WO2021215153A1 - Corps stratifié de couche électroconductrice transmettant la lumière - Google Patents

Corps stratifié de couche électroconductrice transmettant la lumière Download PDF

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WO2021215153A1
WO2021215153A1 PCT/JP2021/011157 JP2021011157W WO2021215153A1 WO 2021215153 A1 WO2021215153 A1 WO 2021215153A1 JP 2021011157 W JP2021011157 W JP 2021011157W WO 2021215153 A1 WO2021215153 A1 WO 2021215153A1
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light
layer
transmitting conductive
conductive layer
argon
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PCT/JP2021/011157
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English (en)
Japanese (ja)
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望 藤野
泰介 鴉田
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日東電工株式会社
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Priority to KR1020227030811A priority Critical patent/KR20230004439A/ko
Priority to CN202180029708.8A priority patent/CN115428100A/zh
Priority to JP2021517074A priority patent/JPWO2021215153A1/ja
Publication of WO2021215153A1 publication Critical patent/WO2021215153A1/fr
Priority to JP2022025297A priority patent/JP7372995B2/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
    • 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
    • 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
    • C23C14/0005—Separation of the coating from the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3464—Sputtering using more than one target
    • 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
    • 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; 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
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/52—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

Definitions

  • the present invention relates to a light-transmitting conductive layer laminate.
  • Patent Document 1 a laminated structure including a glass substrate and a transparent conductive film formed on the upper surface thereof and made of ITO mixed with argon or krypton is known (see, for example, Patent Document 1).
  • a resin layer for example, a polymer substrate
  • a resin layer for example, a polymer substrate
  • the transparent conductive film follows it, it is transparent. There is a problem that the conductive film is cracked.
  • the present invention provides a light-transmitting conductive layer laminate having excellent crack resistance.
  • the present invention (2) includes the light-transmitting conductive layer laminate according to (1), which has a first region containing the noble gas and a second region containing argon in order in the thickness direction.
  • the present invention (4) includes the light-transmitting conductive layer laminate according to any one of (1) to (3), wherein the conductive oxide further contains indium and tin.
  • FIG. 5C is a modified example in which argon and a rare gas having an atomic number larger than that of argon are mixed.
  • FIG. 6 is a graph showing the relationship between the amount of oxygen introduced when the amorphous light-transmitting conductive layer is sputtered and formed and the surface resistance of the amorphous light-transmitting conductive layer.
  • 7A-7B are cross-sectional views of another example of the light-transmitting conductive layer laminate of the present invention, FIG. 7A shows a mode in which the light-transmitting conductive layer is laminated on a functional layer, and FIG. 7B shows light. This is a mode in which the permeable conductive layer is laminated on the transparent base film.
  • a light-transmitting conductive film which is an embodiment of the light-transmitting conductive layer laminate of the present invention, will be described with reference to FIG.
  • the light transmissive conductive film 10 is provided for a touch sensor, a dimming 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.
  • the light-transmitting conductive film 10 is an intermediate member for manufacturing them.
  • the light-transmitting conductive film 10 is a layer that can be distributed independently and can be used industrially.
  • the light-transmitting conductive film 10 has a film shape (film) extending in a plane direction orthogonal to the thickness direction.
  • the light-transmitting conductive film 10 includes a resin layer 11 and a light-transmitting conductive layer 1 in order toward one side in the thickness direction.
  • the resin layer 11 forms the other surface of the light-transmitting conductive film 10 in the thickness direction.
  • the resin layer 11 has a film shape extending in the plane direction.
  • the resin layer 11 is a base material layer.
  • the resin layer 11 has flexibility.
  • the resin layer 11 includes a transparent base film 13 and a functional layer 14 in order toward one side in the thickness direction.
  • the resin layer 11 is preferably not adjacent to the glass substrate.
  • the transparent base film 13 has a film shape extending in the plane direction.
  • the transparent base film 13 forms the other surface of the resin layer 11 in the thickness direction.
  • the material of the transparent base film 13 is a polymer.
  • the polymer include olefin resins such as polyethylene, polypropylene and cycloolefin polymer (COP), and polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate and polyethylene naphthalate, for example, polyacrylate and / or polymethacrylate.
  • (Meta) acrylic resins (acrylic resins and / or methacrylic resins) such as, for example, resins such as polycarbonate resins, polyether sulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, and polystyrene resins.
  • resins such as polycarbonate resins, polyether sulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, and polystyrene resins.
  • a polyester resin is preferable, and PET is more preferable.
  • the transparent base film 13 made of the above material has low heat resistance, it may be difficult to heat it to 200 ° C. or higher (described later) for crystallization.
  • the transparent base film 13 made of the above material is made of the above material. According to No. 13, a light-transmitting conductive film 10 having excellent smoothness and heat stability can be obtained.
  • the thickness of the transparent base film 13 is, for example, 1 ⁇ m or more, preferably 10 ⁇ m or more, more preferably 30 ⁇ m or more, and for example, 300 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and further. It is preferably 75 ⁇ m or less.
  • the total light transmittance (JIS K 7375-2008) of the transparent base film 13 is, for example, 60% or more, preferably 80% or more, more preferably 85% or more, and 100% or less.
  • the functional layer 14 forms one surface of the resin layer 11 in the thickness direction.
