WO2023042849A1 - 透明導電性フィルム - Google Patents

透明導電性フィルム Download PDF

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Publication number
WO2023042849A1
WO2023042849A1 PCT/JP2022/034352 JP2022034352W WO2023042849A1 WO 2023042849 A1 WO2023042849 A1 WO 2023042849A1 JP 2022034352 W JP2022034352 W JP 2022034352W WO 2023042849 A1 WO2023042849 A1 WO 2023042849A1
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Prior art keywords
transparent conductive
conductive layer
layer
film
less
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PCT/JP2022/034352
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English (en)
French (fr)
Japanese (ja)
Inventor
望 藤野
泰介 鴉田
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to CN202280014562.4A priority Critical patent/CN116848595A/zh
Priority to JP2023548482A priority patent/JP7425266B2/ja
Priority to KR1020237023083A priority patent/KR102695635B1/ko
Publication of WO2023042849A1 publication Critical patent/WO2023042849A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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 transparent conductive films.
  • Transparent conductive film that includes a transparent base film made of resin and a transparent conductive layer (transparent conductive layer) in order in the thickness direction.
  • Transparent conductive layers are used, for example, as conductive films for forming transparent electrodes in various devices such as liquid crystal displays, touch panels, and solar cells.
  • the transparent conductive layer is formed, for example, by depositing a conductive oxide on the substrate film by sputtering. Techniques related to such transparent conductive films are described, for example, in Patent Document 1 below.
  • a conventional transparent conductive film is manufactured, for example, as follows. First, an amorphous transparent conductive layer is formed on a substrate film in a film forming chamber of a sputtering film forming apparatus. Next, the transparent conductive layer on the substrate film is heated in a hot air heating oven. This heating converts the transparent conductive layer from amorphous to crystalline (crystallization step). The higher the heating temperature, the higher the crystallinity of the formed crystalline transparent conductive layer and the lower the resistance value of the same layer.
  • the heating temperature in the crystallization process is too high, problems such as dimensional changes and deformation will occur in the resin base film. Therefore, in the crystallization process, it is necessary to heat the transparent conductive layer at a temperature that does not cause such problems (a temperature that is not too high).
  • the resistance value of the transparent conductive layer may rise.
  • An increase in the resistance value of the transparent conductive layer in the transparent conductive film after production is not preferable because it affects device performance.
  • the present invention provides a transparent conductive film suitable for suppressing an increase in the resistance value of the transparent conductive layer due to heating during the device manufacturing process.
  • the present invention [1] is a transparent conductive film comprising a transparent resin substrate and a crystalline transparent conductive layer in this order in the thickness direction, wherein the transparent conductive layer has an atomic number greater than that of argon.
  • the transparent conductive layer containing rare gas atoms has a first resistance value R1 ( ⁇ / ⁇ ) and a second resistance value R2 ( ⁇ / ⁇ ) after heat treatment at 160° C. for 30 minutes. and the ratio of the second resistance value R2 to the first resistance value R1 is 0.650 or more and 0.990 or less.
  • the present invention [2] includes the transparent conductive film according to [1] above, wherein the transparent conductive layer includes an indium-tin composite oxide layer containing less than 10% by mass of tin oxide.
  • the present invention [3] includes the transparent conductive film according to [1] or [2] above, wherein the transparent conductive layer has a thickness of 150 nm or less.
  • the present invention [4] includes the transparent conductive film according to any one of [1] to [3] above, wherein the first resistance value R1 is 220 ⁇ / ⁇ or less.
  • the crystalline transparent conductive layer contains rare gas atoms having an atomic number larger than that of argon, and the transparent conductive layer is heated at 160° C. for 30 minutes.
  • a ratio (R2/R1) of the second resistance value R2 after heat treatment to the first resistance value R1 (before heat treatment) is 0.650 or more and 0.990 or less.
