WO2021187574A1 - 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の製造方法 Download PDF

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Publication number
WO2021187574A1
WO2021187574A1 PCT/JP2021/011149 JP2021011149W WO2021187574A1 WO 2021187574 A1 WO2021187574 A1 WO 2021187574A1 JP 2021011149 W JP2021011149 W JP 2021011149W WO 2021187574 A1 WO2021187574 A1 WO 2021187574A1
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WIPO (PCT)
Prior art keywords
light
conductive layer
film
transmitting conductive
transparent
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Ceased
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PCT/JP2021/011149
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English (en)
French (fr)
Japanese (ja)
Inventor
泰介 鴉田
望 藤野
鷹尾　寛行
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to KR1020227030801A priority Critical patent/KR20220155279A/ko
Priority to JP2021517064A priority patent/JP7451505B2/ja
Priority to CN202180021682.2A priority patent/CN115298756B/zh
Publication of WO2021187574A1 publication Critical patent/WO2021187574A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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
    • B32B7/023—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
    • 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
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • C23C14/56—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
    • 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
    • C23C14/5873—Removal of material
    • 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
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • 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
    • 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
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • 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 method for producing a transparent conductive film.
  • a transparent conductive film having a transparent base film and a transparent conductive layer (light-transmitting conductive layer) in order in the thickness direction is known.
  • the light-transmitting 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. Further, the light-transmitting conductive layer may be used as an antistatic layer included in the device.
  • the light-transmitting conductive layer is formed, for example, by forming a conductive oxide on the base film by a sputtering method.
  • an inert gas such as argon is used as a sputtering gas for colliding with the target (film-forming material supply material) and ejecting atoms on the target surface.
  • a technique relating to such a transparent conductive film is described in, for example, Patent Document 1 below.
  • the light-transmitting conductive layer of the transparent conductive film is required to have low resistance. Especially in transparent electrode applications, the demand is strong.
  • the transparent conductive film may undergo a heating process (a process of raising the temperature and then lowering the temperature).
  • a heating process a process of raising the temperature and then lowering the temperature.
  • cracks may occur in the light-transmitting conductive layer due to the difference in dimensional change rate between the base film and the light-transmitting conductive layer in the transparent conductive film.
  • the generation of cracks in the light-transmitting conductive layer is not preferable from the viewpoint of the production yield of the transparent conductive film and the production yield of the device including the transparent conductive film.
  • the present invention provides a method for producing a transparent conductive film suitable for obtaining a transparent conductive film provided with a light-transmitting conductive layer having low resistance in which cracks are suppressed.
  • the present invention [1] comprises a preparation step of preparing a transparent base material and a process of forming a light-transmitting conductive material on the transparent base material by a sputtering method to form an amorphous light-transmitting conductive layer.
  • a sputtering method of the film forming step which includes a film step, a sputtering gas containing a rare gas having an atomic number larger than that of argon is used, and the film forming pressure is 0.04 Pa or more and 0.9 Pa or less.
  • a method for producing a transparent conductive film, which forms a film of a light-transmitting conductive material, is included.
  • the present invention [2] includes the method for producing a transparent conductive film according to the above [1], wherein the noble gas is krypton and / or xenon.
  • the present invention [3] includes the method for producing a transparent conductive film according to the above [1] or [2], wherein the content ratio of krypton in the sputtering gas is 50% by volume or more.
  • the method for producing a transparent conductive film according to one of the above is included.
  • the present invention [5] includes the method for producing a transparent conductive film according to any one of the above [1] to [4], further comprising a step of heating and crystallizing the light transmissive conductive layer. ..
  • the present invention [6] includes the method for producing a transparent conductive film according to any one of the above [1] to [5], further including a step of patterning the light transmissive conductive layer.
  • a sputtering gas containing a rare gas having an atomic number larger than that of argon is used in the sputtering method in the film forming process, and the film forming pressure is 0.04 Pa or more and 0.9 Pa or less.
  • a light-transmitting conductive material is formed to form an amorphous light-transmitting conductive layer.
  • Such a manufacturing method is suitable for obtaining a transparent conductive film provided with a low-resistance crystalline light-transmitting conductive layer in which the occurrence of cracks is suppressed.
  • FIG. 1A shows the process of preparing a transparent base material
  • FIG. 1C shows a step of crystallizing a light-transmitting conductive layer.
  • FIG. 1B shows the patterning step when the method for producing the transparent conductive film further includes a step of patterning the light-transmitting conductive layer.
  • FIG. 1 is a process diagram of an embodiment of the method for producing a transparent conductive film of the present invention.
  • the present manufacturing method includes a preparation step, a film forming step, and a crystallization step. This manufacturing method is preferably carried out by a roll-to-roll method.