  • the functional layer 14 is arranged on one side of the transparent base film 13 in the thickness direction. Specifically, the functional layer 14 contacts all of one surface of the transparent base film 13 in the thickness direction.
  • the functional layer 14 extends in the plane direction.
  • the functional layer is a layer containing a resin. Examples of the functional layer 14 include a hard coat layer. In such a case, the resin layer 11 includes the transparent base film 13 and the hard coat layer in order toward one side in the thickness direction. In the following description, a case where the functional layer 14 is a hard coat layer will be described.
  • the hard coat layer is a scratch protection layer for making the light transmissive conductive layer 1 less likely to be scratched.
  • the hard coat layer forms one surface of the resin layer 11 in the thickness direction.
  • the hard coat layer is in contact with all of one surface of the transparent base film 13 in the thickness direction.
  • Examples of the material of the hard coat layer include a cured product of the hard coat composition (acrylic resin, urethane resin, etc.) described in JP-A-2016-179686.
  • the thickness of the hard coat layer is, for example, 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, and for example, 10 ⁇ m or less, preferably 5 ⁇ m or less.
  • the thickness of the resin layer 11 is, for example, 1 ⁇ m or more, preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, still more preferably 30 ⁇ m or more, and for example, 310 ⁇ m or less, preferably 210 ⁇ m or less. It is more preferably 110 ⁇ m or less, still more preferably 80 ⁇ m or less.
  • the total light transmittance (JIS K 7375-2008) of the resin layer 11 is, for example, 60% or more, preferably 80% or more, more preferably 85% or more, and for example, 100% or less.
  • the light-transmitting conductive layer 1 forms one surface of the light-transmitting conductive film 10 in the thickness direction.
  • the light-transmitting conductive layer 1 is supported by the resin layer 11 from the other side in the thickness direction.
  • the light-transmitting conductive layer 1 is in contact with all of one surface of the resin layer 11 in the thickness direction.
  • the light-transmitting conductive layer 1 has a first main surface 2 and a second main surface 3 which is arranged so as to face the first main surface 2 at intervals in the thickness direction.
  • the light-transmitting conductive layer 1 is a single layer extending in the plane direction.
  • the first main surface 2 of the light-transmitting conductive layer 1 comes into contact with one surface of the resin layer 11 in the thickness direction.
  • the second main surface 3 of the light transmissive conductive layer 1 is exposed on one side in the thickness direction.
  • Argon is derived from argon contained in the sputtering gas in the production method described later and is mixed in the conductive oxide. In FIG. 2, argon is drawn as a white circle.
  • Noble gas with an atomic number larger than argon examples include krypton, xenon, and radon. These can be used alone or in combination. Preferably, krypton and xenon are mentioned, and more preferably, krypton (specifically, krypton used alone) is mentioned from the viewpoint of achieving both cost and excellent electrical conductivity.
  • the noble gas having an atomic number larger than that of argon is derived from the noble gas contained in the sputtering gas in the production method described later and is mixed in the conductive oxide. In FIG. 2, a noble gas having an atomic number larger than that of argon is drawn as a black circle.
  • the conductive oxide is a matrix that disperses the above-mentioned argon and a rare gas having an atomic number larger than that of argon.
  • the conductive oxide for example, at least one 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 metalloid can be mentioned.
  • the metal oxide may be further doped with the metal atoms and / or metalloid atoms shown in the above group, if necessary.
  • the ratio of the tin oxide content to the total content of indium oxide (In 2 O 3 ) and tin oxide (SnO 2) in the ITO is, for example, 0.1% by mass or more. It is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and even more preferably 10% by mass or more.
  • the ratio of the number of tin atoms to the number of indium atoms in the ITO used is, for example, 0.001 or more, preferably 0.03 or more, more preferably 0.05 or more, still more preferable.
  • the ratio of the tin oxide content to the total content of indium oxide (In 2 O 3 ) and tin oxide (SnO 2 ) in the ITO used is, for example, 20% by mass or less, preferably 15% by mass or less, more preferably. Is 13% by mass or less, more preferably 12% by mass or less.
  • the ratio of the number of tin atoms to the number of indium atoms in the ITO used is, for example, 0.23 or less, preferably 0.16 or less, more preferably 0.14 or less, still more preferable. Is 0.13 or less.
  • the ratio of the tin oxide content is below the above-mentioned upper limit and / or the ratio of the number of tin atoms to the number of indium atoms is below the above-mentioned upper limit, the light-transmitting conductive layer 1 that is easily crystallized by heating is obtained. be able to.
  • 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, for example, from the abundance ratio of the indium atom and the tin atom thus specified.
  • the abundance ratio of indium atoms and tin atoms in ITO and the above-mentioned content ratio of tin oxide can be judged from the content ratios of indium (In 2 O 3 ) and tin oxide (SnO 2) of the ITO target used at the time of sputter film formation. good.
  • the light-transmitting conductive layer 1 includes a first region 4 containing a rare gas having an atomic number larger than that of argon and a second region 5 containing argon in order in the thickness direction. ..
  • the content ratio of the rare gas having an atomic number larger than that of argon is, for example, 0.0001 atom% or more, preferably 0.001 atom% or more, and for example, 1.0 atom% or less. More preferably 0.7 atom% or less, further preferably 0.5 atom% or less, further preferably 0.3 atom% or less, particularly preferably 0.2 atom% or less, most preferably 0.15 atom% or less. Is.
  • the content ratio of the rare gas having an atomic number larger than that of argon is within the above range, the light-transmitting conductive layer 1 is excellent in crack resistance (particularly, crack resistance in a humid environment).
  • the mixing of argon is allowed in the first region 4.
  • the content R rg1 of the rare gas from the high atomic number argon in the first region 4 is higher than the content ratio R rg2 of the rare gas from the high atomic number argon in the second region 5.
  • R rg1 / R rg2 is, for example, 1 excess, preferably 1.2 or more, more preferably 1.5 or more, and, for example, 10,000 or less.