  • the second resistance value R2 after heat treatment 160° C., 30 minutes
  • Such a transparent conductive film is suitable for suppressing an increase in the resistance value of the transparent conductive layer due to heating during the device manufacturing process.
  • FIG. 3A represents a process of preparing a resin film
  • FIG. 3B represents a process of forming a functional layer on the resin film
  • FIG. 3C represents a process of forming a transparent conductive layer on the functional layer
  • FIG. 3D represents the step of crystallizing the transparent conductive layer.
  • the transparent conductive film shown in FIG. 1 it represents the case where the transparent conductive layer is patterned.
  • a transparent conductive film X as one embodiment of the transparent conductive film of the present invention comprises a transparent resin substrate 10 and a transparent conductive layer 20 in the thickness direction D in this order.
  • the transparent conductive film X has a sheet shape extending in a direction perpendicular to the thickness direction D (plane direction).
  • the transparent conductive film X is one element provided in a touch sensor device, a light control device, a photoelectric conversion device, a heat ray control member, an antenna member, an electromagnetic wave shield member, a heater member, a lighting device, an image display device, and the like.
  • the transparent resin base material 10 includes a resin film 11 and a functional layer 12 in this order in the thickness direction D in this embodiment.
  • the resin film 11 is a base material that secures the strength of the transparent conductive film X. Moreover, the resin film 11 is a transparent resin film having flexibility.
  • materials for the resin film 11 include polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyethersulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, and polystyrene resin.
  • Polyester resins include, for example, polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate.
  • Polyolefin resins include, for example, polyethylene, polypropylene, and cycloolefin polymers.
  • acrylic resins include polymethacrylate.
  • polyester resin is preferably used, and PET is more preferably used, for example, from the viewpoint of transparency and strength.
  • the functional layer 12 side surface of the resin film 11 may be subjected to a surface modification treatment.
  • Surface modification treatments include, for example, corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.
  • the thickness of the resin film 11 is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 30 ⁇ m or more.
  • the thickness of the resin film 11 is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, still more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, and particularly preferably, from the viewpoint of ensuring handleability of the resin film 11 in a roll-to-roll system. is 75 ⁇ m or less.
  • the total light transmittance (JIS K 7375-2008) of the resin film 11 is preferably 60% or higher, more preferably 80% or higher, and even more preferably 85% or higher. Such a configuration is applicable when the transparent conductive film X is provided in a touch sensor device, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shield member, a heater member, a lighting device, an image display device, or the like. It is suitable for securing the transparency required for the transparent conductive film X.
  • the total light transmittance of the resin film 11 is, for example, 100% or less.
  • the functional layer 12 is arranged on one side of the resin film 11 in the thickness direction D. In this embodiment, the functional layer 12 contacts the resin film 11 . Further, in the present embodiment, the functional layer 12 is a hard coat layer that makes it difficult for scratches to form on the exposed surface (the upper surface in FIG. 1) of the transparent conductive layer 20 .
  • the hard coat layer is a cured product of a curable resin composition.
  • the curable resin composition contains a curable resin.
  • curable resins include polyester resins, acrylic urethane resins, acrylic resins (excluding acrylic urethane resins), urethane resins (excluding acrylic urethane resins), amide resins, silicone resins, epoxy resins, and melamine resins. . These curable resins may be used alone, or two or more of them may be used in combination. From the viewpoint of ensuring high hardness of the hard coat layer, the curable resin is preferably at least one selected from the group consisting of acrylic urethane resins and acrylic resins.
  • curable resins include ultraviolet curable resins and thermosetting resins.
  • an ultraviolet curable resin is preferable from the viewpoint of improving the production efficiency of the transparent conductive film X because it can be cured without heating to a high temperature.
  • the curable resin composition may contain particles.
  • Particles include, for example, inorganic oxide particles and organic particles.
  • Materials for inorganic oxide particles include, for example, silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide.
  • Materials for the organic particles include, for example, polymethylmethacrylate, polystyrene, polyurethane, acrylic-styrene copolymers, benzoguanamine, melamine, and polycarbonate.
