preferably less than 150 nm, and most preferably 160 nm or less. Such a configuration is suitable for suppressing warpage in the transparent conductive film X provided with the transparent conductive layer 20'obtained by crystallizing the transparent conductive layer 20.
  • the specific resistance of the transparent conductive layer 20 is preferably 4 ⁇ 10 -4 ⁇ ⁇ cm or more, more preferably 4.5 ⁇ 10 -4 ⁇ ⁇ cm or more, still more preferably 5 ⁇ 10 -4 ⁇ ⁇ cm or more, particularly. It is preferably 5.5 ⁇ 10 -4 ⁇ ⁇ cm or more.
  • the specific resistance of the transparent conductive layer 20 is preferably 20 ⁇ 10 -4 ⁇ ⁇ cm or less, more preferably 15 ⁇ 10 -4 ⁇ ⁇ cm or less, still more preferably 10 ⁇ 10 -4 ⁇ ⁇ cm or less, and particularly preferably. It is 8 ⁇ 10 -4 ⁇ ⁇ cm or less.
  • the specific resistance is obtained by multiplying the surface resistance by the thickness.
  • the resistivity can be controlled by, for example, adjusting various conditions when the transparent conductive layer 20 is sputter-deposited.
  • the conditions include, for example, the temperature of the base (transparent resin base material 10 in this embodiment) on which the transparent conductive layer 20 is formed, the amount of oxygen introduced into the film forming chamber, the air pressure in the film forming chamber, and the target. Horizontal magnetic field strength of.
  • the specific resistance of the transparent conductive layer 20 after heat treatment at 165 ° C. for 60 minutes is preferably 2.2 ⁇ 10 -4 ⁇ ⁇ cm or less, 2.0 ⁇ 10 -4 ⁇ ⁇ cm or less, 1.9 ⁇ . It is 10 -4 ⁇ ⁇ cm or less, more preferably 1.8 ⁇ 10 -4 ⁇ ⁇ cm or less.
  • the specific resistance of the transparent conductive layer 20 after heat treatment at 165 ° C. for 60 minutes is preferably 0.1 ⁇ 10 -4 ⁇ ⁇ cm or more, more preferably 0.5 ⁇ 10 -4 ⁇ ⁇ cm or more. More preferably, it is 1.0 ⁇ 10 -4 ⁇ ⁇ cm or more.
  • the total light transmittance (JIS K 7375-2008) of the transparent conductive layer 20 is preferably 60% or more, more preferably 80% or more, still more preferably 85% or more.
  • the total light transmittance (JIS K 7375-2008) of the transparent conductive film X is preferably 60% or more, more preferably 80% or more, and further preferably 85% or more. These configurations are transparent when the transparent conductive film X is provided in a touch sensor, a dimming element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shield member, a heater member, a lighting device, an image display device, or the like. It is suitable for ensuring the transparency required for the conductive film X. Further, the total light transmittance of the transparent conductive layer 20 is, for example, 100% or less.
  • the direction in which the transparent conductive film X shrinks most in the plane direction when it undergoes heat treatment under heating conditions of 165 ° C. and 60 minutes is defined as the third direction.
  • the heat shrinkage rate of the transparent conductive film X after heat treatment at 165 ° C. for 60 minutes in the third direction is from the viewpoint of both suppressing the warp of the transparent conductive film X and suppressing cracks in the transparent conductive layer 20. Therefore, it is preferably 1.2% or less, more preferably 1% or less, and further preferably 0.8% or less.
  • the heat shrinkage rate is, for example, 0% or more.
  • the direction orthogonal to the third direction in the plane direction is defined as the fourth direction.
  • the heat shrinkage rate of the transparent conductive film X in the fourth direction after heat treatment at 165 ° C. for 60 minutes is a viewpoint of suppressing warpage of the transparent conductive film X. Therefore, it is 0.03% or more, preferably 0.05% or more, more preferably 0.1% or more, still more preferably 0.2% or more, and particularly preferably 0.3% or more. From the viewpoint of suppressing warpage of the transparent conductive film X and suppressing cracks in the transparent conductive layer 20, the heat shrinkage rate in the fourth direction is preferably 1.2% or less, more preferably 1% or less. , More preferably 0.8% or less.
  • the third direction in which the heat shrinkage rate of the transparent conductive film X is maximum is, for example, an axis extending in an arbitrary direction in the transparent conductive film X as a reference axis (0 °) and an axis in increments of 15 ° from the reference axis. It is obtained by measuring the dimensional change rate before and after the heat treatment in the direction.
  • the third direction is, for example, the MD direction for the transparent conductive film X (that is, the film running direction in the manufacturing process described later in the roll-to-roll method).
  • the fourth direction is the TD direction orthogonal to each of the MD direction and the thickness direction H.
  • the sample preparation method and the apparatus used for measuring the heat shrinkage rate of the transparent conductive film X are as described later with reference to Examples.
  • Examples of the method for adjusting the heat shrinkage of the transparent conductive film X include adjusting the draw ratio of the resin film 11, adjusting the thickness of the resin film 11, and adjusting the composition and thickness of the functional layer 12 on the surface of the resin film 11. Adjustment can be mentioned. Examples of the method for adjusting the heat shrinkage of the transparent conductive film X include adjusting the temperature and time when the transparent conductive film X is annealed before the transparent conductive layer 20 is formed.
  • the transparent conductive film X is manufactured as follows, for example.
  • the resin film 11 is prepared.
  • the resin film 11 may be annealed, if necessary.
  • the temperature of the annealing treatment is, for example, 100 ° C. or higher, and 200 ° C. or lower, for example.
  • the annealing treatment time is, for example, 1 minute or more, and 600 minutes or less, for example.
  • the functional layer 12 is formed on one surface of the resin film 11 in the thickness direction H.
  • the transparent resin base material 10 is produced by forming the functional layer 12 on the resin film 11.
  • the functional layer 12 can be formed by applying a curable resin composition on the resin film 11 to form a coating film, and then curing the coating film.
  • the curable resin composition contains an ultraviolet-forming resin
  • the coating film is cured by ultraviolet irradiation.
  • the curable resin composition contains a thermosetting resin
  • the coating film is cured by heating.
  • the exposed surface of the functional layer 12 formed on the resin film 11 is surface-modified, if necessary.
  • plasma treatment for example, argon gas is used as the inert gas.
  • the discharge power in the plasma processing is, for example, 10 W or more, and for example, 5000 W or less.
  • the transparent conductive layer 20 is formed on the transparent resin base material 10. Specifically, a material is formed on the functional layer 12 of the transparent resin base material 10 by a sputtering method to form the transparent conductive layer 20.
  • a sputtering film forming apparatus capable of carrying out the film forming process by the roll-to-roll method.
  • the transparent resin is carried while the long transparent resin base material 10 is run from the feeding roll to the winding roll provided in the apparatus.
  • a material is formed on the base material 10 to form a transparent conductive layer 20.
  • a sputtering film forming apparatus provided with one film forming chamber may be used, or sputtering forming provided with a plurality of film forming chambers sequentially arranged along a traveling path of the transparent resin base material 10.
  • a film device may be used (when the transparent conductive layer 20 including the above-mentioned first region 21 and second region 22 is formed, a sputtering film forming apparatus including a plurality of film forming chambers is used).