  • Rare gases having an atomic number higher than that of argon in the first region 4 can be obtained by, for example, Rutherford Backscattering Spectrometry, secondary ion mass spectrometry, laser resonance ionization mass spectrometry, and / or fluorescent X-ray analysis. , But preferably, from the viewpoint of ease of analysis, it is identified by fluorescent X-ray analysis. Details of X-ray fluorescence analysis will be described in Examples. When the Rutherford backscattering analysis is performed on the first region 4 and the light transmissive conductive layer 1 including the first region 4, it cannot be quantified because the noble gas atom content is not equal to or higher than the detection limit value (lower limit value). When the presence of a noble gas atom is identified by performing fluorescent X-ray analysis, it is determined that the light-transmitting conductive layer 1 includes a region having a Kr content ratio of 0.0001 atom% or more.
  • the ratio R1 (thickness ratio) occupied by the first region 4 in the light transmissive conductive layer 1 is, for example, 0.99 or less, preferably 0.95 or less, more preferably 0.9 or less, and further. It is preferably 0.8 or less, particularly preferably 0.7 or less, and for example, 0.01 or more, preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0. .2 or more, especially preferably 0.3 or more.
  • the ratio R1 occupied by the first region 4 is equal to or less than the above upper limit, the light transmissive conductive layer 1 has excellent crack resistance, for example, high temperature (175) after long-term (170 hours) storage at room temperature (24 ° C.).
  • the second region 5 includes the second main surface 3.
  • argon is dispersed with respect to the conductive oxide in the thickness direction and the plane direction.
  • the content ratio of argon is, for example, 0.001 atom% or more, preferably 0.01 atom% or more, and for example, 0.5 atom% or less, preferably 0. It is 4 atom% or less, more preferably 0.3 atom% or less, still more preferably 0.2 atom% or less.
  • the light-transmitting conductive layer 1 is excellent in crack resistance (particularly, crack resistance in a heating environment).
  • the argon content ratio R Ar2 in the second region 5 is higher than the argon content ratio R Ar1 in the first region 4.
  • R Ar2 / R Ar1 is, for example, 1 excess, preferably 1.2 or more, more preferably 1.5 or more, and, for example, 10,000 or less.
  • Argon in the light-transmitting conductive layer 1 is identified (determined to exist) by, for example, Rutherford Backscattering Spectroscopy (RBS), and is also quantified. Details of the Rutherford backscatter analysis method are described in Examples.
  • the light-transmitting conductive layer 1 is, for example, amorphous or crystalline.
  • the crystalline property of the light-transmitting conductive layer 1 is appropriately selected depending on the use and purpose of the light-transmitting conductive film 10.
  • the crystallinity of the light-transmitting conductive layer 1 is determined, for example, by immersing the light-transmitting conductive layer 1 in hydrochloric acid (20 ° C., concentration 5% by mass) for 15 minutes, washing with water and drying, and then performing light-transmitting conductivity. Judgment is made by measuring the resistance between terminals between the terminals 3 with respect to the second main surface 3 of the layer 1 by about 15 mm. In the light-transmitting conductive layer 1 after immersion, washing with water, and drying, when the resistance between terminals (resistance between two terminals) between 15 mm is 10 k ⁇ or less, the light-transmitting conductive layer 1 is crystalline, while the above. When the resistance exceeds 10 k ⁇ , the light-transmitting conductive layer 1 is amorphous.
  • the thickness of the light-transmitting conductive layer 1 is, for example, 5 nm or more, preferably 20 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, and for example, 1000 nm or less, preferably 300 nm. Less than, more preferably 250 nm or less, still more preferably 200 nm or less, still more preferably 160 nm or less, particularly preferably less than 150 nm, most preferably 148 nm or less. When the thickness of the light-transmitting conductive layer 1 is within the above range, the light-transmitting conductive layer 1 is excellent in crack resistance.
  • the ratio of the thickness of the light-transmitting conductive layer 1 to the thickness of the resin layer 11 is, for example, 0.00001 or more, preferably 0.01 or more, more preferably 0.1 or more, and for example, 0. It is 5 or less, preferably 0.25 or less.
  • the specific resistance of the light-transmitting conductive layer 1 is, for example, 5.0 ⁇ 10 -4 ⁇ ⁇ cm or less, preferably 2.5 ⁇ 10. -4 ⁇ ⁇ cm or less, more preferably 2.0 ⁇ 10 -4 ⁇ ⁇ cm or less, still more 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, further 0.5 ⁇ 10 -4 ⁇ ⁇ cm or more, and further 1.0 ⁇ 10 -4 ⁇ ⁇ cm or more.
  • the specific resistance is obtained by multiplying the surface resistance by the thickness.
  • the total content ratio of argon and the rare gas having an atomic number higher than that of argon in the light-transmitting conductive layer 1 is, for example, in the entire thickness direction, for example.
  • 1.2 atom% or less preferably 1.1 atom% or less, more preferably 1.0 atom% or less, still more preferably 0.8 atom% or less, particularly preferably 0.5 atom% or less, still more preferably.
  • It is 0.4 atom% or less, most preferably 0.3 atom% or less, and particularly preferably 0.2 atom% or less.
  • the impurity atom in the light transmissive conductive layer 1 that is, argon and the rare gas having an atomic number larger than that of argon. Since the total content ratio of (and) is small, it is possible to obtain the light-transmitting conductive layer 1 having excellent crack resistance and low specific resistance.
  • a method for manufacturing the light-transmitting conductive film 10 will be described with reference to FIG.
  • a light-transmitting conductive layer 1 is formed on the resin layer 11 by a roll-to-roll method.
  • the resin layer 11 is prepared. Specifically, the hard coat composition is applied to one surface of the transparent base film 13 in the thickness direction and dried, and then the hard coat composition is cured. As a result, the resin layer 11 is prepared in which the transparent base film 13 and the hard coat layer (functional layer 14) are sequentially provided on one side in the thickness direction.
  • the light-transmitting conductive layer 1 is formed into a film by sputtering. Specifically, the light-transmitting conductive layer 1 is formed while the resin layer 11 is conveyed by the sputtering apparatus 30.
  • the sputtering apparatus 30 includes a feeding section 35, a sputtering section 36, and a winding section 37 in this order.
  • the film forming roll 40 includes a cooling device (not shown) configured to cool the film forming roll 40.