  • the surface of the functional layer 12 on the side of the transparent conductive layer 20 may be subjected to surface modification treatment.
  • Surface modification treatments include, for example, corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.
  • the thickness of the functional layer 12 as the hard coat layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and still more preferably 1 ⁇ m or more, from the viewpoint of expressing sufficient scratch resistance in the transparent conductive layer 20 .
  • the thickness of the functional layer 12 as a hard coat layer is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less, from the viewpoint of ensuring the transparency of the functional layer 12 .
  • the thickness of the transparent resin substrate 10 is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, even more preferably 15 ⁇ m or more, and particularly preferably 30 ⁇ m or more.
  • the thickness of the transparent resin substrate 10 is preferably 520 ⁇ m or less, more preferably 320 ⁇ m or less, still more preferably 220 ⁇ m or less, even more preferably 120 ⁇ m or less, and particularly preferably 80 ⁇ m or less.
  • the total light transmittance (JIS K 7375-2008) of the transparent resin substrate 10 is preferably 60% or higher, more preferably 80% or higher, and even more preferably 85% or higher. Such a configuration is applicable when the transparent conductive film X is provided in a touch sensor device, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shield member, a heater member, a lighting device, an image display device, or the like. It is suitable for securing the transparency required for the transparent conductive film X.
  • the total light transmittance of the transparent resin substrate 10 is, for example, 100% or less.
  • the transparent conductive layer 20 is arranged on one side in the thickness direction D of the transparent resin substrate 10 .
  • the transparent conductive layer 20 is in contact with the transparent resin substrate 10 .
  • the transparent conductive layer 20 is a crystalline film having both optical transparency and electrical conductivity.
  • Such a transparent conductive layer 20 is made of, for example, a conductive oxide. The fact that the transparent conductive layer 20 is a crystalline film is suitable for suppressing large fluctuations in the resistance value of the transparent conductive layer 20 due to subsequent heating.
  • the transparent conductive layer (the transparent conductive layer 20 on the transparent resin substrate 10 in the transparent conductive film X) is a crystalline film
  • TEM transmission electron microscope
  • a microtome knife was set at an extremely acute angle with respect to the transparent conductive layer, The knife cuts the transparent conductive layer so as to be substantially parallel to the exposed surface of the transparent conductive layer. Thereby, a transparent conductive layer sample as a sample for planar observation can be obtained.
  • the transparent conductive layer is a crystalline film
  • FE-TEM field emission transmission electron microscope
  • the transparent conductive layer is a crystalline film
  • the transparent conductive layer is immersed in hydrochloric acid having a concentration of 5% by mass at 20° C. for 15 minutes.
  • the transparent conductive layer is washed with water and then dried.
  • the resistance between a pair of terminals separated by a distance of 15 mm between the terminals resistance. In this measurement, when the resistance between terminals is 10 k ⁇ or less, it can be determined that the transparent conductive layer is a crystalline film.
  • conductive oxides include indium-containing conductive oxides and antimony-containing conductive oxides.
  • Indium-containing conductive oxides include, for example, indium tin composite oxide (ITO), indium zinc composite oxide (IZO), indium gallium composite oxide (IGO), and indium gallium zinc composite oxide (IGZO). be done.
  • Antimony-containing conductive oxides include, for example, antimony-tin composite oxide (ATO). From the viewpoint of realizing high transparency and good electrical conductivity, as the conductive oxide, an indium-containing conductive oxide is preferably used, and ITO is more preferably used. This ITO may contain metals or metalloids other than In and Sn in amounts less than the respective contents of In and Sn.
  • the transparent conductive layer 20 (crystalline) preferably includes an indium-tin composite oxide layer (first ITO layer) containing less than 10% by mass of tin oxide.
  • the tin oxide ratio in the ITO layer is specifically 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 forming the same layer.