  • the transparent base material 10 is prepared as shown in FIG. 1A.
  • the transparent base material 10 includes the transparent resin film 11 and the functional layer 12 in this order toward one side in the thickness direction D.
  • the transparent base material 10 has a shape that spreads in a direction (plane direction) orthogonal to the thickness direction D.
  • the transparent base material 10 has an elongated shape.
  • the transparent resin film 11 is a transparent resin film having flexibility.
  • the material of the transparent 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.
  • the acrylic resin include polymethacrylate.
  • polyester resin is preferably used, and PET is more preferably used.
  • the surface of the transparent 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 transparent 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 transparent resin film 11 is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, and particularly preferably 75 ⁇ m or less.
  • the total light transmittance (JIS K 7375-2008) of the transparent resin film 11 is preferably 60% or more, more preferably 80% or more, still more preferably 85% or more.
  • Such a configuration is such that 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 shielding member, a lighting device, an image display device, or the like, the transparent conductive film X is provided. It is suitable for ensuring the transparency required for the sex film X.
  • the total light transmittance of the transparent resin film 11 is, for example, 100% or less.
  • the functional layer 12 is located on one surface of the thickness direction D of the transparent resin film 11. Further, in the present embodiment, the functional layer 12 is a hard coat layer for preventing scratches from being formed on the surface (upper surface in FIGS. 1B and 1C) of the light-transmitting conductive layer 20 described later included in the transparent conductive film X. Is.
  • the hard coat layer is a cured product of a curable resin composition.
  • the resin contained in the curable resin composition include polyester resin, acrylic resin, urethane resin, amide resin, silicone resin, epoxy resin, and melamine resin.
  • the curable resin composition include an ultraviolet curable resin composition and a thermosetting resin composition.
  • an ultraviolet curable resin composition is preferably used 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.
  • Specific examples of the ultraviolet curable fat composition include the composition for forming a hard coat layer described in JP-A-2016-179686.
  • the functional layer 12 as a hard coat layer can be formed by applying a curable resin composition on a transparent 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 (upper surface in FIG. 1A) of the functional layer 12 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 functional layer 12 as the hard coat layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more. Such a configuration is suitable for exhibiting sufficient scratch resistance in the light-transmitting conductive layer 20.
  • the thickness of the functional layer 12 as the hard coat layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, from the viewpoint of ensuring the transparency of the functional layer 12.
  • the thickness of the transparent 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 base material 10 is preferably 310 ⁇ m or less, more preferably 210 ⁇ m or less, still more preferably 110 ⁇ m or less, and particularly preferably 80 ⁇ m or less.
  • the total light transmittance (JIS K 7375-2008) of the transparent base material 10 is preferably 60% or more, more preferably 80% or more, still more preferably 85% or more.
  • Such a configuration is such that 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 shielding member, a lighting device, an image display device, or the like, the transparent conductive film X is provided. It is suitable for ensuring the transparency required for the sex film X.
  • the total light transmittance of the transparent base material 10 is, for example, 100% or less.
  • a light-transmitting conductive material is formed on one surface of the functional layer 12 in the transparent substrate 10 in the thickness direction D by a sputtering method to form an amorphous material.
  • a quality light-transmitting conductive layer 20 is formed.
  • the light-transmitting conductive layer 20 has a shape that spreads in the plane direction on the transparent base material 10.
  • the light-transmitting conductive layer 20 has both light-transmitting property and conductivity.
  • a sputtering film forming apparatus capable of carrying out the film forming process by the roll-to-roll method.
  • a roll-to-roll type sputter film forming apparatus in the film forming process, a long transparent base material 10 is run on the transparent base material 10 while traveling from a feeding roll to a winding roll provided in the apparatus. The material is formed into a film to form the light-transmitting conductive layer 20.
  • a sputtering film forming apparatus provided with one film forming chamber may be used, or a sputtering film forming apparatus including a plurality of film forming chambers sequentially arranged along a traveling path of the transparent substrate 10 may be used.
  • the device may be used.
  • the sputtering gas in the sputtering method, specifically, after vacuum exhausting the film forming chamber provided in the sputtering film forming apparatus, the sputtering gas (inert gas) is introduced into the film forming chamber and arranged on the cathode in the film forming chamber. A negative voltage is applied to the target (light-transmitting conductive material supply material). 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 placed on the functional layer 12 of the transparent base material 10. Is deposited as a light-transmitting conductive material.
  • an inert gas containing a rare gas having an atomic number larger than that of argon (Ar) is used.