  • Examples of the material of the first target 51 include the same materials as those of the above-mentioned conductive oxide.
  • the material of the first target 51 includes a sintered body of a conductive oxide. However, these conductive oxides are not yet mixed with a noble gas having an atomic number larger than that of argon and argon.
  • the first target 51 is configured to apply electric power.
  • a magnet (not shown) is arranged on the opposite side of the film forming roll 40 with respect to the first target 51.
  • the horizontal magnetic field strength on the surface of the first target 51 is, for example, 10 mT or more, preferably 60 mT or more, and for example, 300 mT or less.
  • the first gas supply machine 61 is configured to supply the first sputtering gas to the first film forming chamber 41.
  • the first sputtering gas contains a rare gas having an atomic number larger than that of argon.
  • a rare gas having an atomic number larger than that of argon for example, a rare gas having an atomic number larger than that of argon, and a first mixture containing a reactive gas such as oxygen. Examples include gas.
  • the first mixed gas is mentioned.
  • the second film forming chamber 42 is arranged adjacent to the first film forming chamber 41 in the circumferential direction of the film forming roll 40. As a result, the first film forming chamber 41 and the second film forming chamber 42 are sequentially arranged in the circumferential direction.
  • the second film forming chamber 42 accommodates the second target 52, the second gas supply machine 62, and the discharge port of the second pump 72.
  • the second target 52, the second gas supply machine 62, and the discharge port of the second pump 72 are arranged to face each other with respect to the film forming roll 40 at intervals.
  • Examples of the material of the second target 52 include the same materials as those of the above-mentioned conductive oxide.
  • the material of the second target 52 includes a sintered body of a conductive oxide. However, these conductive oxides are not yet mixed with a noble gas having an atomic number larger than that of argon and argon.
  • the second target 52 is configured to apply electric power.
  • a magnet (not shown) is arranged on the opposite side of the film forming roll 40 with respect to the second target 52.
  • the horizontal magnetic field strength on the surface of the second target 52 is, for example, 10 mT or more, preferably 60 mT or more, and for example, 300 mT or less.
  • the second gas supply machine 62 is configured to supply the second sputtering gas to the second film forming chamber 42.
  • the second sputtering gas include argon, and examples thereof include a second mixed gas containing argon and a reactive gas such as oxygen.
  • a second mixed gas is preferably used. If the second sputtering gas is the second mixed gas, the second gas supply machine 62 includes an argon supply machine 65 and a second oxygen gas supply machine 66, from which argon and oxygen are second. It is supplied to the film forming chamber 42.
  • the take-up unit 37 includes a take-up roll 39 and a discharge port of the take-up side pump 34.
  • the sputtering gas is supplied from the second gas supply machine 62 to the second film forming chamber 42.
  • the pressure of argon (if the sputtering gas is the second mixed gas, the partial pressure of argon) is, for example, 0.02 Pa or more, preferably 0.1 Pa or more, and for example, 1 Pa or less, preferably 0. It is .5 Pa or less.
  • the resin layer 11 is fed from the feeding roll 38.
  • the resin layer 11 moves in order between the first film forming chamber 41 and the second film forming chamber 42 while contacting the surface of the film forming roll 40.
  • the resin layer 11 is cooled by contact with the surface of the film forming roll 40.
  • the amount of the noble gas taken into the first amorphous conductive film 81 is adjusted by the magnetic field strength, the power density of the electric power applied to the first target 51, and / or the pressure in the first film forming chamber 41. Further, the thickness of the first amorphous conductive film 81 is adjusted by the power density of the electric power applied to the first target 51.
  • the amount of the noble gas taken into the second amorphous conductive film 82 is adjusted by the magnetic field strength, the power density of the electric power applied to the second target 52, and / or the pressure in the second film forming chamber 42. Further, the thickness of the second amorphous conductive film 82 is adjusted by the power density of the electric power applied to the second target 52.
  • an amorphous light-transmitting conductive film 10 including the resin layer 11, the first amorphous conductive film 81, and the second amorphous conductive film 82 can be obtained.
  • the light-transmitting conductive layer 1 (amorphous light-transmitting conductive layer 1) is formed on one surface of the resin layer 11 in the thickness direction.
  • the light-transmitting conductive film 10 including the resin layer 11 and the light-transmitting conductive layer 1 is manufactured.
  • the amorphous light-transmitting conductive layer 1 is heated to crystallize the light-transmitting conductive layer 1.
  • the heating temperature is, for example, 80 ° C. or higher, preferably 110 ° C. or higher, more preferably 150 ° C. or higher, and for example, less than 200 ° C., preferably 180 ° C. or lower.
  • the heating time is, for example, 5 minutes or more, preferably 10 minutes or more, more preferably 30 minutes or more, further preferably 1 hour or more, and for example, 5 hours or less, preferably 3 hours or less. be.
  • the total light transmittance (JIS K 7375-2008) of the crystalline light-transmitting conductive film 10 after heating the amorphous light-transmitting conductive layer 1 is, for example, 65% or more, preferably 80%. As mentioned above, it is more preferably 83% or more, and for example, 100% or less, preferably 95% or less.
  • the article includes a light-transmitting conductive film 10 and a member corresponding to each article.
  • 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 resin forming the fixing functional layer includes a known corrosion inhibitor and a migration inhibitor (for example, a material disclosed in Japanese Patent Application Laid-Open No. 2015-0222397) in order to suppress corrosion and migration of the light-transmitting conductive layer 1. Can also be added. Further, 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 resin layer 11 in the light-transmitting conductive film 10 and the member corresponding to each article can be fixed via the fixing functional layer.
  • the light-transmitting conductive layer 1 (including the light-transmitting conductive layer 1 having a pattern shape) is exposed in the light-transmitting conductive film 10. Therefore, the cover layer can be arranged on one surface of the light-transmitting conductive layer 1 in the thickness direction.