  • a sputtering gas in the sputtering method, specifically, while introducing a sputtering gas (inert gas) into the film forming chamber provided in the sputtering film forming apparatus under vacuum conditions, a negative voltage is applied to the target arranged on the cathode in the film forming chamber. Is applied. As a result, a glow discharge is generated to ionize gas atoms, the gas ions collide with the target surface at high speed, the target material is ejected from the target surface, and the ejected target material is used as the functional layer 12 in the transparent resin base material 10. Deposit on top.
  • a sputtering gas in the film forming chamber provided in the sputtering film forming apparatus under vacuum conditions
  • the above-mentioned conductive oxide for forming the transparent conductive layer 20 is used, and ITO is preferably used.
  • the ratio of the content of tin oxide to the total content of tin oxide and indium oxide in ITO is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5. It is 5% by mass or more, preferably 15% by mass or less, more preferably 13% by mass or less, and further preferably 12% by mass or less.
  • the sputtering method is preferably a reactive sputtering method.
  • a reactive gas is introduced into the film forming chamber in addition to the sputtering gas.
  • the transparent conductive layer 20 containing a rare gas atom (atom E) having an atomic number larger than that of argon is formed over the entire area in the thickness direction H (first case), 1 or 2 provided in the sputtering film forming apparatus.
  • the gas introduced into the above-mentioned film forming chamber contains an atom E as a sputtering gas and oxygen as a reactive gas.
  • the atom E as described above, Kr and Xe are mentioned, and Kr is preferably used.
  • the sputtering gas may contain an inert gas other than the atom E. Examples of the inert gas other than the atom E include Ar.
  • the sputtering gas contains an inert gas other than the atom E, the content ratio is preferably 80% by volume or less, more preferably 50% by volume or less.
  • the gas introduced into the film forming chamber for forming the first region 21 is a sputtering gas. It contains atom E as a reactive gas and oxygen as a reactive gas.
  • the sputtering gas may contain an inert gas other than the atom E.
  • the type and content ratio of the inert gas other than the atom E are the same as those described above for the inert gas other than the atom E in the first case.
  • the gas introduced into the film forming chamber for forming the second region 22 contains an inert gas other than the atom E as a sputtering gas and oxygen as a reactive gas.
  • the inert gas other than the atom E include the above-mentioned inert gas as the inert gas other than the atom E in the first case.
  • the ratio of the amount of oxygen introduced to the total amount of sputtering gas and oxygen introduced into the film forming chamber in the reactive sputtering method is, for example, 0.01 flow rate% or more, and for example, 15 flow rate% or less.
  • the air pressure in the film formation chamber during film formation (sputter film formation) by the sputtering method is, for example, 0.02 Pa or more, and for example, 1 Pa or less.
  • the temperature of the transparent resin base material 10 during the sputtering film formation is, for example, 100 ° C. or lower, preferably 50 ° C. or lower, more preferably 30 ° C. or lower, still more preferably 10 ° C. or lower, particularly preferably 0 ° C. or lower, and also.
  • it is ⁇ 50 ° C. or higher, preferably ⁇ 20 ° C. or higher, more preferably ⁇ 10 ° C. or higher, and even more preferably ⁇ 7 ° C. or higher.
  • Examples of the power supply for applying a voltage to the target include a DC power supply, an AC power supply, an MF power supply, and an RF power supply.
  • a DC power source and an RF power source may be used in combination.
  • the absolute value of the discharge voltage during the sputtering film formation is, for example, 50 V or more, and is, for example, 500 V or less, preferably 400 V or less.
  • the transparent conductive film X provided with the amorphous transparent conductive layer 20 can be manufactured.
  • the transparent conductive layer is amorphous, for example, as follows. First, the transparent conductive layer (in the transparent conductive film X, the transparent conductive layer 20 on the transparent resin base material 10) is immersed in hydrochloric acid having a concentration of 5% by mass at 20 ° C. for 15 minutes. Next, the transparent conductive layer is washed with water and then dried. Next, on the exposed plane of the transparent conductive layer (in the transparent conductive film X, the surface of the transparent conductive layer 20 opposite to the transparent resin base material 10), the resistance between the pair of terminals having a separation distance of 15 mm (between terminals). Resistance) is measured. In this measurement, when the resistance between terminals exceeds 10 k ⁇ , the transparent conductive layer is amorphous.
  • the transparent conductive layer 20 in the transparent conductive film X may be patterned as schematically shown in FIG.
  • the transparent conductive layer 20 can be patterned by etching the transparent conductive layer 20 through a predetermined etching mask.
  • the patterned transparent conductive layer 20 functions as, for example, a wiring pattern.
  • the transparent conductive layer 20 in the transparent conductive film X is converted into a crystalline transparent conductive layer 20'(shown in FIG. 5) by heating.
  • the heating means include an infrared heater and an oven (heat medium heating type oven, hot air heating type oven).
  • the heating environment may be either a vacuum environment or an atmospheric environment.
  • heating is carried out in the presence of oxygen.
  • the heating temperature is, for example, 100 ° C. or higher, preferably 120 ° C. or higher, from the viewpoint of ensuring a high crystallization rate.
  • the heating temperature is, for example, 200 ° C. or lower, preferably 180 ° C. or lower, more preferably 170 ° C. or lower, still more preferably 165 ° C.
  • the heating time is, for example, less than 600 minutes, preferably less than 120 minutes, more preferably 90 minutes or less, still more preferably 60 minutes or less, and for example, 1 minute or more, preferably 5 minutes or more.
  • the above-mentioned patterning of the transparent conductive layer 20 may be performed before heating for crystallization, or may be performed after heating for crystallization.
  • the specific resistance of the transparent conductive layer 20' is preferably 2.1 ⁇ 10 -4 ⁇ ⁇ cm or less, 2.0 ⁇ 10 -4 ⁇ ⁇ cm or less, and more preferably 1.9 ⁇ 10 -4 ⁇ ⁇ cm or less. Is 1.8 ⁇ 10 -4 ⁇ ⁇ cm or less.
  • the specific resistance of the transparent conductive layer 20' is preferably 0.1 ⁇ 10 -4 ⁇ ⁇ cm or more, more preferably 0.5 ⁇ 10 -4 ⁇ ⁇ cm or more, and further preferably 1.0 ⁇ 10 ⁇ . It is 4 ⁇ ⁇ cm or more.
  • the transparent conductive layer 20 of the transparent conductive film X contains a rare gas atom having an atomic number larger than that of argon. Such a configuration is suitable for reducing the resistance of the transparent conductive layer 20.
  • the structure in which the transparent conductive layer 20 contains a rare gas atom having an atomic number larger than that of argon is also suitable for heat-shrinking the transparent conductive layer 20 by heat treatment. That is, when the transparent conductive layer 20 contains a rare gas atom having an atomic number larger than that of argon, it is more easily heat-shrinked than when it does not contain such an atom and contains argon.
  • the transparent conductive film X as described above, the heat shrinkage rate of the transparent resin base material 10 in the first direction after the heat treatment is 0.00% or more, or the transparent conductive film X itself. The heat shrinkage rate in the predetermined direction after the heat treatment is 0.03% or more.