  • the noble gas having an atomic number larger than Ar include krypton (Kr), xenon (Xe), and radon (Rn), and Kr and / or Xe are preferably used. From the viewpoint of the production cost of the transparent conductive film X, it is preferable to use Kr as the sputtering gas.
  • the content ratio of Kr in the sputtering gas is, for example, 1% by volume or more, preferably 50% by volume or more, more preferably 99% by volume or more, still more preferably 99.5% by volume or more, particularly. It is preferably 99.9% by volume or more.
  • the content ratio is, for example, 100% by volume or less.
  • the sputtering gas may contain another inert gas such as Ar (an inert gas other than a rare gas having an atomic number larger than that of Ar).
  • 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.
  • oxygen is preferably used as the reactive gas.
  • the ratio of the flow rate of the reactive gas such as oxygen to the total flow rate of the sputtering gas (inert gas) and the reactive gas used in the reactive sputtering method is preferably 0.01 flow rate% or more, more preferably 0. 05 flow rate% or more, more preferably 0.08 flow rate% or more.
  • the same flow rate ratio is, for example, 15 flow rate% or less, preferably 8 flow% or less, more preferably 6 flow% or less, still more preferably 4 flow% or less.
  • the air pressure (deposition pressure) in the film forming chamber into which the gas (sputtering gas and reactive gas in the reactive sputtering method) is introduced after being evacuated is 0.04 Pa or more, preferably 0.08 Pa or more, and more. It is preferably 0.1 Pa or more.
  • the film formation pressure is 0.9 Pa or less, preferably 0.8 Pa or less, and more preferably 0.7 Pa or less.
  • the temperature (deposition temperature) of the transparent substrate 10 in this step is, for example, 100 ° C. or lower, preferably 50 ° C. or lower, more preferably 30 ° C. or lower, still more preferably 25 ° C. or lower, still more preferably 20 ° C. or lower, particularly. It is preferably 15 ° C. or lower, more preferably 10 ° C. or lower, most preferably 5 ° C. or lower, and for example, ⁇ 50 ° C. or higher, preferably ⁇ 20 ° C. or higher, more preferably ⁇ 10 ° C. or higher, still more preferably ⁇ 7. It is above °C.
  • 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 for example, 500 V or less.
  • the horizontal magnetic field strength on the target surface is, for example, 10 mT or more, preferably 20 mT or more, more preferably 30 mT or more, still more preferably 60 mT or more, and for example 300 mT or less, preferably 250 mT or less.
  • Such a configuration is preferable for suppressing the amount of impurities in the light-transmitting conductive layer 20. Suppressing the amount of impurities in the light-transmitting conductive layer 20 helps to reduce the resistance of the light-transmitting conductive layer 20, and also helps to suppress the occurrence of cracks in the light-transmitting conductive layer 20 in the heating process.
  • the light-transmitting conductive material examples include conductive oxides.
  • 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 oxides include indium tin oxide composite oxide (ITO), indium zinc composite oxide (IZO), indium gallium composite oxide (IGO), indium gallium zinc composite oxide (IGZO), and Antimonthin composite oxide (ATO) can be mentioned.
  • the conductive oxide is preferably an indium tin oxide composite oxide (ITO) containing both In and Sn. Is 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 light-transmitting conductive layer 20 is preferably 1. It is by mass% or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more. Such a configuration is suitable for ensuring the durability of the light-transmitting conductive layer 20. Further, from the viewpoint of obtaining the crystalline light-transmitting conductive layer 20 which is easily crystallized by heating, the above ratio of the tin oxide content is preferably 15% by mass or less, more preferably 13% by mass or less, still more preferably 12. It is less than mass%.
  • the above-mentioned content ratio of tin oxide can be adjusted by adjusting the tin oxide concentration in the ITO target used in the sputtering method.
  • 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 tin oxide content ratio in the light-transmitting conductive layer 20 may be non-uniform in the thickness direction D.
  • the light-transmitting conductive layer 20 has a transparent group of a first region 21 having a relatively large tin oxide content and a second region 22 having a relatively small tin oxide content. It may be prepared in order from the material 10 side.
  • the ratio of the tin oxide content to the total content of tin oxide and indium oxide in the first region 21 is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 9% by mass or more, and also. It is preferably 15% by mass or less, more preferably 13% by mass or less, and further preferably 12% by mass or less.
  • the ratio of the tin oxide content to the total content of tin oxide and indium oxide in the second region 22 is preferably 1% by mass or more, more preferably 2 as long as it is smaller than the above-mentioned tin oxide content ratio in the first region 21. It is mass% or more, more preferably 3% by mass or more, preferably 13% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less.