  • the transparent conductive layer 20 including the first ITO layer is crystallized by heating the transparent conductive layer 20' after the amorphous transparent conductive layer 20' including the first ITO layer is formed. It is formed by Including the first ITO layer in the transparent conductive layer 20 is suitable for forming an amorphous transparent conductive layer (transparent conductive layer 20' described later) that suppresses an increase in resistance value due to heating after thermal crystallization. .
  • the proportion of tin oxide in the first ITO layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more, from the viewpoint of ensuring the durability of the transparent conductive layer 20. , more preferably 1.5% by mass or more, particularly preferably 2% by mass or more.
  • the proportion of tin oxide in the first ITO layer is determined from the standpoint of ease of formation of an amorphous transparent conductive layer in the later-described sputtering film formation, and an increase in the resistance value of the transparent conductive layer 20 due to heating after heat crystallization. From the viewpoint of suppressing the is 4% by mass or less.
  • the tin oxide ratio in ITO can be identified, for example, as follows. First, by X-ray Photoelectron Spectroscopy, the abundance ratio of indium atoms (In) and tin atoms (Sn) in ITO as an object to be measured is determined. The ratio of the number of Sn atoms to the number of In atoms in ITO is obtained from the abundance ratios of In and Sn in ITO. This gives the percentage of tin oxide in ITO. Further, the tin oxide ratio in ITO can also be specified from the tin oxide (SnO 2 ) content ratio of the ITO target used for sputtering film formation.
  • the transparent conductive layer 20 may include layers other than the first ITO layer (with a tin oxide content of less than 10% by mass).
  • Other layers include, for example, an ITO layer (second ITO layer) having a tin oxide ratio of 10% by mass or more, and a layer formed of a conductive oxide other than ITO.
  • the other layer is preferably the second ITO layer.
  • the tin oxide ratio of the second ITO layer (tin oxide ratio of 10% by mass or more) is preferably 11% by mass or more, more preferably 12% by mass, from the viewpoint of reducing the resistance value of the transparent conductive layer 20 after thermal crystallization. % or more, more preferably 13 mass % or more. From the viewpoint of ensuring the crystallinity of the transparent conductive layer 20 after heating, the proportion of tin oxide in the second ITO layer is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. be.
  • FIG. 2 illustrates a case where the transparent conductive layer 20 is composed of two layers, a first layer 21 and a second layer 22, as an example of a case where the transparent conductive layer 20 is composed of a plurality of layers including a first ITO layer. show.
  • the first layer 21 or the second layer 22 is the first ITO layer.
  • the second layer 22 is preferably the first ITO layer.
  • the thickness of the transparent conductive layer 20 is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more.
  • the thickness of the transparent conductive layer 20 is preferably 300 nm or less, more preferably 150 nm or less, even more preferably 120 nm or less, still more preferably 100 nm or less, and particularly preferably, from the viewpoint of suppressing cracking of the transparent conductive layer 20 due to heating. is 80 nm or less.
  • the ratio of the thickness of the second layer 22 to the total thickness of the first layer 21 and the second layer 22 is the lowest of the transparent conductive layer 20 . From the viewpoint of resistance, it is preferably 1% or more, more preferably 5% or more, and still more preferably 7% or more. In addition, the ratio of the thickness of the second layer 22 to the total thickness of the first layer 21 and the second layer 22 is preferably 99% or less from the viewpoint of ensuring high crystallinity in the transparent conductive layer 20 after heating. , more preferably 95% or less, still more preferably 90% or less, still more preferably 60% or less, and particularly preferably 50% or less.
  • the transparent conductive layer 20 contains rare gas atoms (atoms E) having an atomic number greater than that of argon.
  • noble gas atoms include krypton (Kr) and xenon (Xe), preferably Kr.
  • the transparent conductive layer 20 may contain argon (Ar).
  • the rare gas atoms in the transparent conductive layer 20 are derived from rare gas atoms used as a sputtering gas in the sputtering method for forming the transparent conductive layer 20, which will be described later.