  • the transparent resin base material 10 does not thermally expand, but thermally shrinks in the same manner as the transparent conductive layer 20.
  • These configurations relating to heat shrinkage are suitable for suppressing the generation of excessive internal stress in the heat-shrinked transparent conductive layer 20 after the heat treatment for crystallization of the transparent conductive layer 20.
  • the transparent conductive film X as described above is suitable for obtaining the transparent conductive film X provided with the low-resistance crystalline transparent conductive layer 20'in which the occurrence of cracks is suppressed. Specifically, it is as shown in the examples described later.
  • the transparent conductive film X is used in a state where it is fixed to an article and the transparent conductive layer 20 is patterned as needed.
  • the transparent conductive film X is attached to the article via, for example, a fixing functional layer.
  • Examples of articles include elements, members, and devices. That is, examples of the article with a transparent conductive film include an element with a transparent conductive film, a member with a transparent conductive film, and a device with a transparent conductive film.
  • Examples of the element include a dimming element and a photoelectric conversion element.
  • Examples of the dimming element include a current-driven dimming element and an electric field-driven dimming element.
  • Examples of the current-driven dimming element include an electrochromic (EC) dimming element.
  • Examples of the electric field drive type dimming element include a PDLC (polymer dispersed liquid crystal) dimming element, a PNLC (polymer network liquid crystal) dimming element, and an SPD (suspended particle device) dimming element.
  • Examples of the photoelectric conversion element include a solar cell and the like.
  • Examples of the solar cell include an organic thin-film solar cell and a dye-sensitized solar cell.
  • Examples of the member include an electromagnetic wave shield member, a heat ray control member, a heater member, and an antenna member.
  • Examples of the device include a touch sensor device, a lighting device, and an image display device.
  • the fixing functional layer examples include an adhesive layer and an adhesive layer.
  • the material of the fixing function layer any material having transparency and exhibiting the fixing function can be used without particular limitation.
  • the fixing functional layer is preferably formed of a resin.
  • the resin include acrylic resin, silicone resin, polyester resin, polyurethane resin, polyamide resin, polyvinyl ether resin, vinyl acetate / vinyl chloride copolymer, modified polyolefin resin, epoxy resin, fluororesin, natural rubber, and synthetic rubber. Be done.
  • Acrylic resin is preferable as the resin because it exhibits adhesive properties such as cohesiveness, adhesiveness, and appropriate wettability, is excellent in transparency, and is excellent in weather resistance and heat resistance.
  • a corrosion inhibitor may be added to the fixing functional layer (resin forming the fixing functional layer) in order to suppress corrosion of the transparent conductive layer 20.
  • a migration inhibitor (for example, a material disclosed in Japanese Patent Application Laid-Open No. 2015-0222397) may be added to the fixing functional layer (resin forming the fixing functional layer) in order to suppress migration of the transparent conductive layer 20.
  • the fixing functional layer (resin forming the fixing functional layer) may be blended with an ultraviolet absorber in order to suppress deterioration of the article when it is used outdoors.
  • the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxalic acid anilides compounds, cyanoacrylate compounds, and triazine compounds.
  • the transparent conductive layer 20 (including the transparent conductive layer 20 after patterning) in the transparent conductive film X. Is exposed.
  • the cover layer may be arranged on the exposed surface of the transparent conductive layer 20.
  • the cover layer is a layer that covers the transparent conductive layer 20, and can improve the reliability of the transparent conductive layer 20 and suppress functional deterioration due to damage to the transparent conductive layer 20.
  • Such a cover layer is preferably formed of a dielectric material, more preferably of a composite material of a resin and an inorganic material. Examples of the resin include the above-mentioned resins for the fixing functional layer.
  • the inorganic material examples include inorganic oxides and fluorides.
  • the inorganic oxide examples include silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide, and calcium oxide.
  • the fluoride examples include magnesium fluoride.
  • the cover layer may contain the above-mentioned corrosion inhibitor, migration inhibitor, and ultraviolet absorber.
  • the present invention will be specifically described below with reference to examples.
  • the present invention is not limited to the examples.
  • the specific numerical values such as the compounding amount (content), the physical property value, the parameter, etc. described below are the compounding amounts corresponding to them described in the above-mentioned "mode for carrying out the invention”. It can be replaced with an upper limit (numerical value defined as “less than or equal to” or “less than”) or a lower limit (numerical value defined as "greater than or equal to” or “greater than or equal to”) such as content), physical property value, and parameter.
  • Example 1 First, a roll of a long first transparent resin base material S 1 (product name "KB film CANIA", thickness 54 ⁇ m, biaxially stretched PET film with double-sided hard coat layer, manufactured by Kimoto Co., Ltd.) was prepared.
  • the substrate comprises a long polyethylene terephthalate (PET) film as a transparent resin film, a first hard coat layer on one side of the film, and a second hard coat layer on the other side.
  • PET polyethylene terephthalate
  • the first hard coat layer on the first transparent resin substrate S 1 to form an amorphous transparent conductive layer having a thickness of 130 nm (sputtering process).
  • a sputtering film forming apparatus DC magnetron sputtering apparatus capable of carrying out a film forming process by a roll-to-roll method was used.
  • the conditions for sputter film formation in this example are as follows.
  • a sintered body of indium oxide and tin oxide (tin oxide concentration was 10% by mass) was used.
  • a DC power source was used as the power source for applying the voltage to the target (horizontal magnetic field strength on the target was 90 mT).
  • Film forming temperature (first temperature of the transparent resin substrate S 1 having a transparent conductive layer is laminated) was -5 ° C.. Further, after the film forming chamber is evacuated until the ultimate vacuum degree in the film forming chamber of the apparatus reaches 0.9 ⁇ 10 -4 Pa, Kr as a sputtering gas and Kr as a reactive gas are used in the film forming chamber. Oxygen was introduced, and the air pressure in the film forming chamber was set to 0.2 Pa.
  • the ratio of the oxygen introduction amount to the total introduction amount of Kr and oxygen introduced into the film forming chamber is about 2.6 flow rate%, and the oxygen introduction amount is the specific resistance-oxygen introduction amount curve as shown in FIG.
  • the value of the specific resistance of the formed ITO film was adjusted to be 6.7 ⁇ 10 -4 ⁇ ⁇ cm within the region R of.
  • the resistivity-oxygen introduction amount curve shown in FIG. 6 depends on the oxygen introduction amount of the specific resistance of the transparent conductive layer when the transparent conductive layer is formed by the reactive sputtering method under the same conditions as above except for the oxygen introduction amount. Gender can be investigated and created in advance.
