WO2021187572A1 - 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

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WO2021187572A1
WO2021187572A1 PCT/JP2021/011146 JP2021011146W WO2021187572A1 WO 2021187572 A1 WO2021187572 A1 WO 2021187572A1 JP 2021011146 W JP2021011146 W JP 2021011146W WO 2021187572 A1 WO2021187572 A1 WO 2021187572A1
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layer
light
transmitting conductive
conductive layer
base material
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PCT/JP2021/011146
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English (en)
French (fr)
Japanese (ja)
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望 藤野
順平 小笹
健太 森地
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日東電工株式会社
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Priority to CN202180021982.0A priority Critical patent/CN115298761A/zh
Priority to JP2021517070A priority patent/JP7213961B2/ja
Priority to KR1020227030807A priority patent/KR20220155284A/ko
Publication of WO2021187572A1 publication Critical patent/WO2021187572A1/ja
Priority to JP2022177317A priority patent/JP2023017917A/ja

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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
    • 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
    • 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
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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

Definitions

  • the present invention relates to a transparent conductive film and a method for producing the transparent conductive film.
  • optical films such as transparent conductive films are known to be used for optical applications such as touch panels.
  • a transparent conductive film having a film base material and a polycrystalline layer of indium tin oxide formed on the film base material has been proposed (see, for example, Patent Document 1). ).
  • an amorphous layer of indium tin oxide is arranged on the surface of the film substrate in the presence of argon gas by sputtering, and then the amorphous layer is heated. It is obtained by crystallizing the amorphous layer of indium tin oxide.
  • such a polycrystalline layer may be heated again.
  • a heating step may be required when forming a member necessary for producing a touch sensor, a photoelectric conversion element, or the like on a transparent conductive film.
  • a step of applying a metal-containing paste on a polycrystalline layer and heating the touch sensor to form a routing wiring of the touch sensor can be mentioned. In such a case, it is required to suppress the change in the resistance value of the polycrystalline layer (excellent in heating stability) before and after heating.
  • an inorganic base material such as a glass base material is applied, and the base material temperature when the indium tin oxide layer (transparent conductive layer) is sputtered is set to a high temperature (for example, 230 ° C.). It can be realized by setting the above).
  • the film base material polymer film
  • the base material temperature cannot be set to a high temperature (the base material temperature is usually less than 200 ° C., preferably less than 200 ° C.). Therefore, the prior art including Patent Document 1 has not been able to realize a transparent conductive film having sufficiently excellent heating stability.
  • the present invention is to provide a transparent conductive film having excellent heating stability and a method for producing the transparent conductive film.
  • the present invention [1] includes a base material layer and a light-transmitting conductive layer in this order, the base material layer contains a resin layer, and the light-transmitting conductive layer contains krypton atoms and / or xenon atoms. , A transparent conductive film.
  • the present invention [2] includes the transparent conductive film according to the above [1], wherein the thickness of the light-transmitting conductive layer is 60 nm or more and 100 nm or less.
  • the present invention [3] is the transparent conductive film according to the above [1] or [2], wherein the light-transmitting conductive layer is crystalline and contains crystal grains having a particle size of 35 nm or more. Includes.
  • the transparent conductive film according to any one of the above [1] to [3], wherein the light-transmitting conductive layer contains an indium tin composite oxide.
  • the present invention [5] includes the transparent conductive film according to any one of the above [1] to [4], wherein the light-transmitting conductive layer has a pattern shape.
  • a light-transmitting conductive layer is arranged on a base material layer by a sputtering method targeting a material constituting the light-transmitting conductive layer in the presence of krypton and / or xenon, and the base material is described.
  • the layer is a method for producing a transparent conductive film, which comprises a resin layer.
  • a light-transmitting conductive layer is arranged on a base material layer by a sputtering method targeting a material constituting the light-transmitting conductive layer in the presence of krypton and / or xenon. do.
  • the sputtering gas is taken into the light-transmitting conductive layer.
  • the sputtering gas (krypton atom and / or xenone atom) is incorporated into the light-transmitting conductive layer. Can be suppressed.
  • the transparent conductive film of the present invention is excellent in heating stability.
  • FIG. 1 is a schematic view showing an embodiment of the transparent conductive film of the present invention.
  • FIG. 2 is a schematic view showing an embodiment of the method for producing a transparent conductive film of the present invention
  • FIG. 2A shows a step of preparing a base material layer in the first step
  • FIG. 2B shows a first step.
  • a step of arranging an amorphous light-transmitting conductive layer by sputtering on one surface in the thickness direction of the base material layer is shown
  • FIG. 2C shows that the amorphous light-transmitting conductive layer is heated.
  • the process of forming the crystalline light-transmitting conductive layer is shown.
  • FIG. 3 is a graph showing the relationship between the amount of oxygen gas introduced when the amorphous light-transmitting conductive layer is arranged in the first step and the resistance value of the amorphous light-transmitting conductive layer.
  • FIG. 4 is a schematic view showing an embodiment in which the light-transmitting conductive layer of the transparent conductive film shown in FIG. 1 is patterned.
  • FIG. 5 is a schematic view showing a modified example of the transparent conductive film (when the base material layer does not have a transparent base material and is composed of only a functional layer).
  • the transparent conductive film 1 has a film shape (including a sheet shape) having a predetermined thickness, extends in a plane direction orthogonal to the thickness direction, and has a flat upper surface and a flat lower surface.