  • Such a configuration in which the light-transmitting conductive layer 20 has the first region 21 and the second region 22 is such that the light-transmitting conductive layer 20 can be easily crystallized in the crystallization step described later and the light-transmitting conductive layer.
  • the light transmissive conductive layer 20 having the first region 21 and the second region 22 uses, for example, a sputtering film forming apparatus provided with two film forming chambers, and the tin oxide concentration is high in the sputtering method in both film forming chambers. It can be formed by using different ITO targets.
  • 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 50%. It is more preferably 60% or more, still more preferably 64% 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 less than 50%, more preferably 40% or less, still more preferably 36% or less.
  • the configuration regarding the ratio of the thickness of each of the first region 21 and the second region 22 is preferable from the viewpoint of realizing a low specific resistance in the light-transmitting conductive layer 20 after crystallization.
  • FIG. 2 although the boundary between the first region 21 and the second region 22 is drawn by a virtual line, when the compositions of the first region 21 and the second region 22 are not significantly different, the first The boundary between the region 21 and the second region 22 may not be clearly discriminated.
  • the tin oxide content ratio may gradually change in the thickness direction D.
  • the tin oxide content may gradually increase or decrease as the distance from the transparent base material 10 increases in the thickness direction D.
  • a partial region in which the tin oxide content gradually increases as the distance from the transparent base material 10 increases is located on the transparent base material 10, and the portion that is oxidized as the distance from the transparent base material 10 increases.
  • the partial region where the tin content gradually decreases may be located on the opposite side of the transparent base material 10.
  • a partial region in which the Kr content ratio gradually decreases as the distance from the transparent base material 10 increases is located on the transparent base material 10 side, and the Kr content increases as the distance from the transparent base material 10 increases.
  • the partial region where the ratio gradually increases may be located on the side opposite to the transparent base material 10.
  • the light-transmitting conductive layer 20 may contain a rare gas atom having an atomic number larger than that of Ar (a rare gas atom such as Kr used as a sputtering gas).
  • the light-transmitting conductive layer 20 has a content ratio of a rare gas atom (Kr or the like) having an atomic number larger than that of Ar, preferably 1.0 atomic% or less, more preferably 0.7 atomic% or less, and further preferably 0.
  • a region of 5 atomic% or less, more preferably 0.3 atomic% or less, very preferably 0.2 atomic% or less, particularly preferably less than 0.1 atomic% is included in at least a part of the thickness direction D.
  • the content ratio of the noble gas atom having an atomic number larger than Ar in the region is, for example, 0.0001 atomic% or more.
  • the light-transmitting conductive layer 20 satisfies the above-mentioned content ratio of the rare gas atom having an atomic number larger than Ar in the entire area in the thickness direction D.
  • the content ratio of rare gas atoms (Kr, etc.) having an atomic number larger than Ar in the light-transmitting conductive layer 20 is preferably 1.0 atomic% or less, more preferably 1.0 atomic% or less in the entire thickness direction D.
  • These configurations are suitable for achieving good crystal growth and forming large crystal grains when heated to crystallize the light transmissive conductive layer 20, and therefore a low resistance crystalline light transmissive conductive layer. It is suitable for obtaining 20 (the larger the crystal grains in the crystalline light-transmitting conductive layer 20, the lower the resistance of the light-transmitting conductive layer 20).
  • the presence or absence of noble gas atoms in the light transmissive conductive layer 20 is identified by, for example, fluorescent X-ray analysis described later with respect to Examples.
  • the presence or absence and content of rare gas atoms in the light-transmitting conductive layer 20 are identified by, for example, Rutherford Backscattering Spectrometry.
  • the presence or absence of rare gas atoms such as Kr in the light transmissive conductive layer 20 is identified by, for example, fluorescent X-ray analysis described later with respect to Examples.
  • the noble gas atom content cannot be quantified because it is not above the detection limit value (lower limit value), and according to the fluorescent X-ray analysis, the noble gas atom.
  • the existence of is identified, it is determined that the light-transmitting conductive layer includes a region in which the content ratio of rare gas atoms such as Kr is 0.0001 atomic% or more.
  • the amorphous light-transmitting conductive layer 20 is formed as described above.
  • the amorphous light-transmitting conductive layer 20 can be formed by adjusting the film formation temperature and / or adjusting the flow rate ratio of the reactive gas.
  • the light-transmitting conductive layer is amorphous or crystalline can be determined, for example, as follows. First, the light-transmitting conductive layer (in the case of the transparent conductive film X, the light-transmitting conductive layer 20 on the transparent base material 10) is immersed in hydrochloric acid having a concentration of 5% by mass at 20 ° C. for 15 minutes (hydrochloric acid treatment). .. Next, the light-transmitting conductive layer is washed with water and then dried.