  • the transparent conductive layer (thickness 130 nm, amorphous) of the transparent conductive film of Example 1 is composed of a single Kr-containing ITO film.
  • Example 2 In the formation of the transparent conductive layer, a first sputter film formation in which a first region (thickness 52 nm) of the transparent conductive layer is formed on the first transparent resin base material S1 and a first of the transparent conductive layers on the first region.
  • the transparent conductive film of Example 3 was produced in the same manner as the transparent conductive film of Example 1 except that the second sputter film formation for forming two regions (thickness 78 nm) was sequentially carried out.
  • the conditions for the first sputter film formation in this example are as follows.
  • a target a sintered body of indium oxide and tin oxide (tin oxide concentration was 10% by mass) was used.
  • a DC power source was used as the power source for applying the voltage to the target (horizontal magnetic field strength on the target was 90 mT).
  • the film formation temperature was ⁇ 5 ° C.
  • Kr as a sputtering gas and oxygen as a reactive gas are introduced into the first film forming chamber.
  • the air pressure in the first film forming chamber was set to 0.2 Pa.
  • the amount of oxygen introduced into the first film forming chamber was adjusted so that the value of the specific resistance of the formed ITO film was 6.5 ⁇ 10 -4 ⁇ ⁇ cm.
  • the conditions for the second sputter film formation in this example are as follows. After setting the ultimate vacuum degree in the second film forming chamber of the apparatus to 0.9 ⁇ 10 -4 Pa, Ar as a sputtering gas and oxygen as a reactive gas were introduced into the second film forming chamber. The air pressure in the second film forming chamber was set to 0.4 Pa. The amount of oxygen introduced into the second film forming chamber was adjusted so that the value of the specific resistance of the formed ITO film was 6.5 ⁇ 10 -4 ⁇ ⁇ cm. In this embodiment, the other conditions in the second sputter film formation are the same as those in the first sputter film formation.
  • the transparent conductive layer (thickness 130 nm, amorphous) of the transparent conductive film of Example 2 has a first region (thickness 52 nm) made of a Kr-containing ITO film and a second region (thickness) made of an Ar-containing ITO film. is 78 nm) and has a first transparent resin substrate S 1 side.
  • the ratio of the thickness of the first region to the thickness of the transparent conductive layer is 40%, and the ratio of the thickness of the second region is 60%.
  • Example 3 Except that the first transparent resin substrate S 1 prior to the sputtering process and annealing process, in the same manner as the transparent conductive film of Example 2, to thereby form a transparent conductive film of Example 3.
  • a hot air oven was used for the annealing treatment. Specifically, the first transparent resin substrate S 1, (the same is true below the annealing treatment) to travel is not a to pass through the hot air oven at a roll-to-roll process. In the annealing treatment, the temperature was 160 ° C. and the treatment time was 6 minutes.
  • the transparent conductive layer (thickness 130 nm, amorphous) of the transparent conductive film of Example 3 has a first region (thickness 52 nm) made of a Kr-containing ITO film and a second region (thickness) made of an Ar-containing ITO film. is 78 nm) and has a first transparent resin substrate S 1 side.
  • the ratio of the thickness of the first region to the thickness of the transparent conductive layer is 40%, and the ratio of the thickness of the second region is 60%.
  • Example 4 A transparent conductive film of Example 4 was produced in the same manner as the transparent conductive film of Example 3 except for the following.
  • the first sputter film formation was carried out under the conditions of the second sputter film formation in Example 1, and the Ar-containing ITO film having a thickness of 78 nm was formed by the first sputter film formation.
  • the second sputter film formation after the first sputter film formation was carried out under the conditions of the first sputter film formation in Example 1, and the Kr-containing ITO film having a thickness of 52 nm was formed by the second sputter film formation.
  • the transparent conductive layer (thickness 130 nm, amorphous) of the transparent conductive film of Example 4 has a second region (thickness 78 m) made of an Ar-containing ITO film and a first region (thickness) made of a Kr-containing ITO film. is 52 nm) and has a first transparent resin substrate S 1 side.
  • the ratio of the thickness of the first region to the thickness of the transparent conductive layer is 40%, and the ratio of the thickness of the second region is 60%.
  • the second transparent resin substrate S 2 is elongated in the first place of the transparent resin substrate S 1 (product name "DIAFOIL T910E125", thickness 125 [mu] m, a biaxially stretched film, Mitsubishi Chemical Co., Ltd.) for the use of rolls Except for the above, the transparent conductive film of Example 5 was produced in the same manner as the transparent conductive film of Example 1.
  • the second transparent resin base material S 2 includes a long PET film as a transparent resin film and an adhesion improving layer on one surface of the film.
  • the transparent conductive layer (thickness 130 nm, amorphous) of the transparent conductive film of Example 5 is composed of a single Kr-containing ITO film.
  • Example 6 A transparent conductive film of Example 6 was produced in the same manner as the transparent conductive film of Example 1 except for the following matters in the sputtering film formation.
  • a mixed gas of krypton and argon (Kr85% by volume, Ar15% by volume) was used as the sputtering gas.
  • the air pressure in the film forming chamber was set to 0.2 Pa.
  • the amount of oxygen introduced into the film forming chamber was adjusted so that the value of the specific resistance of the ITO film was 5.5 ⁇ 10 -4 ⁇ ⁇ cm.
  • the thickness of the ITO film formed was set to 150 nm.
  • the transparent conductive layer (thickness 150 nm, amorphous) of the transparent conductive film of Example 6 is composed of a single ITO film containing Kr and Ar.
  • Comparative Example 1 Third transparent resin substrate S 3 that is elongated in the first place of the transparent resin substrate S 1 (product name "GF-125JBN", thickness 127 [mu] m, a biaxially stretched film, Mitsubishi Chemical Co., Ltd.) for the use of rolls A transparent conductive film of Comparative Example 1 was produced in the same manner as the transparent conductive film of Example 4 except for the above.
  • Third transparent resin substrate S 3 comprises a PET film long as the transparent resin film, a refractive index adjusting layer, and a hard coat layer, in order in the thickness direction.
  • the transparent conductive layer (thickness 130 nm, amorphous) of the transparent conductive film of Comparative Example 1 has a second region (thickness 78 m) made of an Ar-containing ITO film and a first region (thickness) made of a Kr-containing ITO film. and is 52 nm), a third transparent resin substrate S 3 side.
  • Comparative Example 2 A transparent conductive film of Comparative Example 2 was produced in the same manner as the transparent conductive film of Example 1 except for the following. The first place of the transparent resin substrate S 1 using a third transparent resin substrate S 3. Before sputtering process, and the third transparent resin substrate S 3 annealed. In the annealing treatment, the temperature was 180 ° C. and the treatment time was 6 minutes.
  • the transparent conductive layer (thickness 130 nm, amorphous) of the transparent conductive film of Comparative Example 2 is composed of a single Kr-containing ITO film.