  • the cover layer is a layer that covers the light-transmitting conductive layer 1, and can improve the reliability of the light-transmitting conductive layer 1 and suppress functional deterioration due to scratches.
  • the material of 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.
  • the above-mentioned article is excellent in reliability because it includes the above-mentioned light-transmitting conductive film 10. Specifically, since the touch sensor, the light control element, the photoelectric conversion element, the heat ray control member, the antenna, the electromagnetic wave shield member, the image display device, the heater member, and the illumination include the above-mentioned light transmissive conductive film 10. Excellent reliability.
  • the light-transmitting conductive layer 1 is mixed with a rare gas having an atomic number larger than that of argon and argon, the formation of the above-mentioned cracks can be suppressed.
  • Such a touch sensor, a light control element, a photoelectric conversion element, a heat ray control member, an antenna, an electromagnetic wave shield member, a heater member, an image display device, and a heater include the above-mentioned light transmissive conductive film 10 in which cracks are suppressed. Because it is prepared, it has excellent reliability.
  • Modification example In the modified example, 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 first region 4 mixed with a rare gas having an atomic number larger than that of argon includes the first main surface 2 in contact with the resin layer 11.
  • the second region 5 mixed with argon may include the first main surface 2.
  • the second region 5 comes into contact with the resin layer 11.
  • the first region 4 and the second region 5 may be alternately and repeatedly arranged.
  • the first region 4, the second region 5, the first region 4, and the second region 5 are arranged in order toward one side in the thickness direction.
  • the second region 5, the first region 4, the second region 5, and the first region 4 are arranged in order toward one side in the thickness direction.
  • the first region 4 may be further arranged in a configuration in which the first region 4 and the second region 5 are alternately and repeatedly arranged toward one side in the thickness direction.
  • the second region 5 may be further arranged in a configuration in which the second region 5 and the first region 4 are alternately and repeatedly arranged toward one side in the thickness direction. Further, the first region 4, the second region 5, and the first region 4 may be arranged in order in the thickness direction. Further, the second region 5, the first region 4, and the second region 5 may be arranged in order in the thickness direction.
  • argon and a rare gas having an atomic number larger than that of argon may be mixed (uniformly dispersed) without having the first region 4 and the second region 5.
  • a sputtering gas containing both argon and a rare gas having an atomic number larger than that of argon is supplied from the gas supply machine to the film forming chamber. More specifically, the rare gas supply machine 63 supplies both argon and a rare gas having an atomic number larger than that of argon.
  • the amorphous light-transmitting conductive layer 1 is made of a third amorphous conductive film 83.
  • argon and a rare gas having an atomic number larger than that of argon are mixed (uniformly dispersed).
  • the third amorphous conductive film 83 is heated to crystallize it.
  • the light-transmitting conductive layer 1 in the light-transmitting conductive film 10, is in contact with all of one surface of the resin layer 11 in the thickness direction, but the light-transmitting conductive layer 1 is not shown. It may be patterned so that any region remains. That is, there may be a region where the light-transmitting conductive layer 1 does not exist on the resin layer 11. By patterning, it can be suitably used for touch sensors, dimming elements, photoelectric conversion elements and the like.
  • the resin layer 11 can further include other functional layers.
  • the anti-blocking layer 12 arranged on the other surface in the thickness direction of the transparent base film 13 can be provided.
  • the anti-blocking layer 12 imparts blocking resistance to the respective surfaces of the plurality of light-transmitting conductive films 10 that come into contact with each other when the light-transmitting conductive films 10 are laminated in the thickness direction.
  • the resin layer 11 can further provide an easy-adhesion layer between the anti-blocking layer 12 and the transparent base film 13.
  • the resin layer 11 may be provided with an intermediate layer (not shown) made of an inorganic layer on one side of the transparent base film 13.
  • the intermediate layer improves the surface hardness of the resin layer 11, adjusts the optical physical characteristics (specifically, the refractive index) of the light-transmitting conductive film 10, and receives the light-transmitting conductive layer 1 from the resin layer 11. It has the function of relieving stress at an intermediate point.
  • the intermediate layer can be provided at an arbitrary position with respect to the transparent base film 13, the functional layer 14, and the anti-blocking layer 12 with respect to one side in the thickness direction of the light transmissive conductive film 10, and is provided with a plurality of layers. You may.
  • the resin layer 11 includes a transparent base film 13, a functional layer 14, and an intermediate layer in this order toward one side in the thickness direction. Further, the resin layer 11 includes, for example, an intermediate layer, an anti-blocking layer 12, a transparent base film 13, and a functional layer 14 in this 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.
  • the functional layer 14 may be an optical adjustment layer (not shown).
  • the resin layer 11 includes a transparent base film 13 and an optical adjustment layer in this 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 1 and adjusts the optical physical characteristics (specifically, the refractive index) of the light transmissive conductive film 10.
  • the functional layer 14 may be a peeling functional layer (not shown).
  • the resin layer 11 includes a transparent base film 13 and a 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 transparent base film 13. If the resin layer 11 includes a peeling functional layer, the light-transmitting conductive layer 1 can be peeled from the transparent base film 13.
  • the peeled light-transmitting conductive layer 1 can be used, for example, by transferring and bonding to another member constituting the touch sensor.
  • the functional layer 14 may be an easy-adhesion layer (not shown).