  • the transparent conductive film 1 is provided in a touch sensor, a light control element, a photoelectric conversion element, a heat ray control member, an antenna, an electromagnetic wave shield member, an image display device, a heater member (light transmissive heater), lighting, and the like, which will be described later.
  • One member, the transparent conductive film 1 is an intermediate member for manufacturing them.
  • the transparent conductive film 1 is a device that is distributed independently and can be used industrially.
  • the transparent conductive film 1 includes a base material layer 2 and a light-transmitting conductive layer 3 in order toward one side in the thickness direction. More specifically, the transparent conductive film 1 includes a base material layer 2 and a light-transmitting conductive layer 3 arranged on the upper surface (one side in the thickness direction) of the base material layer 2. Preferably, the transparent conductive film 1 includes only the base material layer 2 and the light transmitting conductive layer 3.
  • the thickness of the transparent conductive film 1 is, for example, 300 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, still more preferably 100 ⁇ m or less, and for example, 1 ⁇ m or more, preferably 10 ⁇ m or more. ..
  • Base material layer 2 is a transparent base material for ensuring the mechanical strength of the transparent conductive film 1.
  • the base material layer 2 has a film shape.
  • the base material layer 2 is arranged on the entire lower surface of the light-transmitting conductive layer 3 so as to come into contact with the lower surface of the light-transmitting conductive layer 3.
  • the base material layer 2 includes a transparent base material 4 and a functional layer 5 as a resin layer.
  • the base material layer 2 includes a transparent base material 4 and a functional layer 5 in order toward one side in the thickness direction.
  • the base material layer 2 includes a transparent base material 4 and a functional layer 5 arranged on one surface of the transparent base material 4 in the thickness direction.
  • the transparent base material 4 has a film shape.
  • the transparent base material 4 is made of, for example, a polymer film. As a result, the transparent conductive film 1 is excellent in manufacturing efficiency.
  • the transparent conductive film 1 (crystalline light-transmitting conductive layer 3) is reheated from the viewpoint of imparting dimensional stability of the transparent conductive film 1.
  • this transparent conductive film 1 is excellent in heating stability.
  • Examples of the material of the transparent base material 4 include olefin resins such as polyethylene, polypropylene, and cycloolefin polymers, and polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, such as polymethacrylate.
  • Meta) acrylic resin (acrylic resin and / or methacrylic resin), for example, polycarbonate resin, melamine resin, polystyrene resin and the like, preferably olefin resin, polyester resin, (meth) acrylic resin, polycarbonate resin, melamine resin and the like.
  • These include, more preferably polyester resin, and even more preferably polyethylene terephthalate (PET).
  • the transparent base material 4 made of the above material has low heat resistance, it cannot be applied to a heating step of 200 ° C. or higher (specifically, a second step described later), but such a transparent base material 4 can be used. According to this, it is possible to obtain a transparent conductive film 1 having excellent smoothness and heating stability.
  • the transparent base material 4 has transparency. Specifically, the total light transmittance (JIS K 7375-2008) of the transparent base material 4 is, for example, 60% or more, preferably 80% or more, and more preferably 85% or more.
  • the thickness of the transparent substrate 4 is, for example, 1 ⁇ m or more, preferably 10 ⁇ m or more, preferably 30 ⁇ m or more, and for example, 300 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably. , 60 ⁇ m or less.
  • the functional layer 5 is arranged on one side of the transparent base material 4 in the thickness direction.
  • the functional layer 5 has a film shape.
  • Examples of the functional layer 5 include a hard coat layer.
  • the base material layer 2 includes the transparent base material 4 and the hard coat layer in order toward one side in the thickness direction.
  • the functional layer 5 is a hard coat layer
  • the hard coat layer is a scratch protection layer for making it difficult for the transparent conductive film 1 to be scratched.
  • the material of the hard coat layer is, for example, a hard coat composition.
  • the hard coat composition include the mixture described in JP-A-2016-179686.
  • the mixture contains, for example, a resin (binder resin) such as an acrylic resin or a urethane resin.
  • the thickness of the hard coat layer is, for example, 0.1 ⁇ m or more, and for example, 10 ⁇ m or less, preferably 5 ⁇ m or less.
  • the number of base material layers 2 in the transparent conductive film 1 is not particularly limited, and is preferably 1. 3. 3.
  • Light-transmitting conductive layer The light-transmitting conductive layer 3 is a transparent layer that exhibits excellent conductivity.
  • the light-transmitting conductive layer 3 has a film shape.
  • the light-transmitting conductive layer 3 is arranged on the entire upper surface (one surface in the thickness direction) of the base material layer 2 (hard coat layer) so as to be in contact with one surface in the thickness direction of the base material layer 2.
  • the material of the light transmissive conductive layer 3 for example, at least selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W.
  • Metal oxides containing one type of metal and / or metalloid can be mentioned.
  • the metal oxide may be further doped with the metal atoms shown in the above group, if necessary.
  • the light-transmitting conductive layer 3 include, for example, indium tin oxide composite oxide (ITO), indium gallium composite oxide (IGO), indium zinc composite oxide (IZO), and indium gallium zinc composite oxide (IGZO).
  • ITO indium tin oxide composite oxide
  • IGO indium gallium composite oxide
  • IZO indium zinc composite oxide
  • IGZO indium gallium zinc composite oxide
  • an antimony-containing oxide such as an anti-monstin composite oxide (ATO), preferably an indium-containing oxide, more preferably an indium tin composite oxide (ITO).
  • the specific resistance can be lowered.