  • Comparative Example 3 A transparent conductive film of Comparative Example 3 was produced in the same manner as the transparent conductive film of Example 1 except for the following. The first place of the transparent resin substrate S 1 using a third transparent resin substrate S 3. In the sputtering film formation, Ar is used as the sputtering gas, the pressure in the film formation chamber is 0.4 Pa, and the amount of oxygen introduced into the film formation chamber is such that the specific resistance value of the ITO film is 6.2 ⁇ 10 -4 ⁇ . An ITO film having a thickness of 150 nm was formed while adjusting the thickness to cm.
  • the transparent conductive layer (thickness 130 nm, amorphous) of the transparent conductive film of Comparative Example 3 is composed of a single Ar-containing ITO film.
  • the transparent conductive layer (thickness 130 nm, amorphous) of the transparent conductive film of Comparative Example 4 is composed of a single Ar-containing ITO film.
  • ⁇ thickness> The thicknesses of the transparent resin base material, the hard coat layer, the adhesion improving layer, and the refractive index adjusting layer were measured by a film thickness meter (product name "Digital Dial Gauge DG-205", manufactured by Peacock).
  • each transparent conductive layer in Examples 1 to 6 and Comparative Examples 1 to 4 was measured by FE-TEM observation. Specifically, first, a cross-section observation sample of each transparent conductive film in Examples 1 to 6 and Comparative Examples 1 to 4 was prepared by the FIB microsampling method. In the FIB microsampling method, an FIB device (trade name "FB2200", manufactured by Hitachi) was used, and the acceleration voltage was set to 10 kV. Next, the thickness of the transparent conductive layer in the cross-section observation sample was measured by FE-TEM observation. In the FE-TEM observation, an FE-TEM device (trade name "JEM-2800", manufactured by JEOL) was used, and the acceleration voltage was set to 200 kV.
  • FE-TEM observation an FE-TEM device (trade name "JEM-2800", manufactured by JEOL) was used, and the acceleration voltage was set to 200 kV.
  • the thickness of the lower layer of each transparent conductive layer in Examples 2 to 4 and Comparative Example 1 (the first region in Examples 2 and 4 and the second region in Example 3 and Comparative Example 1) is an upper layer above the lower layer.
  • a cross-section observation sample was prepared from the intermediate product before forming (the second region in Examples 2 and 4, and the first region in Example 3 and Comparative Example 1), and the sample was measured by FE-TEM observation. ..
  • the thickness of the upper layer of each transparent conductive layer in Examples 2 to 4 and Comparative Example 1 was obtained by subtracting the thickness of the lower layer from the total thickness of the transparent conductive layer.
  • the heat shrinkage rate of each of the transparent conductive films of Examples 1 to 6 and Comparative Examples 1 to 4 after being heat-treated was examined. Specifically, first, three first sample films having a size of 10 cm on the first side and 10 cm on the second side were prepared for each transparent conductive film.
  • the first side is a side extending in the MD direction for the transparent conductive film (that is, the film running direction in the above-mentioned manufacturing process in the roll-to-roll method) (the same applies to the first sample film described later).
  • the second side is a side extending in the TD direction (that is, a direction orthogonal to the running direction of the film) for the transparent conductive film (the same applies to the first sample film described later).
  • each first sample film was measured by a non-contact CNC image measuring machine (trade name "QV ACCEL606-PRO", manufactured by Mitutoyo Co., Ltd.) (first measurement).
  • the first sample film was heat-treated in a hot air oven. In the heat treatment, the heating temperature was 165 ° C. and the heating time was 60 minutes.
  • the shape of each first sample film cooled to room temperature after the heat treatment was measured by the non-contact CNC image measuring machine (second measurement). Then, based on the shape data obtained by the first measurement and the shape data obtained by the second measurement, the direction in which the heat shrinkage rate due to the above heat treatment is maximum in any of the first sample films (first). It was identified that (1 direction) is the MD direction.
  • the average of the heat shrinkage rates of the six second sides of the three first sample films for each transparent conductive film due to heat treatment was determined as the first heat shrinkage rate T1 (%) in the second direction. ..
  • the values are shown in Table 1. Assuming that the length before shrinkage is L1 and the length after shrinkage is L2, the heat shrinkage rate (%) is represented by [(L1-L2) / L1] ⁇ 100.
  • the heat shrinkage rate of each of the transparent conductive films of Examples 1 to 6 and Comparative Examples 1 to 4 after being heat-treated was examined. Specifically, first, three first sample films having a size of 10 cm on the first side and 10 cm on the second side were prepared for each transparent conductive film. Next, the first sample film was immersed in hydrochloric acid having a concentration of 5% by mass at 20 ° C. for 30 minutes. As a result, the transparent conductive layer was removed from the first sample film to obtain a second sample film made of a transparent resin base material. After that, the above-mentioned first measurement, heat treatment, and second measurement were performed on the second sample film in the same manner as performed on the first sample film in the process of deriving the first heat shrinkage rate T1. bottom.
  • the direction in which the heat shrinkage rate due to the above heat treatment is maximum in any of the second sample films (first). It was identified that (1 direction) is the MD direction. Further, the average value of the heat shrinkage rate due to the heat treatment of the total of six second sides of the three second sample films for each transparent conductive film is obtained as the second heat shrinkage rate T2 (%) in the second direction. rice field.
  • the transparent conductive film whose temperature was lowered to room temperature after the heat treatment was subdivided into a size of 5 cm ⁇ 5 cm, and 30 samples for observation were obtained.
  • each sample was observed with an optical microscope to check for cracks.
  • the suppression of the occurrence of cracks in the transparent conductive layer of the transparent conductive film the case where the number of samples in which cracks were confirmed in the transparent conductive layer is 15 or less is evaluated as "good", and 16 or more are evaluated. Some cases were evaluated as "bad”.
  • the evaluation results are shown in Table 1.
  • the transparent conductive film of the present invention can be used as a feed material for a conductor film for forming a pattern of transparent electrodes in various devices such as liquid crystal displays, touch panels, and optical sensors.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Human Computer Interaction (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)
  • Physical Vapour Deposition (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Photovoltaic Devices (AREA)
  • Liquid Crystal (AREA)
PCT/JP2021/011148 2020-03-19 2021-03-18 透明導電性フィルム、および透明導電性フィルムの製造方法 Ceased WO2021187573A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202180022424.6A CN115298764A (zh) 2020-03-19 2021-03-18 透明导电性薄膜和透明导电性薄膜的制造方法
JP2021545721A JP7308960B2 (ja) 2020-03-19 2021-03-18 透明導電性フィルム、および透明導電性フィルムの製造方法
KR1020227030820A KR20220156824A (ko) 2020-03-19 2021-03-18 투명 도전성 필름 및 투명 도전성 필름의 제조 방법
JP2022093446A JP2022133292A (ja) 2020-03-19 2022-06-09 透明導電性フィルム、および透明導電性フィルムの製造方法