  • the resin layer 11 includes a transparent base film 13 and an easy-adhesion layer in order toward one side in the thickness direction.
  • the easy-adhesion layer improves the adhesion between the transparent base film 13 and the light-transmitting conductive layer 1.
  • the functional layer 14 may be a plurality of layers. That is, the functional layer 14 can optionally include 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 resin layer 11 may be provided with the transparent base film 13, the easy-adhesion layer, the hard coat layer, and the optical adjustment layer in order toward one side in the thickness direction, and the resin layer 11 may be provided with the resin layer 11 in order.
  • the transparent base film 13, the peeling functional layer, the hard coat layer and / or the optical adjusting layer may be provided in order toward one side in the thickness direction.
  • the resin layer 11 includes the transparent base film 13, the peeling function layer, the hard coat layer and / or the optical adjustment layer in order toward one side in the thickness direction, the light transmissive conductive film 10 is used.
  • the laminate including the hard coat layer and / or the optical adjustment layer and the light transmissive conductive layer 1 can be peeled off.
  • the resin layer 11 may not include the transparent base film 13 and may consist only of the functional layer 14.
  • the light-transmitting conductive layer laminate 20 does not have a film shape, and has a resin layer 11 (hard coat layer and / or an optical adjustment layer) and a light-transmitting conductive layer 1 in order in the thickness direction.
  • the light-transmitting conductive film 10 has a film shape.
  • the resin layer 11 may not include the functional layer 14 and may consist of only the transparent base film 13. That is, the light-transmitting conductive film 10 has the transparent base film 13 and the light-transmitting conductive layer 1 in order in the thickness direction.
  • the resin layer 11 may be provided with a transparent base material (not shown) containing glass in the functional layer 14. That is, although not shown, the light-transmitting conductive film 10 can include the light-transmitting conductive layer 1, the transparent base film 13, and the glass substrate in order in the thickness direction. At this time, the fixing functional layer is interposed between the glass substrate and the transparent base film 13. That is, the light-transmitting conductive film 10 can be provided with the light-transmitting conductive layer 1, the transparent base film 13, the fixing functional layer (preferably the adhesive layer), and the glass substrate in this order in the thickness direction.
  • 1 is exemplified as a suitable number of the light-transmitting conductive layer 1 in the light-transmitting conductive film 10, but for example, although not shown, it may be 2.
  • each of the two light-transmitting conductive layers 1 is arranged on both sides of the resin layer 11 in the thickness direction. That is, in this modification, the number of light-transmitting conductive layers 1 with respect to one resin layer 11 is preferably 2.
  • Example 1 An ultraviolet curable hard coat composition containing an acrylic resin is applied to one surface in the thickness direction of a transparent base film 13 made of a long PET film (manufactured by Toray Industries, Inc., thickness 50 ⁇ m), and this is irradiated with ultraviolet rays to cure.
  • a hard coat layer which is an example of the functional layer 14 having a thickness of 2 ⁇ m, was formed. As a result, the resin layer 11 including the transparent base film 13 and the hard coat layer was prepared.
  • the resin layer 11 was set in the sputtering apparatus 30. Subsequently, in the sputtering apparatus 30, the feeding side pump 33, the winding side pump 34, the first pump 71, and the second pump 72 are driven to set the ultimate vacuum degree to 0.9 ⁇ 10 -4 Pa. , The resin layer 11 was degassed. Further, the temperature of the film forming roll 40 was set to ⁇ 8 ° C.
  • the materials of the first target 51 and the second target were both sintered bodies of indium oxide and tin oxide. In the sintered body, the ratio of the tin oxide content to the total content of indium oxide and tin oxide was 10% by mass. In the sintered body, the ratio of the number of tin atoms to the number of indium atoms (number of tin atoms / number of indium atoms) is 0.102.
  • the resin layer 11 was conveyed from the feeding portion 35 toward the winding portion 37 along the film forming roll 40.
  • the first film forming chamber 41 krypton was supplied from the rare gas supply machine 63 and oxygen was supplied from the first oxygen gas supply machine 64 while driving the first pump 71.
  • the pressure of the first film forming chamber 41 to 0.2 Pa and sputtering the first target 51 (power supply: DC, horizontal magnetic field strength on the first target: 90 mT)
  • the first amorphous conductivity having a thickness of 66 nm is obtained.
  • a film 81 (first region 4) was formed.
  • the second film forming chamber 42 while driving the second pump 72, argon was supplied from the argon feeder 65, and oxygen was supplied from the second oxygen gas feeder 66.
  • the pressure of the second film forming chamber 42 is 0.4 Pa, and the second target 52 is sputtered (power supply: DC, horizontal magnetic field strength on the second target: 90 mT) to obtain a second amorphous conductor having a thickness of 64 nm.
  • a film 82 (second region 5) was formed.
  • the amount of oxygen introduced from the first oxygen gas supply machine 64 and the second oxygen gas supply machine 66 is the first region X of the surface resistance-oxygen introduction amount curve and is amorphous.
  • the surface resistance of the light transmissive conductive layer 1 was adjusted to 50 ⁇ / ⁇ .
  • the ratio of oxygen gas to the total amount of krypton gas and oxygen gas introduced was about 2.5% of the flow rate.
  • the ratio of oxygen gas to the total amount of argon gas and oxygen gas introduced was about 1.5 flow rate%.
  • the first amorphous conductive film 81 and the second amorphous conductive film 82 were sequentially formed on one side in the thickness direction of the resin layer 11.
  • the resin layer 11 and the amorphous light-transmitting conductive layer 1 were formed into a light-transmitting conductive film 10.
  • Example 2 A second mixed gas ( containing Ar and O 2 ) is supplied to the first film forming chamber 41 so that the pressure of the first film forming chamber 41 is 0.4 Pa, and the second amorphous conductive film 82 having a thickness of 42 nm (the first). After the 2 regions 5) are formed by sputtering, the first mixed gas ( containing Kr and O 2 ) is supplied to the second film forming chamber 42 so that the pressure of the second film forming chamber 42 is 0.2 Pa and the thickness is 75 nm.