  • the content ratio of tin oxide is, for example, 0.5% by mass or more, preferably 3% by mass or more, based on the total amount of tin oxide and indium oxide. More preferably, it is 5% by mass or more, further preferably 8% by mass or more, particularly preferably 9% by mass or more, and for example, 20% by mass or less, preferably 15% by mass or less, more preferably. It is 12% by mass or less.
  • the tin oxide content is equal to or higher than the above lower limit, lowering the resistance is promoted.
  • the content ratio of tin oxide is not more than the above-mentioned upper limit, the light-transmitting conductive layer 3 is excellent in heating stability.
  • the light-transmitting conductive layer 3 can include a region in which the proportion of tin oxide is 8% by mass or more.
  • the surface resistance value can be reduced.
  • the light-transmitting conductive layer 3 has a first region 11 as an example of a region in which the ratio of tin oxide is 8% by mass or more, and a first region 11 having a ratio of tin oxide lower than the ratio of tin oxide in the first region 11. Includes 2 regions 12 and.
  • the light-transmitting conductive layer 3 includes a layered first region 11 and a layered second region 12 arranged on one surface of the first region 11 in the thickness direction in order. The boundary between the first region 11 and the second region 12 is not confirmed by observation with a measuring device, and it is permissible that the boundary is unclear.
  • the light-transmitting conductive layer 3 may have a concentration gradient in which the tin oxide concentration gradually increases from one surface in the thickness direction to the other surface.
  • a desired crystallization rate can be obtained by adjusting the ratio of the region.
  • the proportion of tin oxide in the first region 11 is preferably 9% by mass or more, more preferably 10% by mass or more, and 20% by mass or less.
  • the ratio of the thickness of the first region 11 to the thickness of the light-transmitting conductive layer 3 is, for example, more than 50%, preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. Further, for example, it is 99% or less, preferably 97% or less.
  • the ratio of the thickness of the first region 11 is equal to or greater than the above lower limit, the ratio of tin oxide in the light transmissive conductive layer 3 can be increased, and therefore the surface resistance value can be sufficiently reduced.
  • the proportion of tin oxide in the second region 12 is, for example, less than 8% by mass, preferably 7% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less, and for example. It is 1% by mass or more, preferably 2% by mass or more, and more preferably 3% by mass or more.
  • the ratio of the thickness of the second region 12 to the thickness of the light transmissive conductive layer 3 is, for example, 1% or more, preferably 3% or more, and for example, 50% or less, preferably 30% or less. It is preferably 20% or less, more preferably 10% or less.
  • the ratio of the ratio of tin oxide in the first region 11 to the ratio of tin oxide in the second region 12 is, for example, 1.5.
  • the above is preferably 2 or more, more preferably 2.5 or more, and for example, 5 or less, preferably 4 or less.
  • the tin oxide concentration in each of the light-transmitting conductive layer 3, the first region 11 and the second region 12 is measured by X-ray photoelectron spectroscopy.
  • the tin oxide content can be estimated from the target component (known) used when forming the amorphous light-transmitting conductive layer 3 by sputtering.
  • the light-transmitting conductive layer 3 contains a trace amount of sputtering gas (krypton atom and / or xenon atom), which will be described in detail later.
  • sputtering gas krypton atom and / or xenon atom
  • the content of the sputtering gas (cryptone atom and / or xenone atom) in the light transmissive conductive layer 3 is, for example, 1.0 atom% or less, preferably 0.5 atom% or less, more preferably 0.2 atom. % Or less, more preferably 0.1 atomic% or less, and particularly preferably less than 0.1 atomic%.
  • the lower limit of the above content is the corresponding ratio when the presence of krypton atom and / or xenon atom can be confirmed by the fluorescent X-ray analyzer, and is at least 0.0001 atomic% or more.
  • the light-transmitting conductive layer 3 is crystalline or amorphous.
  • the specific resistance can be reduced.
  • the crystallinity of the light-transmitting conductive layer 3 is determined by, for example, immersing the transparent conductive film 1 in hydrochloric acid (20 ° C., concentration 5% by mass) for 15 minutes, washing with water and drying, and then the light-transmitting conductive layer. It can be determined by measuring the resistance between terminals within about 15 mm with respect to the surface on the 3rd side. In the transparent conductive film 1 after immersion, washing with water, and drying, when the resistance between terminals between 15 mm is 10 k ⁇ or less, the light-transmitting conductive layer 3 is crystalline, while the resistance exceeds 10 k ⁇ . , The light-transmitting conductive layer 3 is amorphous.
  • the light-transmitting conductive layer 3 has transparency. Specifically, the total light transmittance (JIS K 7375-2008) of the light-transmitting conductive layer 3 is, for example, 60% or more, preferably 80% or more, and more preferably 85% or more.
  • the thickness of the light transmissive conductive layer 3 is, for example, 10 nm or more, preferably 20 nm or more, more preferably 40 nm or more, still more preferably 50 nm or more, particularly preferably 60 nm or more, and for example, 1000 nm or less. It is preferably less than 300 nm, more preferably 250 nm or less, still more preferably 180 nm or less, particularly preferably less than 150 nm, and particularly preferably 140 nm or less.
  • the heating stability of the transparent conductive film 1 can be further improved.
  • the thickness of the light-transmitting conductive layer 3 is not more than the above upper limit, the heating stability of the transparent conductive film 1 can be further improved.
  • the thickness of the light-transmitting conductive layer 3 can be measured by observing the cross section of the transparent conductive film 1 using, for example, a transmission electron microscope.