  • the transparent conductive layer 20 is a film (sputtered film) formed by a sputtering method.
  • the transparent conductive layer 20 containing atoms E is formed by forming an amorphous transparent conductive layer 20′ containing atoms E and then crystallizing the transparent conductive layer 20′ by heating. be.
  • the content of the atom E in the transparent conductive layer 20 is suitable for forming an amorphous transparent conductive layer (transparent conductive layer 20' described later) that suppresses an increase in resistance value due to heating after thermal crystallization.
  • Methods for identifying whether or not the transparent conductive layer 20 contains atoms E include, for example, fluorescent X-ray analysis and Rutherford Backscattering Spectrometry (RBS).
  • the content of atoms E such as Kr in the transparent conductive layer 20 is preferably 1 atomic % or less, more preferably 0.5 atomic % or less, still more preferably 0.3 atomic % or less, in the entire thickness direction D, and particularly Preferably, it is 0.2 atomic % or less.
  • Such a configuration is suitable for achieving good crystal growth when the amorphous transparent conductive layer 20 ′ is crystallized by heating, and is therefore suitable for obtaining the transparent conductive layer 20 with low resistance.
  • the content of atoms E in the transparent conductive layer 20 is preferably 0.0001 atomic % or more in the entire thickness direction D.
  • Methods for identifying the content of rare gas atoms in the transparent conductive layer 20 include, for example, fluorescent X-ray analysis and Rutherford backscattering spectroscopy (RBS).
  • the transparent conductive layer 20 may include a layer containing the atom E (atom E containing layer) and a layer not containing the atom E (atom E non-containing layer).
  • the atom E-free layer is, for example, a layer formed by sputter deposition using argon as the sputtering gas.
  • the atoms E are contained in the first layer 21 or the second layer 22 . From the viewpoint of ensuring the crystallinity of the transparent conductive layer 20 after heating, the first layer 21 preferably contains atoms E.
  • the ratio of the thickness of the atom E-containing layer to the total thickness of the atom E-containing layer and the atom E-free layer is From the viewpoint of increasing the crystallinity of the transparent conductive layer 20 and improving the transmittance, it is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more, still more preferably 30% or more, and particularly preferably 40%. That's it. From the viewpoint of reducing the dimensional shrinkage of the transparent conductive layer 20 after heating, the same ratio is preferably 99% or less, more preferably 90% or less, even more preferably 80% or less, even more preferably 70% or less, and particularly preferably 60% or less.
  • the transparent conductive layer 20 has a first resistance value R1 ( ⁇ / ⁇ ) and a second resistance value R2 ( ⁇ / ⁇ ) after heat treatment under heating conditions of 160° C. and 30 minutes.
  • the resistance values R1 and R2 are each represented by surface resistivity. Surface resistivity can be measured by the four-probe method according to JIS K7194 (1994). Specifically, the method of measuring the resistance values R1 and R2 is as described later with regard to the examples.
  • the ratio R2/R1 of the second resistance value R2 to the first resistance value R1 is 0.990 or less, preferably 0.950 or less, more preferably 0.950 or less, from the viewpoint of suppressing an increase in resistance value due to subsequent heating of the transparent conductive layer 20. is 0.900 or less, more preferably 0.880 or less.
  • the ratio R2/R1 is 0.650 or more, preferably 0.700 or more, and more preferably 0.800 or more.
  • the difference R1-R2 between the first resistance value R1 and the second resistance value R2 is preferably 1.5 ⁇ / ⁇ or more from the viewpoint of suppressing an increase in the resistance value of the transparent conductive layer 20 due to subsequent heating. It is more preferably 3 ⁇ / ⁇ or more, still more preferably 4 ⁇ / ⁇ or more, still more preferably 5 ⁇ / ⁇ or more, and particularly preferably 6 ⁇ / ⁇ or more.