  • the resistance between the pair of terminals having a separation distance of 15 mm. Measure (resistance between terminals). In this measurement, when the resistance between terminals exceeds 10 k ⁇ , the light-transmitting conductive layer is amorphous (the light-transmitting conductive layer 20 after the film forming step and after the following crystallization step is amorphous. It can be judged based on the standard).
  • the light-transmitting conductive layer is crystalline (it is the standard that the light-transmitting conductive layer 20 after the following crystallization step is crystalline). Can be judged based on).
  • the thickness of the amorphous light-transmitting conductive layer 20 is, for example, 10 nm or more, preferably 40 nm or more, more preferably more than 40 nm, still more preferably 70 nm or more, still more preferably 100 nm or more, and particularly preferably 130 nm. That is all. Such a configuration is suitable for reducing the resistance of the light-transmitting conductive layer 20 after crystallization.
  • the thickness of the light-transmitting conductive layer 20 is preferably 1000 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less, particularly preferably 160 nm or less, and most preferably less than 150 nm. Such a configuration is suitable for suppressing warpage in the produced transparent conductive film X.
  • the surface resistance of the amorphous light-transmitting conductive layer 20 is, for example, 800 ⁇ / ⁇ or less, preferably 100 ⁇ / ⁇ or less, more preferably 50 ⁇ / ⁇ or less, still more preferably 15 ⁇ / ⁇ or less, and particularly preferably 13 ⁇ / ⁇ . It is as follows.
  • the surface resistance of the amorphous light-transmitting conductive layer 20 is, for example, 1 ⁇ / ⁇ or more.
  • the surface resistance can be measured by the 4-terminal method based on JIS K7194.
  • the surface resistance of the amorphous light-transmitting conductive layer 20 can be controlled, for example, by adjusting the film-forming temperature and / or adjusting the flow rate ratio of the reactive gas in the film-forming step.
  • the specific resistance of the amorphous light-transmitting conductive layer 20 is 4 ⁇ 10 -4 ⁇ ⁇ cm or more, preferably 4.5 ⁇ 10 -4 ⁇ ⁇ cm or more, more preferably 4.8 ⁇ 10 ⁇ . It is 4 ⁇ ⁇ cm or more, more preferably 5 ⁇ 10 -4 ⁇ ⁇ cm or more, and particularly preferably 5.2 ⁇ 10 -4 ⁇ ⁇ cm or more.
  • the specific resistance of the amorphous light-transmitting conductive layer 20 is preferably 12 ⁇ 10 -4 ⁇ ⁇ cm or less, more preferably 11 ⁇ 10 -4 ⁇ ⁇ cm or less, and further preferably 10.5 ⁇ 10 -4. It is ⁇ ⁇ cm or less. Such a configuration regarding the specific resistance is suitable for reducing the resistance of the light-transmitting conductive layer 20 after crystallization. The specific resistance is obtained by multiplying the surface resistance by the thickness.
  • the specific resistance of the amorphous light-transmitting conductive layer 20 after heat treatment at 155 ° C. for 1 hour is preferably 2.2 ⁇ 10 -4 ⁇ ⁇ cm or less, more preferably 2.0 ⁇ 10 -4. It is ⁇ ⁇ cm or less, more preferably 1.9 ⁇ 10 -4 ⁇ ⁇ cm or less.
  • Such a configuration is transparent when the transparent conductive film X is provided in the touch sensor, the dimming element, the photoelectric conversion element, the heat ray control member, the antenna member, the electromagnetic wave shielding member, the lighting device, the image display device, and the like. It is suitable for ensuring the low resistance required for the light-transmitting conductive layer 20 of the conductive film X.
  • the specific resistance of the amorphous light-transmitting conductive layer 20 after heat treatment at 155 ° C. for 1 hour is, for example, 0.1 ⁇ 10 -4 ⁇ ⁇ cm or more, preferably 0.5 ⁇ 10 -4. It is ⁇ ⁇ cm or more, more preferably 1 ⁇ 10 -4 ⁇ ⁇ cm or more.
  • the total light transmittance (JIS K 7375-2008) of the amorphous light-transmitting conductive layer 20 is preferably 60% or more, more preferably 80% or more, still more preferably 85% or more. Such a configuration is suitable for ensuring the transparency of the light-transmitting conductive layer 20 after crystallization. Further, the total light transmittance of the amorphous light-transmitting conductive layer 20 is, for example, 100% or less.
  • the light-transmitting conductive layer 20 is converted (crystallized) from amorphous to crystalline by heating.
  • the heating means include an infrared heater and an oven.
  • 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. or lower, from the viewpoint of suppressing the influence of heating on the transparent base material 10.