Applications Claiming Priority (26)

Application Number Priority Date Filing Date Title
JP2020049864 2020-03-19
JP2020-049864 2020-03-19
JP2020074853 2020-04-20
JP2020-074854 2020-04-20
JP2020-074853 2020-04-20
JP2020074854 2020-04-20
JP2020-134833 2020-08-07
JP2020134832 2020-08-07
JP2020134833 2020-08-07
JP2020-134832 2020-08-07
JP2020140240 2020-08-21
JP2020140239 2020-08-21
JP2020-140241 2020-08-21
JP2020-140239 2020-08-21
JP2020140241 2020-08-21
JP2020-140240 2020-08-21
JP2020-140238 2020-08-21
JP2020140238 2020-08-21
JP2020149474 2020-09-04
JP2020-149474 2020-09-04
JP2020181349 2020-10-29
JP2020-181349 2020-10-29
JP2020200422 2020-12-02
JP2020200421 2020-12-02
JP2020-200422 2020-12-02
JP2020-200421 2020-12-02

Publications (1)

Publication Number Publication Date
WO2021187573A1 true WO2021187573A1 (ja) 2021-09-23

Family

ID=77770986

Family Applications (10)

Application Number Title Priority Date Filing Date
PCT/JP2021/011148 Ceased WO2021187573A1 (ja) 2020-03-19 2021-03-18 透明導電性フィルム、および透明導電性フィルムの製造方法
PCT/JP2021/011160 Ceased WO2021187583A1 (ja) 2020-03-19 2021-03-18 透明導電層および透明導電性フィルム
PCT/JP2021/011162 Ceased WO2021187585A1 (ja) 2020-03-19 2021-03-18 透明導電性フィルム
PCT/JP2021/011163 Ceased WO2021187586A1 (ja) 2020-03-19 2021-03-18 透明導電性フィルム
PCT/JP2021/011164 Ceased WO2021187587A1 (ja) 2020-03-19 2021-03-18 透明導電性フィルム
PCT/JP2021/011161 Ceased WO2021187584A1 (ja) 2020-03-19 2021-03-18 透明導電層および透明導電性フィルム
PCT/JP2021/011166 Ceased WO2021187589A1 (ja) 2020-03-19 2021-03-18 透明導電層および透明導電性シート
PCT/JP2021/011159 Ceased WO2021187582A1 (ja) 2020-03-19 2021-03-18 透明導電層および透明導電性フィルム
PCT/JP2021/011156 Ceased WO2021187581A1 (ja) 2020-03-19 2021-03-18 透明導電性フィルム、および透明導電性フィルムの製造方法
PCT/JP2021/011165 Ceased WO2021187588A1 (ja) 2020-03-19 2021-03-18 透明導電層および透明導電性シート

Family Applications After (9)

Application Number Title Priority Date Filing Date
PCT/JP2021/011160 Ceased WO2021187583A1 (ja) 2020-03-19 2021-03-18 透明導電層および透明導電性フィルム
PCT/JP2021/011162 Ceased WO2021187585A1 (ja) 2020-03-19 2021-03-18 透明導電性フィルム
PCT/JP2021/011163 Ceased WO2021187586A1 (ja) 2020-03-19 2021-03-18 透明導電性フィルム
PCT/JP2021/011164 Ceased WO2021187587A1 (ja) 2020-03-19 2021-03-18 透明導電性フィルム
PCT/JP2021/011161 Ceased WO2021187584A1 (ja) 2020-03-19 2021-03-18 透明導電層および透明導電性フィルム
PCT/JP2021/011166 Ceased WO2021187589A1 (ja) 2020-03-19 2021-03-18 透明導電層および透明導電性シート
PCT/JP2021/011159 Ceased WO2021187582A1 (ja) 2020-03-19 2021-03-18 透明導電層および透明導電性フィルム
PCT/JP2021/011156 Ceased WO2021187581A1 (ja) 2020-03-19 2021-03-18 透明導電性フィルム、および透明導電性フィルムの製造方法
PCT/JP2021/011165 Ceased WO2021187588A1 (ja) 2020-03-19 2021-03-18 透明導電層および透明導電性シート

Country Status (6)