  • the difference R1-R2 is preferably 10 ⁇ / ⁇ or less, more preferably 9.5 ⁇ / ⁇ or less, and still more preferably 9 ⁇ / ⁇ . Below, it is particularly preferably 8 ⁇ / ⁇ or less.
  • the first resistance value R1 is preferably 240 ⁇ / ⁇ or less, more preferably 220 ⁇ / ⁇ or less, even more preferably 200 ⁇ / ⁇ or less, and even more preferably 180 ⁇ / ⁇ or less. It is more preferably 160 ⁇ / ⁇ or less, and particularly preferably 150 ⁇ / ⁇ or less.
  • the first resistance value R1 is, for example, 1 ⁇ / ⁇ or more.
  • the first resistance value R1 can be controlled, for example, by adjusting various conditions when the transparent conductive layer 20 is formed by sputtering (the same applies to the second resistance value R2).
  • the conditions include, for example, the temperature of the base (transparent resin substrate 10 in this embodiment) on which the transparent conductive layer 20 is formed, the amount of oxygen introduced into the film formation chamber, the pressure in the film formation chamber, and the target of horizontal magnetic field strength.
  • the second resistance value R2 is preferably 240 ⁇ / ⁇ or less, more preferably 220 ⁇ / ⁇ or less, even more preferably 200 ⁇ / ⁇ or less, and even more preferably 180 ⁇ / ⁇ or less. It is more preferably 160 ⁇ / ⁇ or less, and particularly preferably 150 ⁇ / ⁇ or less.
  • the second resistance value R2 is, for example, 1 ⁇ / ⁇ or more.
  • the total light transmittance (JIS K 7375-2008) of the transparent conductive layer 20 is preferably 60% or higher, more preferably 80% or higher, still more preferably 85% or higher. Such a configuration is suitable for ensuring transparency in the transparent conductive layer 20 . Moreover, the total light transmittance of the transparent conductive layer 20 is, for example, 100% or less.
  • the transparent conductive film X is produced, for example, as follows.
  • a resin film 11 is prepared.
  • the functional layer 12 is formed on one surface of the resin film 11 in the thickness direction D.
  • a transparent resin substrate 10 is produced by forming the functional layer 12 on the resin film 11 .
  • the above-mentioned functional layer 12 as a hard coat layer can be formed by applying a curable resin composition on the resin film 11 to form a coating film, and then curing the coating film.
  • the curable resin composition contains an ultraviolet curable resin
  • the coating film is cured by ultraviolet irradiation.
  • the curable resin composition contains a thermosetting resin
  • the coating is cured by heating.
  • the exposed surface of the functional layer 12 formed on the resin film 11 is subjected to surface modification treatment as necessary.
  • argon gas for example, is used as an inert gas.
  • the discharge power in the plasma treatment is, for example, 10 W or more and, for example, 5000 W or less.
  • an amorphous transparent conductive layer 20' is formed on the transparent resin substrate 10 (transparent conductive layer forming step). Specifically, a sputtering method is used to form a film of material on the functional layer 12 of the transparent resin substrate 10 to form an amorphous transparent conductive layer 20 ′.
  • the transparent conductive layer 20' is an amorphous film having both light transmittance and conductivity (the transparent conductive layer 20' is converted into the crystalline transparent conductive layer 20 by heating in the crystallization step described later. ).
  • the sputtering method it is preferable to use a sputtering film forming apparatus that can carry out the film forming process by a roll-to-roll method.
  • a sputtering film forming apparatus that can carry out the film forming process by a roll-to-roll method.
  • the long transparent resin substrate 10 is run from a supply roll provided in the apparatus to a take-up roll, and the transparent A material is deposited on the resin base material 10 to form the transparent conductive layer 20'.
  • a sputtering film forming apparatus having one film forming chamber may be used, or a sputtering film forming apparatus having a plurality of film forming chambers arranged in order along the running path of the transparent resin substrate 10 may be used.
  • a film apparatus may be used (when forming the transparent conductive layer 20′ including the first layer 21 and the second layer 22 described above, a sputtering film forming apparatus having two or more film forming chambers is used. do).