  • the heating time is, for example, less than 120 minutes, preferably 90 minutes or less, more preferably 60 minutes or less, and for example, 1 minute or more, preferably 5 minutes or more.
  • the transparent conductive film X includes a transparent base material 10 and a light-transmitting conductive layer 20 having both light-transmitting property and conductivity in this order toward one side in the thickness direction D.
  • the transparent 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 lighting device, an image display device, and the like.
  • the thickness of the light-transmitting conductive layer 20 after crystallization is, for example, the same as the thickness of the amorphous light-transmitting conductive layer 20, for example, 10 nm. It is more than 40 nm, more preferably 70 nm or more, still more preferably 100 nm or more, and particularly preferably 130 nm or more. Such a configuration is suitable for reducing the resistance of the light-transmitting conductive layer 20 in the transparent conductive film X.
  • the thickness of the crystalline light-transmitting conductive layer 20 is the same as that of the amorphous light-transmitting conductive layer 20, for example, preferably 1000 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less. Especially preferably, it is 160 nm or less. Such a configuration is suitable for suppressing warpage in the transparent conductive film X.
  • the surface resistance of the crystalline light-transmitting conductive layer 20 is, for example, 200 ⁇ / ⁇ or less, preferably 100 ⁇ / ⁇ or less, more preferably 80 ⁇ / ⁇ or less, still more preferably 30 ⁇ / ⁇ or less, and particularly preferably 20 ⁇ / ⁇ or less. Is.
  • Such a configuration is 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 shielding member, a lighting device, an image display device, or the like. It is suitable for ensuring the low resistance required for the light-transmitting conductive layer 20 of the conductive film X.
  • the surface resistance of the crystalline light-transmitting conductive layer 20 is, for example, 0.1 ⁇ / ⁇ or more.
  • the specific resistance of the crystalline light-transmitting conductive layer 20 is preferably 2.2 ⁇ 10 -4 ⁇ ⁇ cm or less, more preferably 2 ⁇ 10 -4 ⁇ ⁇ cm or less, and further preferably 1.9 ⁇ 10 ⁇ . It is 4 ⁇ ⁇ cm or less.
  • Such a configuration is 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 shielding member, a lighting device, an image display device, or the like. It is suitable for ensuring the low resistance required for the light-transmitting conductive layer 20 of the conductive film X.
  • the specific resistance of the crystalline light-transmitting conductive layer 20 is, for example, 0.1 ⁇ 10 -4 ⁇ ⁇ cm or more, preferably 0.5 ⁇ 10 -4 ⁇ ⁇ cm or more, more preferably 1 ⁇ 10 -4 ⁇ ⁇ cm or more. ⁇ It is cm or more.
  • the total light transmittance (JIS K 7375-2008) of the crystalline light-transmitting conductive layer 20 is preferably 60% or more, more preferably 80% or more, still more preferably 85% or more.
  • Such a configuration is 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 shielding member, a lighting device, an image display device, or the like. It is suitable for ensuring the transparency required for the conductive film X.
  • the total light transmittance of the crystalline light-transmitting conductive layer 20 is, for example, 100% or less.
  • the light-transmitting conductive layer 20 in the transparent conductive film X may be patterned as schematically shown in FIG. 3 (patterning step).
  • the light-transmitting conductive layer 20 can be patterned by etching the light-transmitting conductive layer 20 through a predetermined etching mask.
  • the patterned light-transmitting conductive layer 20 functions as, for example, a wiring pattern.
  • the patterning step may be carried out before the above-mentioned crystallization step. In that case, the light-transmitting conductive layer 20 is crystallized by heating after the patterning step.
  • an inert gas containing a rare gas having an atomic number larger than that of argon is used as the sputtering gas, and the film forming pressure is high.
  • Light transmission under the conditions of 0.04 Pa or more and 0.9 Pa or less preferably 0.08 Pa or more, more preferably 0.1 Pa or more, and preferably 0.8 Pa or less, more preferably 0.7 Pa or less).
  • a conductive material is formed to form an amorphous light-transmitting conductive layer 20.
  • Such a manufacturing method is suitable for obtaining a transparent conductive film X provided with a low-resistance crystalline light-transmitting conductive layer 20 in which the occurrence of cracks is suppressed. Specifically, it is as shown in Examples and Comparative Examples described later.
  • Kr and / or Xe are preferably used as the sputtering gas in the film forming step.
  • the content ratio of Kr in the sputtering gas is preferably 50% by volume or more, more preferably 99% by volume or more, still more preferably 99.5% by volume or more, particularly preferably 99.5% by volume or more, as described above. Is 99.9% by volume or more.