  • the specific resistance of the light transmissive conductive layer 3 is, for example, 5.0 ⁇ 10 -4 ⁇ ⁇ cm or less, preferably 2.5 ⁇ 10 -4 ⁇ ⁇ cm or less, more preferably 2.4 ⁇ 10 ⁇ . 4 ⁇ ⁇ cm or less, more preferably 2.2 ⁇ 10 -4 ⁇ ⁇ cm or less, particularly preferably 2.0 ⁇ 10 -4 ⁇ ⁇ cm or less, particularly preferably 1.8 ⁇ 10 -4 ⁇ ⁇ Cm or less, and for example 0.1 ⁇ 10 -4 ⁇ ⁇ cm or more, preferably 0.5 ⁇ 10 -4 ⁇ ⁇ cm or more, more preferably 1.0 ⁇ 10 -4 ⁇ ⁇ cm. It is cm or more, more preferably 1.01 ⁇ 10 -4 ⁇ ⁇ cm or more.
  • the resistivity can be measured by the 4-terminal method in accordance with JIS K7194.
  • the surface resistance value of the light transmissive conductive layer 3 is, for example, 200 ⁇ / ⁇ or less, preferably 80 ⁇ / ⁇ or less, more preferably 60 ⁇ / ⁇ or less, still more preferably 50 ⁇ / ⁇ or less, and particularly preferably 30 ⁇ . / ⁇ or less, most preferably 20 ⁇ / ⁇ or less, and usually 0 ⁇ / ⁇ or more, and 1 ⁇ / ⁇ or more.
  • the surface resistance value can be measured by the 4-terminal method in accordance with JIS K7194.
  • the number of the light-transmitting conductive layers 3 in the transparent conductive film 1 is not particularly limited, and is preferably 1. Specifically, the number of light-transmitting conductive layers 3 with respect to one base material layer 2 is preferably 1. 4. Method for Producing Transparent Conductive Film Next, refer to FIG. 2 for a method for producing the transparent conductive film 1, in particular, a method for producing the transparent conductive film 1 in which the light transmissive conductive layer 3 is amorphous. ,explain.
  • the method for producing the transparent conductive film 1 is that the material constituting the light-transmitting conductive layer 3 is targeted by sputtering in the presence of krypton and / or xenone.
  • a first step of arranging an amorphous light-transmitting conductive layer 3 on one surface of the base material layer 2 in the thickness direction is provided. Further, in this manufacturing method, each layer is arranged in order by, for example, a roll-to-roll method.
  • the base material layer 2 is prepared.
  • a diluted solution of the hard coat composition is applied to one surface of the transparent base material 4 in the thickness direction, and after drying, the hard coat composition is cured by irradiation with ultraviolet rays. As a result, a hard coat layer (functional layer 5) is formed on one surface of the transparent base material 4 in the thickness direction.
  • the amorphous light-transmitting conductive layer 3 is arranged on one surface of the base material layer 2 in the thickness direction by sputtering.
  • krypton gas and / or xenon gas are opposed to a target made of the material of the light-transmitting conductive layer 3 in the thickness direction of the base material layer 2.
  • the target material is sputtered in the presence of xenon gas alone).
  • a magnet is arranged on the side opposite to the base material layer 2 with respect to the target.
  • the horizontal magnetic field strength on the target surface is, for example, 10 mT or more, preferably 60 mT or more, and for example, 300 mT or less.
  • the temperature of the base material layer 2 when forming the light-transmitting conductive layer 3 by sputtering is not particularly limited, but preferably cools the base material layer 2.
  • the temperature of the base material layer 2 is, for example, 15 ° C. or lower, more preferably 10 ° C. or lower, still more preferably 5 ° C. or lower, particularly preferably 0 ° C. or lower, and for example,-.
  • the temperature is 50 ° C. or higher, preferably ⁇ 30 ° C., more preferably ⁇ 20 ° C. or higher.
  • the base material layer 2 When the temperature is equal to or lower than the above temperature, the base material layer 2 can be cooled during sputtering, outgas (water or organic solvent) is less likely to be emitted from the base material layer 2, and impurity components in the light transmissive conductive layer 3 can be reduced. Therefore, a light-transmitting conductive layer 3 having low resistivity and excellent heating stability can be obtained.
  • the temperature is above the above temperature, deterioration of the physical properties of the base material layer 2 can be suppressed.
  • the partial pressure of krypton gas and / or xenon gas in the sputtering apparatus is, for example, 0.1 Pa or more, preferably 0.3 Pa or more, and for example, 10 Pa or less, preferably 5 Pa or less, more preferably. It is 1 Pa or less.
  • a reactive gas such as oxygen can be present in addition to krypton gas and / or xenon gas.
  • the amount of the reactive gas introduced can be estimated from the surface resistance of the amorphous light-transmitting conductive layer 3.
  • the film quality (surface resistance) of the amorphous light-transmitting conductive layer 3 changes depending on the amount of the reactive gas introduced into the amorphous light-transmitting conductive layer 3, which is the purpose.
  • the amount of the reactive gas introduced can be adjusted according to the surface resistance of the amorphous light-transmitting conductive layer 3.
  • the amount of the reactive gas introduced is adjusted in the range X of FIG. It is preferable to obtain a crystalline light-transmitting conductive layer 3.
  • the amount of the reactive gas introduced is not limited, but when the reactive gas is oxygen, the ratio of the amount of oxygen introduced to the total amount of krypton gas and / or xenone gas and oxygen introduced is, for example, 0.01 flow rate%.