  • a sputtering gas in the sputtering method, while introducing a sputtering gas (inert gas) under vacuum conditions into a film forming chamber provided in a sputtering film forming apparatus, a negative voltage is applied to a target placed on a cathode in the film forming chamber. is applied. As a result, glow discharge is generated to ionize the gas atoms, the gas ions collide with the target surface at high speed, the target material is ejected from the target surface, and the ejected target material is deposited on the transparent resin substrate 10.
  • the target material for example, the sintered body of the conductive oxide described above with regard to the transparent conductive layer 20 is used.
  • the sputtering gas include rare gases.
  • Noble gases include, for example, argon and krypton.
  • the sputtering gas may be a mixed gas of multiple rare gases.
  • the sputtering method is preferably a reactive sputtering method.
  • oxygen as a reactive gas is introduced into the deposition chamber in addition to the sputtering gas.
  • the ratio of the introduction amount of oxygen to the total introduction amount of the sputtering gas and oxygen introduced into the deposition chamber is, for example, 0.01 flow % or more and, for example, 15 flow % or less.
  • the sputtering film forming apparatus includes 1 or
  • the gas introduced into the two or more deposition chambers contains atoms E as sputtering gas and oxygen as reactive gas.
  • Atoms E include Kr and Xe, preferably Kr, as described above.
  • the sputtering gas may contain an inert gas other than the atoms E. Examples of inert gases other than atoms E include Ar.
  • the sputtering gas contains an inert gas other than atoms E, the content is preferably 80% by volume or less, more preferably 50% by volume or less.
  • the gas introduced into the film formation chamber for forming the atom E-containing layer is sputtering It contains atoms E as gas and oxygen as reactive gas.
  • the sputtering gas may contain an inert gas other than the atoms E.
  • the type and content of the inert gas other than the atom E are the same as those described above for the inert gas other than the atom E in the first case.
  • the gas introduced into the deposition chamber for forming the layer not containing atom E contains inert gas other than atom E as sputtering gas and oxygen as reactive gas. Examples of inert gases other than atoms E include Ar.
  • the atmospheric pressure in the film formation chamber during film formation by the sputtering method is, for example, 0.02 Pa or more and, for example, 1 Pa or less.
  • the temperature of the transparent resin substrate 10 during sputtering film formation is, for example, 180° C. or lower.
  • the temperature of the transparent resin substrate 10 during sputtering film formation is preferably set to It is 20° C. or lower, more preferably 10° C. or lower, still more preferably 5° C. or lower, still more preferably 0° C. or lower, and particularly preferably -5° C. or lower.
  • the temperature is, for example, -50°C or higher, -20°C or higher, or -10°C or higher.
  • the power supply for applying voltage to the target includes, for example, a DC power supply, an AC power supply, an MF power supply, and an RF power supply.
  • a DC power supply and an RF power supply may be used together.
  • the absolute value of the discharge voltage during sputtering film formation is, for example, 50 V or higher and, for example, 500 V or lower.
  • the amorphous transparent conductive layer 20' is converted into the crystalline transparent conductive layer 20 by heating under vacuum (crystallization step).
  • a vacuum heating device with a contact heating unit is used.
  • Contact heating units include, for example, heated rolls and heated blocks.
  • a vacuum heating apparatus equipped with a heating roll is preferable for carrying out the crystallization process by the roll-to-roll method. That is, in this step, it is preferable to heat the transparent conductive layer 20' on the transparent resin substrate 10 by bringing it into contact with a heating roll in a vacuum heating device.
  • Contact heating with a heating roll is suitable for efficiently crystallizing the transparent conductive layer 20' under vacuum.
  • the heating temperature is preferably 120°C or higher, more preferably 140°C or higher, and even more preferably 160°C or higher, from the viewpoint of ensuring a high crystallization rate.