  • the functional layer 12 may be an adhesion improving layer for realizing high adhesion of the light-transmitting conductive layer 20 to the transparent base material 10.
  • the configuration in which the functional layer 12 is an adhesion improving layer is suitable for ensuring the adhesion between the transparent base material 10 and the light-transmitting conductive layer 20.
  • the functional layer 12 may be an index-matching layer for adjusting the reflectance of the surface of the transparent base material 10 (one surface in the thickness direction D).
  • the configuration in which the functional layer 12 is the refractive index adjusting layer makes it difficult to visually recognize the pattern shape of the light-transmitting conductive layer 20 when the light-transmitting conductive layer 20 on the transparent base material 10 is patterned. Suitable.
  • the functional layer 12 may be a peeling functional layer for practically peeling the light-transmitting conductive layer 20 from the transparent base material 10.
  • the structure in which the functional layer 12 is a peeling functional layer is suitable for peeling the light-transmitting conductive layer 20 from the transparent base material 10 and transferring the light-transmitting conductive layer 20 to another member.
  • the functional layer 12 may be a composite layer in which a plurality of layers are connected in the thickness direction D.
  • the composite layer preferably includes two or more layers selected from the group consisting of a hard coat layer, an adhesion improving layer, a refractive index adjusting layer, and a peeling functional layer.
  • Such a configuration is suitable for complex expression of the above-mentioned functions of each selected layer in the functional layer 12.
  • the functional layer 12 includes an adhesion improving layer, a hard coat layer, and a refractive index adjusting layer on the transparent resin film 11 in this order toward one side in the thickness direction D.
  • the functional layer 12 includes a peeling functional layer, a hard coat layer, and a refractive index adjusting layer on the transparent resin film 11 in this order toward one side in the thickness direction D.
  • the transparent conductive film X is used in a state where it is attached to an article and the light transmissive conductive layer 20 is patterned as needed.
  • the transparent conductive film X is attached to the article, for example, via 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 light-transmitting 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 light-transmitting conductive layer 20. good.
  • 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. Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxalic acid anilides compounds, cyanoacrylate compounds, and triazine compounds.
  • the light-transmitting conductive layer 20 (the light-transmitting conductive layer 20 after patterning) is formed in the transparent conductive film X. (Including) is exposed.
  • the cover layer may be arranged on the exposed surface of the light-transmitting conductive layer 20.
  • the cover layer is a layer that covers the light-transmitting conductive layer 20, and can improve the reliability of the light-transmitting conductive layer 20 and suppress functional deterioration due to damage to the light-transmitting 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.
  • Examples of the inorganic material include inorganic oxides and fluorides.
  • Examples of the inorganic oxide include silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide, and calcium oxide.
  • Examples of the fluoride 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 An ultraviolet curable resin containing an acrylic resin was applied to one surface of a long PET film (thickness 50 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) as a transparent resin film to form a coating film. Next, the coating film was cured by ultraviolet irradiation to form a hard coat layer (thickness 2 ⁇ m). In this way, a transparent base material including a transparent resin film and a hard coat layer as a functional layer was produced.
  • a light-transmitting conductive layer was formed on the hard coat layer of the transparent substrate by the reactive sputtering method.
  • a sputtering film forming apparatus capable of carrying out the film forming process by a roll-to-roll method was used.
  • This sputtering film forming apparatus includes a first film forming chamber (upstream film forming chamber) and a second film forming chamber (downstream side forming film forming chamber) arranged in order along the traveling path of the transparent substrate. It is a magnetron sputtering device.
  • the first region of the light-transmitting conductive layer is formed on the transparent substrate by the film formation by the sputtering method (1st sputtering film formation), and the reactivity in the 2nd film formation chamber.
  • a second region of the light-transmitting conductive layer was formed on the first region by film formation by a sputtering method (second sputtering film formation).
  • the conditions for the first sputter film formation are as follows.
  • a first target which is a sintered body of indium oxide and tin oxide (ITO having a tin oxide concentration of 10% by mass)
  • the power source for applying a voltage to the target is a DC power source.
  • the horizontal magnetic field strength on the target was 90 mT.
  • the film formation temperature (the temperature of the transparent base material on which the light-transmitting conductive layer is laminated) was set to ⁇ 5 ° C. Further, after the first film forming chamber is evacuated until the ultimate vacuum degree in the first film forming chamber reaches 0.9 ⁇ 10 -4 Pa, the first film forming chamber is reactive with Kr as a sputtering gas.
  • Oxygen as a gas was introduced, and the air pressure in the first film forming chamber was set to 0.1 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 1.5 flow rate%.