  • the above and for example, less than 5% by mass, preferably less than 4.5% by mass. If the amount of oxygen introduced is within the above range, it can be surely set within the range of region X in FIG.
  • the surface resistance of the amorphous light-transmitting conductive layer 3 is, for example, 300 ⁇ / ⁇ or less, preferably 200 ⁇ / ⁇ or less, more preferably 150 ⁇ / ⁇ or less, and for example.
  • the reactive gas is introduced so as to be 30 ⁇ / ⁇ or more, preferably 70 ⁇ / ⁇ or more.
  • the pressure in the sputtering apparatus is the total pressure of the partial pressure of the krypton gas and / or the xenon gas and the partial pressure of the reactive gas.
  • the first target and the second target having different tin oxide concentrations may be arranged in order in the sputtering apparatus along the transport direction of the base material layer 2.
  • the material of the first target is, for example, ITO (tin oxide concentration: 8% by mass or more) in the first region 11 described above.
  • the material of the second target is, for example, ITO (tin oxide concentration: less than 8% by mass) in the second region 12 described above.
  • the amorphous light-transmitting conductive layer 3 is arranged on one surface of the base material layer 2 in the thickness direction.
  • the amorphous light-transmitting conductive layer 3 When the amorphous light-transmitting conductive layer 3 is formed by sputtering using the first target and the second target described above, the amorphous light-transmitting conductive layer 3 has a tin oxide concentration.
  • the first amorphous layer and the second amorphous layer which are different from each other, are provided in order toward one side in the thickness direction.
  • the materials of the first amorphous layer and the second amorphous layer are the same as the materials of the first target and the second target, respectively.
  • the tin oxide concentration in ITO of the first amorphous layer is, for example, 8% by mass or more.
  • the tin oxide concentration in ITO of the second amorphous layer is, for example, less than 8% by mass.
  • the ratio of the thickness of the first amorphous layer to the thickness of the amorphous light-transmitting conductive layer 3 is, for example, more than 50%, preferably 70% or more, more preferably 80% or more, still more preferably. It is 90% or more, and for example, 99% or less, preferably 97% or less.
  • the ratio of the thickness of the second amorphous layer to the thickness of the light-transmitting conductive layer 3 is, for example, 1% or more, preferably 3% or more, and for example, 50% or less, preferably 30% or less. , More preferably 20% or less, still more preferably 10% or less.
  • a transparent conductive film 1 (sometimes referred to as an amorphous laminated film) composed of the base material layer 2 and the amorphous light-transmitting conductive layer 3 is obtained.
  • the amorphous light transmitting conductive layer 3 is heated after the first step described above to crystallize.
  • the second step of forming the quality light-transmitting conductive layer 3 is carried out.
  • the method for producing the transparent conductive film 1 targets the material constituting the light transmitting conductive layer 3 in the presence of krypton and / or xenone.
  • the first step of arranging the amorphous light-transmitting conductive layer 3 on one surface in the thickness direction of the base material layer 2 and the amorphous light-transmitting conductive layer 3 are heated to be crystalline.
  • a second step of forming the light-transmitting conductive layer 3 of the above is provided.
  • the second step is carried out after the first step described above.
  • the amorphous laminated film is heated.
  • the amorphous light-transmitting conductive layer 3 is heated by a heating device such as an infrared heater or an oven.
  • the heating temperature is, for example, 80 ° C. or higher, preferably 110 ° C. or higher, and for example, less than 200 ° C., preferably 180 ° C. or lower, more preferably 160 ° C. or lower, and heating.
  • the time is, for example, 1 minute or more, preferably 10 minutes or more, more preferably 30 minutes or more, and for example, 5 hours or less, preferably 3 hours or less.
  • the amorphous light-transmitting conductive layer 3 is crystallized, and the crystalline light-transmitting conductive layer 3 is formed.
  • the crystalline light-transmitting conductive layer 3 is the first amorphous layer. And the first region 11 and the second region 12 corresponding to the second amorphous layer, respectively.
  • the transparent conductive film 1 including the base material layer 2 and the crystalline light-transmitting conductive layer 3 in this order is manufactured.
  • the transparent conductive film 1 including the base material layer 2 and the amorphous or crystalline light-transmitting conductive layer 3 in this order is manufactured.
  • the light-transmitting conductive layer 3 is, for example, 35 nm or more, preferably 100 nm or more, more preferably 200 nm or more, still more preferably 250 nm or more.
  • the particle size is 300 nm or more, most preferably 400 nm or more, further 480 nm or more, further 550 nm or more, and for example, 2000 nm or less, preferably 1000 nm or less, more preferably 600 nm or less. Contains crystal grains having.
  • the particle size is within the above range (particularly, if it is 35 nm or more), the specific resistance of the light-transmitting conductive layer 3 can be reduced, and the heating stability of the transparent conductive film 1 can be further improved. It can be further improved.
  • the carrier density of the crystalline light-transmitting conductive layer 3 is not particularly limited, but is, for example, 30 ⁇ 10 19 cm -3 or more, preferably 70 ⁇ 10 19 cm -3 or more, more preferably 90 ⁇ 10 19 cm -3 or more, more preferably 100 ⁇ 10 19 cm -3 or more, and 300 ⁇ 10 19 cm -3 or less, preferably 200 ⁇ 10 19 cm -3 or less, more preferably 190 ⁇ 10 It is 19 cm -3 or less.