Country Link
US (2) US20230127104A1 (https=)
JP (15) JP7237150B2 (https=)
KR (11) KR20220156819A (https=)
CN (10) CN115298763A (https=)
TW (10) TW202145262A (https=)
WO (10) WO2021187573A1 (https=)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022092190A2 (ja) * 2020-10-29 2022-05-05 日東電工株式会社 透明導電性フィルム、および透明導電性フィルムの製造方法
WO2022202715A1 (ja) * 2021-03-23 2022-09-29 日東電工株式会社 電極
US20230391969A1 (en) * 2021-08-06 2023-12-07 Nitto Denko Corporation Laminate
CN116348293B (zh) * 2021-08-06 2024-04-02 日东电工株式会社 层叠体
JP7509852B2 (ja) * 2022-11-10 2024-07-02 日東電工株式会社 透明導電性フィルム
WO2024166683A1 (ja) * 2023-02-08 2024-08-15 日東電工株式会社 調光フィルム
JP7549117B1 (ja) 2023-12-21 2024-09-10 日東電工株式会社 調光フィルム
JP2024131595A (ja) 2023-03-16 2024-09-30 日東電工株式会社 透明導電性フィルム
JP2024131594A (ja) 2023-03-16 2024-09-30 日東電工株式会社 透明導電性フィルム
JP7768443B1 (ja) * 2025-03-21 2025-11-12 住友ベークライト株式会社 積層体、及び積層体の製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05334924A (ja) * 1992-05-29 1993-12-17 Tonen Corp 透明導電薄膜の製造法

Family Cites Families (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61279003A (ja) * 1985-06-05 1986-12-09 コニカ株式会社 透明導電性フイルム
JPH0658476B2 (ja) * 1985-06-19 1994-08-03 株式会社日立製作所 液晶表示素子用基板の製造方法
JPH07258827A (ja) * 1994-03-25 1995-10-09 Mitsubishi Electric Corp 金属薄膜，その形成方法，半導体装置およびその製造方法
JPH07262829A (ja) * 1994-03-25 1995-10-13 Hitachi Ltd 透明導電膜及びその形成方法
JP4010587B2 (ja) * 1995-12-20 2007-11-21 三井化学株式会社 透明導電性積層体及びそれを用いたエレクトロルミネッセンス発光素子
JP2000038654A (ja) * 1998-07-21 2000-02-08 Nippon Sheet Glass Co Ltd 透明導電膜付き基板の製造方法、透明導電膜付き基板およびそれを用いた液晶表示素子
JP3549089B2 (ja) 1998-07-28 2004-08-04 セントラル硝子株式会社 透明導電膜付きガラス基板とその製法
JP2000238178A (ja) * 1999-02-24 2000-09-05 Teijin Ltd 透明導電積層体
JP2000282225A (ja) * 1999-04-01 2000-10-10 Nippon Sheet Glass Co Ltd 透明導電膜形成方法及び該方法より形成された透明導電膜
JP4132458B2 (ja) * 1999-08-23 2008-08-13 Ｔｄｋ株式会社 有機ｅｌ素子
JP2002371355A (ja) * 2001-06-14 2002-12-26 Nitto Denko Corp 透明薄膜の製造方法
JP2002371350A (ja) * 2001-06-14 2002-12-26 Nitto Denko Corp 透明積層体の製造方法
JP4177709B2 (ja) 2002-05-20 2008-11-05 株式会社日本触媒 繊維状の金属酸化物微粒子
WO2004105055A1 (ja) * 2003-05-26 2004-12-02 Nippon Soda Co., Ltd. 透明導電膜付透光性基板
WO2006033166A1 (ja) * 2004-09-24 2006-03-30 Tadahiro Ohmi 有機ｅｌ発光素子、その製造方法および表示装置
JP4618707B2 (ja) * 2004-03-19 2011-01-26 日東電工株式会社 電解質膜および固体高分子型燃料電池
JP4882262B2 (ja) * 2005-03-31 2012-02-22 凸版印刷株式会社 透明導電膜積層体の製造方法
JP4899443B2 (ja) * 2005-11-22 2012-03-21 大日本印刷株式会社 導電性基板
US7867636B2 (en) * 2006-01-11 2011-01-11 Murata Manufacturing Co., Ltd. Transparent conductive film and method for manufacturing the same
JP2010080358A (ja) * 2008-09-29 2010-04-08 Hitachi Ltd 透明導電膜付基板、及びそれを用いた表示素子及び太陽電池
JP2010162746A (ja) * 2009-01-14 2010-07-29 Jsr Corp 透明導電性積層フィルム及びそれを用いたタッチパネル
JP2010177161A (ja) * 2009-02-02 2010-08-12 Toyobo Co Ltd 透明導電性フィルム
KR101656118B1 (ko) * 2009-09-18 2016-09-08 파나소닉 아이피 매니지먼트 가부시키가이샤 태양 전지, 태양 전지 모듈 및 태양 전지 시스템
JP6023402B2 (ja) * 2010-12-27 2016-11-09 日東電工株式会社 透明導電性フィルムおよびその製造方法
JP4960511B1 (ja) * 2011-01-26 2012-06-27 株式会社東芝 半導体発光素子及びその製造方法
JP5729595B2 (ja) 2011-03-11 2015-06-03 三菱マテリアル株式会社 太陽電池用透明導電膜およびその製造方法
JP5244950B2 (ja) * 2011-10-06 2013-07-24 日東電工株式会社 透明導電性フィルム
JP2013193440A (ja) * 2012-03-22 2013-09-30 Sekisui Nano Coat Technology Co Ltd 光透過性導電性フィルム、その製造方法及びその用途
CN103999166B (zh) * 2012-06-07 2018-01-09 日东电工株式会社 透明导电性膜
JP5620967B2 (ja) 2012-11-22 2014-11-05 日東電工株式会社 透明導電性フィルム
JP6261987B2 (ja) * 2013-01-16 2018-01-17 日東電工株式会社 透明導電フィルムおよびその製造方法
JP6227321B2 (ja) * 2013-08-05 2017-11-08 リンテック株式会社 プロテクトフィルム付き透明導電性フィルム
JP2015146244A (ja) * 2014-02-03 2015-08-13 凸版印刷株式会社 透明導電性フィルムおよびこの製造方法
WO2015178298A1 (ja) * 2014-05-20 2015-11-26 日東電工株式会社 透明導電性フィルムおよびその製造方法
KR20170008195A (ko) * 2014-05-20 2017-01-23 닛토덴코 가부시키가이샤 투명 도전성 필름
CN106460161B (zh) * 2014-11-07 2018-12-04 捷客斯金属株式会社 Ito溅射靶及其制造方法和ito透明导电膜及ito透明导电膜的制造方法
US20170271613A1 (en) * 2014-12-03 2017-09-21 Joled Inc. Organic light-emitting device
WO2016158606A1 (ja) * 2015-03-31 2016-10-06 東洋紡株式会社 透明導電性フィルム
JP6553451B2 (ja) * 2015-08-25 2019-07-31 日東電工株式会社 透明樹脂フィルム、透明導電性フィルムおよびそれを用いたタッチパネル
JP6159490B1 (ja) * 2015-09-30 2017-07-05 積水化学工業株式会社 光透過性導電フィルム、及び、アニール処理された光透過性導電フィルムの製造方法
JP6412539B2 (ja) * 2015-11-09 2018-10-24 日東電工株式会社 光透過性導電フィルムおよび調光フィルム
JP6654865B2 (ja) * 2015-11-12 2020-02-26 日東電工株式会社 非晶質透明導電性フィルム、ならびに、結晶質透明導電性フィルムおよびその製造方法
JP7046497B2 (ja) 2016-09-02 2022-04-04 日東電工株式会社 液晶調光部材、光透過性導電フィルム、および液晶調光素子
CN109073940B (zh) * 2016-04-01 2022-03-08 日东电工株式会社 液晶调光构件、透光性导电薄膜、及液晶调光元件
WO2017170760A1 (ja) * 2016-04-01 2017-10-05 日東電工株式会社 光透過性フィルム
CN109313962A (zh) * 2016-06-10 2019-02-05 日东电工株式会社 透明导电性薄膜及触摸面板
JP6803191B2 (ja) * 2016-10-14 2020-12-23 株式会社カネカ 透明導電性フィルムの製造方法
JP6490262B2 (ja) * 2017-05-09 2019-03-27 日東電工株式会社 光透過性導電層付きフィルム、調光フィルムおよび調光装置
JP2018192634A (ja) * 2017-05-12 2018-12-06 株式会社ダイセル カールが抑制されたハードコートフィルム及びその製造方法
JP7264807B2 (ja) * 2017-12-28 2023-04-25 日東電工株式会社 光透過性導電フィルム、その製造方法、調光フィルム、および、調光部材
CN108486550B (zh) * 2018-04-27 2020-06-16 华南理工大学 一种金属氧化物透明导电薄膜的制备方法及其产品和用途
JP7054651B2 (ja) * 2018-06-19 2022-04-14 日東電工株式会社 下地層付きフィルム、透明導電性フィルム、透明導電性フィルム積層体および画像表示装置