  • a light-transmitting conductive film 10 was obtained in the same manner as in Example 1 except that the first amorphous conductive film 81 (first region 4) was formed by sputtering.
  • the light-transmitting conductive film 10 of Example 2 corresponds to the light-transmitting conductive film 10 shown in FIG.
  • Example 3 The thickness of the first amorphous conductive film 81 (first region 4) and the thickness of the second amorphous conductive film 82 (second region 5) are as shown in Table 1, so that the first target A light-transmitting conductive film 10 was obtained in the same manner as in Example 1 except that the power densities of 51 and the second target 52 were adjusted.
  • Example 4 to Example 5 The amount of oxygen introduced from the first oxygen gas supply machine 64 and the second oxygen gas supply machine 66 is the region X of the surface resistance-oxygen introduction amount curve shown in FIG.
  • the surface resistance is adjusted to 65 ⁇ / ⁇ , and the thickness of the first amorphous conductive film 81 (first region 4) and the thickness of the second amorphous conductive film 82 (second region 5) are shown in the table.
  • a light-transmitting conductive film 10 was obtained in the same manner as in Example 1 except that the power densities of the first target 51 and the second target 52 were adjusted so as described in 1.
  • Example 6 A mixed gas of krypton and argon (85% by volume of krypton, 15% by volume of argon) is supplied from the rare gas supply machine 63, oxygen is supplied from the first oxygen gas supply machine 64, and oxygen of the first oxygen gas supply machine 64 is supplied.
  • the introduction amount is the first region X of the surface resistance-oxygen introduction amount curve shown in FIG. 6, and the surface resistance of the amorphous light-transmitting conductive layer 1 is 39 ⁇ / ⁇ (total introduction amount of krypton gas and oxygen gas).
  • the ratio of the oxygen gas to the gas gas is adjusted to be about 2.6% of the flow rate), and by adjusting the power density of the first target 51, the third non-third gas having a thickness of 148 nm is formed in the first film forming chamber 41.
  • the crystalline conductive film 83 was formed and the second amorphous conductive film 82 (second region 5) was not formed in the second film forming chamber 42.
  • a transmissive conductive film 10 was obtained.
  • the light-transmitting conductive film 10 of Example 6 corresponds to the light-transmitting conductive film 10 shown in FIG. 5C.
  • Comparative Example 1 A second mixed gas ( containing Ar and O 2 ) is supplied to each of the first film forming chamber 41 and the second film forming chamber 42, and the pressure of the first film forming chamber 41 and the second film forming chamber 42 is reduced to 0.
  • a light transmissive conductive film 10 was obtained in the same manner as in Example 1 except that the value was changed to 4 Pa.
  • Comparative Example 2 The first mixed gas ( containing Kr and O 2 ) is supplied to each of the first film forming chamber 41 and the second film forming chamber 42, and the pressure of the first film forming chamber 41 and the second film forming chamber 42 is reduced to 0.
  • a light transmissive conductive film 10 was obtained in the same manner as in Example 1 except that the value was changed to 2 Pa.
  • Comparative Example 3 The first mixed gas ( containing Kr and O 2 ) is supplied to each of the first film forming chamber 41 and the second film forming chamber 42, and the pressure of the first film forming chamber 41 and the second film forming chamber 42 is reduced to 0. Except for changing to 2Pa and adjusting the power densities of the first target 51 and the second target 52 so that the thickness of the first amorphous conductive film 81 (first region 4) becomes as shown in Table 1. Obtained a light-transmitting conductive film 10 in the same manner as in Example 4.
  • a cross-section observation sample of the light-transmitting conductive layer 1 of each Example and Comparative Example was prepared by the FIB microsampling method, and then the light-transmissive conductive layer in the cross-section observation sample was prepared by FE-TEM observation (cross-section observation). The thickness of 1 was measured. Details of the device and measurement conditions are as follows.
  • FIB microsampling method FIB device Hitachi FB2200 Acceleration voltage: 10kV
  • the thickness of the second amorphous conductive film 82 (second region 5) of Examples 1 and 3 to 5 was calculated by the following formula.
  • Example 2 Thinth of the first amorphous conductive film of Example 2 and the thickness of the second amorphous conductive film]
  • a sample was collected immediately after the formation of the second amorphous conductive film 82 and not yet the first amorphous conductive film 81 was formed, and the second amorphous conductive film of the sample was collected.
  • the thickness of 82 (second region 5) was determined by FE-TEM observation (cross-sectional observation).
  • the thickness of the first amorphous conductive film 81 (first region 4) of Example 2 was calculated by the following formula.
  • Thickness of the first amorphous conductive film 81 Thickness of the light-transmitting conductive layer 1-Thickness of the second amorphous conductive film 82
  • Example 6 Thin of the third amorphous conductive film of Example 6
  • the thickness of the third amorphous conductive film 83 immediately after sputtering was determined by FE-TEM observation (cross-sectional observation).
  • Comparative Example 1 since the contamination of Kr was not confirmed by the quantitative analysis of Kr using the above-mentioned scanning fluorescent X-ray analyzer, Table 1 shows Examples 1 to 6 and Comparative Examples 2 to 2. The " ⁇ specific detection limit value in the thickness of the light transmissive conductive layer 1 attached to the measurement" described in 3 is not indicated.
  • the light-transmitting conductive film 10 was stored in an environment of 24 ° C. for 170 hours. Then, three light-transmitting conductive films 10 cut into a size of 5 cm ⁇ 50 cm were prepared and heated in a hot air oven at 175 ° C. for 1 hour. As a result, the light-transmitting conductive layer 1 in the light-transmitting conductive film 10 was crystallized. Then, the light-transmitting conductive film 10 was divided into 15 sections having a size of 5 cm ⁇ 10 cm, the surface of the light-transmitting conductive layer 1 in each section was visually observed, and the crack level was evaluated according to the following criteria.
  • the light-transmitting conductive layer laminate of the present invention is used for, for example, a touch sensor, a dimming element, a photoelectric conversion element, a heat ray control member, an antenna, an electromagnetic wave shield member, an image display device, a heater member, and lighting.