  • the carrier density is within the above range, the light-transmitting conductive layer 3 having excellent low resistivity can be obtained.
  • the mobility of the crystalline light-transmitting conductive layer 3 is not particularly limited, but is, for example, 15 cm 2 / V ⁇ s or more, preferably 20 cm 2 / V ⁇ s or more, more preferably 25 cm 2 / V ⁇ s. Above, more preferably 27 cm 2 / V ⁇ s or more, particularly preferably 28 cm 2 / V ⁇ s or more, and 50 cm 2 / V ⁇ s or less, preferably 40 cm 2 / V ⁇ s or less. .. When the mobility is within the above range, the light-transmitting conductive layer 3 having excellent low resistivity can be obtained.
  • the carrier density and mobility can be measured using a Hall effect measuring device (for example, trade name "HL5500PC", manufactured by Bio-Rad).
  • the amorphous light-transmitting conductive layer 3 is arranged by sputtering in the presence of krypton gas and / or xenon gas.
  • the sputtering gas is taken into the amorphous light-transmitting conductive layer 3.
  • the sputtering gas (krypton atom and / or xenone atom) is amorphous because a krypton atom and / or a xenone atom having a larger atomic weight than argon is used as the sputtering gas instead of the commonly used argon. It is possible to suppress the incorporation into the light-transmitting conductive layer 3 of the above.
  • Such an amorphous light-transmitting conductive layer 3 becomes a crystalline light-transmitting conductive layer 3 in the second step.
  • the crystalline light-transmitting conductive layer 3 contains krypton atoms and / or xenon atoms, the amount of krypton atoms and / or xenon atoms incorporated is suppressed as described above. Therefore, the transparent conductive film 1 is excellent in heating stability.
  • the light-transmitting conductive layer 3 can be patterned in the transparent conductive film 1. That is, the light-transmitting conductive layer 3 has a pattern shape.
  • the transparent conductive film 1 has a pattern portion 7 having a light-transmitting conductive layer 3 and a non-patterned portion 8 having no light-transmitting conductive layer 3.
  • the light-transmitting conductive layer 3 is crystallized.
  • this transparent conductive film 1 is used for various articles.
  • articles include touch sensors, dimming elements (voltage-driven dimming elements such as PDLC, PNLC and SPD, current-driven dimming elements such as electrochromic (EC)), and photoelectric conversion elements (organic thin-film solar cells).
  • electrodes of solar cell elements typified by dye-sensitized solar cells), heat ray control members (near-infrared reflection and / or absorption members and far-infrared reflection and / or absorption members), antennas (light-transmitting antennas) , Electromagnetic wave shield member, image display device, heater member (light transmissive heater), and illumination.
  • the article includes a transparent conductive film 1 and a member corresponding to each article.
  • Such an article can be obtained by fixing the transparent conductive film 1 and the member corresponding to each article.
  • the light-transmitting conductive layer 3 (including the light-transmitting conductive layer 3 having a pattern shape) in the transparent conductive film 1 and the member corresponding to each article are fixed via the fixing functional layer. ..
  • Examples of the fixing functional layer include an adhesive layer and an adhesive layer.
  • the fixing functional layer any material having transparency 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.
  • an acrylic resin is preferably selected as the resin from the viewpoint of excellent optical transparency, exhibiting adhesive properties such as appropriate wettability, cohesiveness and adhesiveness, and excellent weather resistance and heat resistance. NS.
  • the fixing functional layer contains a known corrosion inhibitor and a migration inhibitor (for example, Japanese Patent Application Laid-Open No. 2015-022397) in order to suppress corrosion and migration of the light-transmitting conductive layer 3. (Disclosure material) can also be added.
  • a known ultraviolet absorber may be added to the fixing functional layer (resin forming the fixing functional layer) 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 base material layer 2 in the transparent conductive film 1 and the member corresponding to each article can be fixed via the fixing functional layer.
  • the light-transmitting conductive layer 3 (including the light-transmitting conductive layer 3 having a pattern shape) is exposed in the transparent conductive film 1. Therefore, the cover layer can be arranged on the upper surface of the light-transmitting conductive layer 3.
  • the cover layer is a layer that covers the light-transmitting conductive layer 3, and can improve the reliability of the light-transmitting conductive layer 3 and suppress functional deterioration due to scratches.
  • the cover layer is preferably a dielectric.
  • the cover layer is formed from a mixture of resin and inorganic materials.
  • the resin include the resin exemplified by the fixing functional layer.
  • the inorganic material include materials exemplified by the material of the intermediate layer described later.
  • a corrosion inhibitor, a migration inhibitor, and an ultraviolet absorber can be added to the cover layer (mixture of resin and inorganic material) from the same viewpoint as the above-mentioned fixing functional layer.
  • Such articles include the transparent conductive film 1 of the present invention. , Excellent heating stability. 5.
  • the same members and processes as in one embodiment are designated by the same reference numerals, and detailed description thereof will be omitted. Further, the modified example can exhibit the same action and effect as that of one embodiment, except for special mention. Further, one embodiment and a modification thereof can be combined as appropriate.
  • the light-transmitting conductive layer 3 does not include the second region in which the proportion of tin oxide is less than 8% by mass, and may include only the first region 11 in which the proportion of tin oxide is 8% by mass or more.
  • the functional layer 5 was a hard coat layer, but an optical adjustment layer can be arranged as the functional layer 5.
  • the base material layer 2 includes the transparent base material 4 and the optical adjustment layer in order toward one side in the thickness direction.