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05334924A (ja) * 1992-05-29 1993-12-17 Tonen Corp 透明導電薄膜の製造法

Also Published As

Publication number Publication date
JP7073589B2 (ja) 2022-05-23
JP7273930B2 (ja) 2023-05-15
JP7213941B2 (ja) 2023-01-27
TW202144871A (zh) 2021-12-01
WO2021187586A1 (ja) 2021-09-23
WO2021187589A1 (ja) 2021-09-23
JPWO2021187585A1 (https=) 2021-09-23
JP2022019756A (ja) 2022-01-27
JP6987321B1 (ja) 2021-12-22
KR20220155287A (ko) 2022-11-22
WO2021187584A1 (ja) 2021-09-23
JPWO2021187588A1 (https=) 2021-09-23
JP7073588B2 (ja) 2022-05-23
TW202139214A (zh) 2021-10-16
US20230127104A1 (en) 2023-04-27
JP7240514B2 (ja) 2023-03-15
KR20220155283A (ko) 2022-11-22
JPWO2021187581A1 (https=) 2021-09-23
CN115280430A (zh) 2022-11-01
KR20240011876A (ko) 2024-01-26
JPWO2021187584A1 (https=) 2021-09-23
JP7278372B2 (ja) 2023-05-19
US20230131985A1 (en) 2023-04-27
KR20220156825A (ko) 2022-11-28
CN115298763A (zh) 2022-11-04
TW202145258A (zh) 2021-12-01
JPWO2021187582A1 (https=) 2021-09-23
TW202141537A (zh) 2021-11-01
TW202145262A (zh) 2021-12-01
KR20220156826A (ko) 2022-11-28
TW202143252A (zh) 2021-11-16
WO2021187582A1 (ja) 2021-09-23
CN115335924A (zh) 2022-11-11
WO2021187581A1 (ja) 2021-09-23
JP7237150B2 (ja) 2023-03-10
JP6971433B1 (ja) 2021-11-24
KR20220156819A (ko) 2022-11-28
CN115280429A (zh) 2022-11-01
WO2021187583A1 (ja) 2021-09-23
JP2022033120A (ja) 2022-02-28
KR20220155281A (ko) 2022-11-22
KR20220156824A (ko) 2022-11-28
TW202141536A (zh) 2021-11-01
CN115298762A (zh) 2022-11-04
KR20220156820A (ko) 2022-11-28
JPWO2021187586A1 (https=) 2021-09-23
WO2021187588A1 (ja) 2021-09-23
JP7308960B2 (ja) 2023-07-14
JPWO2021187589A1 (https=) 2021-09-23
CN115298764A (zh) 2022-11-04
CN115315759A (zh) 2022-11-08
JPWO2021187573A1 (https=) 2021-09-23
KR20220155282A (ko) 2022-11-22
JP6974656B1 (ja) 2021-12-01
JP6970861B1 (ja) 2021-11-24
TW202141535A (zh) 2021-11-01
WO2021187585A1 (ja) 2021-09-23
CN115280430B (zh) 2024-06-14
CN115315760A (zh) 2022-11-08
JPWO2021187587A1 (https=) 2021-09-23
TWI819287B (zh) 2023-10-21
TWI885098B (zh) 2025-06-01
CN115335924B (zh) 2024-03-26
JP2022118005A (ja) 2022-08-12
WO2021187587A1 (ja) 2021-09-23
JP2022133292A (ja) 2022-09-13
JP2022105579A (ja) 2022-07-14
CN115280428A (zh) 2022-11-01
KR20220155288A (ko) 2022-11-22
TW202147345A (zh) 2021-12-16
JPWO2021187583A1 (https=) 2021-09-23
TW202145263A (zh) 2021-12-01
CN115298759A (zh) 2022-11-04

Similar Documents

Publication Publication Date Title
JP6970861B1 (ja) 透明導電性フィルム、および透明導電性フィルムの製造方法
JP7451505B2 (ja) 透明導電性フィルムの製造方法
WO2021187572A1 (ja) 透明導電性フィルムおよび透明導電性フィルムの製造方法
JP7556912B2 (ja) 透明導電性フィルムの製造方法
JP7565936B2 (ja) 光透過性導電膜および透明導電性フィルム
WO2022092190A2 (ja) 透明導電性フィルム、および透明導電性フィルムの製造方法
JP7654592B2 (ja) 透明導電性フィルム
JP7425266B2 (ja) 透明導電性フィルム
JP7240513B2 (ja) 透明導電性フィルム
WO2023042848A1 (ja) 透明導電性フィルム
WO2021187578A1 (ja) 光透過性導電膜および透明導電性フィルム
WO2021187576A1 (ja) 透明導電性フィルム

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021545721

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21770583

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21770583

Country of ref document: EP

Kind code of ref document: A1