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  • Physical Vapour Deposition (AREA)

Abstract

Ce film électroconducteur transmettant la lumière (10) comprend, dans l'ordre dans la direction de l'épaisseur, une couche de résine (11) et une couche électroconductrice transmettant la lumière (1). La couche électroconductrice transmettant la lumière (1) présente une première surface principale (2) et une seconde surface principale (3) qui est disposée en regard d'un côté de direction d'épaisseur de la première surface principale (2) avec un espace interposé entre celles-ci. La première surface principale (1) ou la seconde surface principale (3) entre en contact avec la couche de résine (11). La couche électroconductrice transmettant la lumière (1) présente une couche unique qui s'étend dans la direction de surface. La couche électroconductrice transmettant la lumière (1) comporte un oxyde électroconducteur. L'oxyde électroconducteur contient de l'argon et un gaz rare présentant un nombre atomique supérieur à celui de l'argon.
PCT/JP2021/011157 2020-04-20 2021-03-18 Corps stratifié de couche électroconductrice transmettant la lumière WO2021215153A1 (fr)

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KR1020227030811A KR20230004439A (ko) 2020-04-20 2021-03-18 광투과성 도전층 적층체
CN202180029708.8A CN115428100A (zh) 2020-04-20 2021-03-18 透光性导电层层叠体
JP2021517074A JPWO2021215153A1 (fr) 2020-04-20 2021-03-18
JP2022025297A JP7372995B2 (ja) 2020-04-20 2022-02-22 光透過性導電層積層体の製造方法および光透過性導電層積層体

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CN116348293B (zh) * 2021-08-06 2024-04-02 日东电工株式会社 层叠体

Citations (1)

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JP2000038654A (ja) * 1998-07-21 2000-02-08 Nippon Sheet Glass Co Ltd 透明導電膜付き基板の製造方法、透明導電膜付き基板およびそれを用いた液晶表示素子

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JPH05334924A (ja) * 1992-05-29 1993-12-17 Tonen Corp 透明導電薄膜の製造法
JPH07262829A (ja) 1994-03-25 1995-10-13 Hitachi Ltd 透明導電膜及びその形成方法
JPH1036961A (ja) * 1996-07-22 1998-02-10 Sumitomo Metal Mining Co Ltd スパッタリング法による成膜方法
KR20070030620A (ko) 2005-09-13 2007-03-16 삼성에스디아이 주식회사 전극 증착방법 및 이로써 제조된 유기 발광 표시장치

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
JP2000038654A (ja) * 1998-07-21 2000-02-08 Nippon Sheet Glass Co Ltd 透明導電膜付き基板の製造方法、透明導電膜付き基板およびそれを用いた液晶表示素子

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TW202141531A (zh) 2021-11-01
CN115428100A (zh) 2022-12-02
JP7372995B2 (ja) 2023-11-01
JP2022067102A (ja) 2022-05-02
KR20230004439A (ko) 2023-01-06
JPWO2021215153A1 (fr) 2021-10-28

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