  • the optical adjustment layer is a layer that suppresses the visibility of the pattern formed from the light transmissive conductive layer 3 and adjusts the optical physical characteristics (specifically, the refractive index) of the transparent conductive film 1.
  • the material of the optical adjustment layer is, for example, an optical adjustment composition.
  • Examples of the optical adjustment composition include the mixture described in JP-A-2016-179686.
  • the mixture contains, for example, a resin such as an acrylic resin (binder resin) and inorganic and / or organic particles (preferably inorganic particles such as zirconia).
  • a resin such as an acrylic resin (binder resin) and inorganic and / or organic particles (preferably inorganic particles such as zirconia).
  • the thickness of the optical adjustment layer 8 is, for example, 0.05 ⁇ m or more, and is, for example, 1 ⁇ m or less.
  • a diluted solution of the optical adjustment composition is applied to one surface in the thickness direction of the transparent base material 4, and after drying, the optical adjustment composition is cured by irradiation with ultraviolet rays.
  • a peeling functional layer can be arranged.
  • the base material layer 2 includes the transparent base material 4 and the peeling function layer in order toward one side in the thickness direction.
  • the peeling functional layer is a layer (easy peeling layer) that can be easily peeled off from the light-transmitting conductive layer 3.
  • the light-transmitting conductive layer 3 can be peeled from the transparent conductive film 1.
  • the peeled light-transmitting conductive layer 3 can be used, for example, by transferring and bonding to another member constituting the touch sensor.
  • an easy-adhesion layer can be arranged as the functional layer 5.
  • the base material layer 2 includes the transparent base material 4 and the easy-adhesion layer in order toward one side in the thickness direction.
  • the easy-adhesion layer is a layer for ensuring the adhesion between the transparent base material 4 and the layer formed on the easy-adhesion layer. For example, the adhesion between the transparent base material 4 and the light-transmitting conductive layer 3 is maintained. Can be improved.
  • the functional layer 5 may be a plurality of layers.
  • the base material layer 2 can optionally include, as the functional layer 5, two or more layers selected from the group consisting of a hard coat layer, an optical adjustment layer, a peeling functional layer, and an easy-adhesion layer.
  • the base material layer 2 may be provided with the transparent base material 4, the easy-adhesion layer, the hard coat layer, and the optical adjustment layer in order toward one side in the thickness direction, and the base material layer 2 may be provided.
  • the transparent base material 4, the peeling function layer, the hard coat layer and / or the optical adjustment layer may be provided in order toward one side in the thickness direction.
  • the transparent conductive film 1 is hard.
  • the laminate including the coat layer and / or the optical adjustment layer and the light transmissive conductive layer 3 can be peeled off.
  • the base material layer 2 may not include the functional layer 5 and may be composed of only the transparent base material 4.
  • the base material layer 2 may not include the transparent base material 4 and may be composed of only the functional layer 5.
  • Examples of the transparent conductive film 1 provided with such a base material layer 2 include the above-mentioned laminate (a laminate having a hard coat layer and / or an optical adjustment layer and a light-transmitting conductive layer 3).
  • the transparent conductive film 1 includes a base material layer 2 (functional layer 5) and a light-transmitting conductive layer 3 in order toward one side in the thickness direction.
  • the base material layer 2 can also be composed of a transparent base material 4 containing glass and a functional layer 5.
  • the base material layer 2 may be provided with an anti-blocking layer (not shown) on the other surface of the transparent base material 4.
  • the base material layer 2 includes an anti-blocking layer, a transparent base material 4, and a functional layer 5 in order toward one side in the thickness direction.
  • the anti-blocking layer imparts blocking resistance to the respective surfaces of the plurality of transparent conductive films 1 in contact with each other when the transparent conductive films 1 are laminated in the thickness direction.
  • the anti-blocking layer has a film shape.
  • the material of the anti-blocking layer is, for example, an anti-blocking composition.
  • anti-blocking composition examples include the mixture described in JP-A-2016-179686.
  • the mixture contains, for example, a resin such as an acrylic resin (binder resin) and inorganic and / or organic particles (preferably organic particles such as polystyrene).
  • a resin such as an acrylic resin (binder resin) and inorganic and / or organic particles (preferably organic particles such as polystyrene).
  • the thickness of the anti-blocking layer is, for example, 0.1 ⁇ m or more, and for example, 10 ⁇ m or less.
  • a diluted solution of the anti-blocking composition is applied to the other surface of the transparent base material 4 in the thickness direction, dried, and then the anti-blocking composition is cured by irradiation with ultraviolet rays.
  • a functional layer 5 such as an easy-adhesion layer can be further provided between the anti-blocking layer and the transparent base material 4.
  • the base material layer 2 may be provided with an intermediate layer (not shown) made of an inorganic layer on one side of the transparent base material 4.
  • the intermediate layer has a function of improving the surface hardness of the base material layer 2 and relaxing the stress received by the light-transmitting conductive layer 3 from the base material layer 2 at an intermediate point.
  • the intermediate layer can be provided at an arbitrary position with respect to the transparent base material 4, the functional layer 5, and the anti-blocking layer with respect to one side in the thickness direction of the transparent conductive film, and a plurality of layers may be provided.
  • the base material layer 2 includes a transparent base material 4, a functional layer 5, and an intermediate layer in order toward one side in the thickness direction.
  • the base material layer 2 includes, for example, an intermediate layer, an anti-blocking layer, a transparent base material 4, and a functional layer 5 in order toward one side in the thickness direction.