  • the oxygen introduction amount was adjusted so that the value of the surface resistance of the formed film was 50 ⁇ / ⁇ within the region R of the surface resistance-oxygen introduction amount curve.
  • the surface resistance-oxygen introduction amount curve shown in FIG. 4 shows the surface resistance of the light-transmitting conductive layer when the light-transmitting conductive layer is formed by the reactive sputtering method under the same conditions as above except for the oxygen introduction amount.
  • the dependence on the amount of oxygen introduced can be investigated and created in advance.
  • a second target which is a sintered body of indium oxide and tin oxide (ITO having a tin oxide concentration of 3% by mass), was used as the target.
  • ITO indium oxide and tin oxide
  • Other conditions in the second sputter film formation are the same as those in the first sputter film formation.
  • the transparent conductive film of Example 1 was produced.
  • the light-transmitting conductive layer (thickness 100 nm, amorphous) of the transparent conductive film of Example 1 contains a first region (thickness 95 nm) composed of Kr-containing ITO (tin oxide concentration 10% by mass) and Kr. It has a second region (thickness 5 nm) composed of ITO (tin oxide concentration 3% by mass) in order from the transparent substrate side.
  • each of the transparent conductive films of Examples 2 to 5 was produced in the same manner as the transparent conductive film of Example 1 except that it was set to 0.8 Pa (Example 5).
  • Example 6 In the first sputter film formation, the atmospheric pressure was set to 0.2 Pa instead of 0.1 Pa, and the thickness of the first region to be formed was set to 142 nm instead of 95 nm, and in the second spatter film formation, It was carried out in the same manner as the transparent conductive film of Example 1 except that the atmospheric pressure was set to 0.2 Pa instead of 0.1 Pa and the thickness of the formed second region was set to 8 nm instead of 5 nm.
  • the transparent conductive film of Example 6 was prepared. The total thickness of the light-transmitting conductive layer of this transparent conductive film is 150 nm.
  • Example 7 In the first sputter film formation, the atmospheric pressure was set to 0.2 Pa instead of 0.1 Pa, and the thickness of the first region to be formed was set to 38 nm instead of 95 nm, and in the second spatter film formation, It was carried out in the same manner as the transparent conductive film of Example 1 except that the atmospheric pressure was set to 0.2 Pa instead of 0.1 Pa and the thickness of the formed second region was set to 2 nm instead of 5 nm.
  • the transparent conductive film of Example 7 was prepared. The total thickness of the light-transmitting conductive layer of this transparent conductive film is 40 nm.
  • Example 8 Examples except that Ar was used instead of Kr as the sputtering gas in the second sputtering film formation, and the above-mentioned first target (ITO having a tin oxide concentration of 10% by mass) was used instead of the second target.
  • the transparent conductive film of Example 8 was produced in the same manner as the transparent conductive film of Example 8.
  • the transparent conductive film of Example 9 was produced in the same manner as the transparent conductive film of Example 9.
  • Comparative Example 1 In the first and second sputter film formations, the transparency of Comparative Example 1 was the same as that of the transparent conductive film of Example 1 except that the air pressure in each film formation chamber was set to 1.0 Pa instead of 0.1 Pa. A conductive film was produced.
  • the transparent conductive film of Comparative Example 2 was prepared and carried out in the same manner as the transparent conductive film of Example 2 except that Ar was used instead of Kr as the sputtering gas.
  • the transparent conductive film of Comparative Example 3 was produced in the same manner as the transparent conductive film of Example 5, and the transparent conductive film of Comparative Example 4 was produced in the same manner as the transparent conductive film of Comparative Example 1.
  • each light-transmitting conductive layer in Examples 1 to 9 and Comparative Examples 1 to 4 was measured by FE-TEM observation. Specifically, first, a cross-section observation sample of each light-transmitting conductive layer in Examples 1 to 9 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 light-transmitting 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.
  • a cross-section observation sample is prepared from the intermediate product before forming the second region on the first region, and the FE-TEM of the sample is prepared. Measured by observation. The thickness of the second region of each light-transmitting conductive layer was obtained by subtracting the thickness of the first region from the total thickness of the light-transmitting conductive layer.
  • each sample was observed with an optical microscope to check for cracks.
  • the case where the number of samples in which cracks are confirmed in the light-transmitting conductive layer is 15 or less is evaluated as “ ⁇ ” and is 16 to 25.
  • the case was evaluated as “ ⁇ ”, and the case of 26 or more sheets was evaluated as “x”.
  • the same operation and evaluation as the above operation and evaluation were carried out except that the heating temperature in the heat treatment was changed to 155 ° C. or 165 ° C. instead of 140 ° C. The results of these evaluations are listed in Table 1.
  • the transparent conductive film produced by 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.

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