  • the intermediate layer is preferably an inorganic dielectric, and its surface resistance value is, for example, 1 ⁇ 10 6 ⁇ / ⁇ or more, preferably 1 ⁇ 10 8 ⁇ / ⁇ or more.
  • the material of the intermediate layer is composed of, for example, an inorganic oxide such as silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide and calcium oxide, and a fluoride such as magnesium fluoride.
  • the composition of the inorganic functional layer may or may not be a chemical composition.
  • 1 is exemplified as a suitable number of the light-transmitting conductive layer 3 in the transparent conductive film 1, but for example, although not shown, it may be 2.
  • each of the two light-transmitting conductive layers 3 is arranged on both sides of the base material layer 2 in the thickness direction. That is, in a preferred example of this modification, the number of light-transmitting conductive layers 3 with respect to one base material layer 2 is preferably 2.
  • Example 1 Production of transparent conductive film Example 1 (First step) An ultraviolet curable resin made of an acrylic resin was applied to one surface of a film base material made of a PET film roll (manufactured by Toray Industries, Inc., thickness 50 ⁇ m) as a transparent base material, and cured by ultraviolet irradiation. As a result, a hard coat layer having a thickness of 2 ⁇ m was formed. As a result, a base material layer was obtained.
  • the base material layer was placed in a vacuum sputtering apparatus, and the base material layer was degassed by sufficiently vacuum exhausting so that the ultimate vacuum degree was 0.9 ⁇ 10 -4 Pa. Then, while transporting the base material layer along the film forming roll, indium oxide and tin oxide are baked under reduced pressure (0.4 Pa) in which krypton as a sputtering gas and oxygen as a reactive gas are introduced.
  • ITO indium oxide and tin oxide
  • oxygen oxygen as a reactive gas
  • An amorphous light-transmitting conductive layer (first amorphous layer having a tin oxide concentration of 10% by mass) was formed.
  • the amount of oxygen introduced was adjusted so that the region X of the resistance-oxygen curve shown in FIG. 3 and the surface resistance of the amorphous light-transmitting conductive layer were 45 ⁇ / ⁇ (total introduction of krypton and oxygen).
  • the ratio of the amount of oxygen introduced to the amount is about 1.4% by mass).
  • an amorphous laminated film composed of a base material layer and an amorphous light-transmitting conductive layer was obtained.
  • the obtained amorphous laminated film was heated in a hot air oven at 155 ° C. for 1 hour.
  • the amorphous light-transmitting conductive layer was used as a crystalline light-transmitting conductive layer, and a transparent conductive film composed of a base material layer and a crystalline light-transmitting conductive layer was obtained.
  • Example 3 A second target made of ITO having a tin oxide concentration of 3% by mass was further installed in the vacuum sputtering apparatus of Example 1 to form a first amorphous layer having a thickness of 60 nm (tin oxide concentration of 10% by mass). After that, a second amorphous layer having a thickness of 3 nm (tin oxide concentration is 3% by mass) is continuously formed on one surface of the first amorphous layer, and an amorphous light-transmitting conductive layer is formed.
  • a transparent conductive film was obtained in the same manner as in Example 1 except that the amount of oxygen introduced was adjusted so that the surface resistance of the above was 120 ⁇ / ⁇ .
  • Example 4 and Comparative Examples 2 to 4 Transparent conductivity is the same as in Example 3, except that the sputtering gas, the thicknesses of the first and second regions, and the surface resistance of the amorphous light-transmitting conductive layer are changed according to the description in Table 1. I got a film. 2. Evaluation ⁇ Thickness measurement> (Thickness of transparent substrate and hard coat layer) The thickness of the transparent base material and the thickness of the hard coat layer were measured using a film thickness meter (Digital Dial Gauge DG-205 manufactured by Peacock). The results are shown in Table 1.
  • Example 3 Thin of light-transmitting conductive layer
  • Example 4 Comparative Example 2, Comparative Example 3 and Comparative Example 4
  • the thickness of the first region is set on one surface in the thickness direction of the first region before the second region is arranged.
  • a cross-section observation sample in which only the first region was formed was prepared, and the sample was measured by FE-TEM observation.
  • the thickness of the second region was calculated by subtracting the thickness of the first region from the thickness of the light-transmitting conductive layer. The results are shown in Table 1.
  • FIB device Hitachi FB2200
  • acceleration voltage 10kV
  • FE-TEM device JEOL JEM-2800
  • acceleration voltage 200kV ⁇ Evaluation of resistance value>
  • R1 and R1' specific resistance of the light-transmitting conductive layer were measured by the four-terminal method according to JIS K7194 (1994). The results are shown in Table 1.
  • the heating stability was evaluated as the ratio (R2 / R1) of the surface resistance (R2) to the surface resistance (R1).
  • the heating stability (R2 / R1) is an evaluation of the amount of change in the resistance value when the crystalline light-transmitting conductive layer is reheated, and the closer the value is to 1, the more stable the heating is. Shows excellent sex. The results are shown in Table 1.
  • the transparent conductive film and the method for manufacturing the transparent conductive film of the present invention include a touch sensor, a dimming element, a photoelectric conversion element, a heat ray control member, an antenna, an electromagnetic wave shielding member, an image display device, and a heater member (light transmitting heater). , And, preferably used in lighting.
  • Transparent conductive film 1 Transparent conductive film 2 Base material layer 3 Light-transmitting conductive layer 4 Transparent base material

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