  • the heating temperature is preferably less than 200° C., more preferably 180° C. or less, and even more preferably 170° C. or less, from the viewpoint of suppressing the influence of heating on the transparent resin substrate 10 .
  • the heating time is preferably 10 seconds or longer, preferably 30 seconds or longer, and more preferably 45 seconds or longer. From the viewpoint of shortening the tact time in this step, the heating time is preferably 60 minutes or less, more preferably 30 minutes or less, even more preferably 10 minutes or less, and particularly preferably 5 minutes or less.
  • the series of processes from the transparent conductive layer forming step to the crystallization step described above are carried out on one continuous line while the work film is run in a roll-to-roll manner. More preferably, the work film is never exposed to the atmosphere during the process in one continuous line.
  • the transparent conductive film X is manufactured as described above.
  • the transparent conductive layer 20 in the transparent conductive film X may be patterned as schematically shown in FIG. By etching the transparent conductive layer 20 through a predetermined etching mask, the transparent conductive layer 20 can be patterned. The patterning of the transparent conductive layer 20 may be performed before the crystallization process described above or after the crystallization process. The patterned transparent conductive layer 20 functions, for example, as a wiring pattern.
  • the crystalline transparent conductive layer 20 contains rare gas atoms having an atomic number greater than that of argon.
  • the fact that the transparent conductive layer 20 is a crystalline film is suitable for suppressing large fluctuations in the resistance value of the transparent conductive layer 20 due to subsequent heating.
  • the transparent conductive layer 20 containing rare gas atoms having an atomic number greater than that of argon is suitable for forming an amorphous transparent conductive layer 20' that suppresses an increase in resistance value due to heating after thermal crystallization. .
  • the first resistance value R1 (before heat treatment) is , preferably 0.650 or more, preferably 0.70 or more, more preferably 0.80 or more, and preferably 0.990 or less, more preferably 0.950 or less, further preferably 0.900 or less , and particularly preferably 0.880 or less. That is, in the transparent conductive film, the second resistance value R2 after heat treatment (160° C., 30 minutes) is moderately smaller than the first resistance value R1 before heat treatment.
  • the transparent conductive film as described above is suitable for suppressing an increase in the resistance value of the transparent conductive layer due to heating during the device manufacturing process.
  • the functional layer 12 may be an adhesion improving layer for achieving high adhesion of the transparent conductive layer 20 to the transparent resin substrate 10 .
  • the configuration in which the functional layer 12 is an adhesion improving layer is suitable for ensuring adhesion between the transparent resin substrate 10 and the transparent conductive layer 20 .
  • the functional layer 12 may be a refractive index adjusting layer (index-matching layer) for adjusting the reflectance of the surface (one side in the thickness direction D) of the transparent resin substrate 10 .
  • the configuration in which the functional layer 12 is a refractive index adjusting layer is suitable for making the pattern shape of the transparent conductive layer 20 less visible when the transparent conductive layer 20 on the transparent resin substrate 10 is patterned.
  • the functional layer 12 may be a peeling functional layer for practically peeling the transparent conductive layer 20 from the transparent resin substrate 10 .
  • the configuration in which the functional layer 12 is a peeling functional layer is suitable for peeling the transparent conductive layer 20 from the transparent resin substrate 10 and transferring the transparent conductive layer 20 to another member.
  • the functional layer 12 may be a composite layer in which a plurality of layers are arranged in the thickness direction D.
  • the composite layer preferably includes two or more layers selected from the group consisting of a hard coat layer, an adhesion improving layer, a refractive index adjusting layer, and a release functional layer.
  • Such a configuration is suitable for compositely expressing the above-described functions of each selected layer in the functional layer 12 .
  • the functional layer 12 includes an adhesion improving layer, a hard coat layer, and a refractive index adjusting layer on the resin film 11 toward one side in the thickness direction D in this order.
  • the functional layer 12 includes, on the resin film 11, a release functional layer, a hard coat layer, and a refractive index adjusting layer in this order toward one side in the thickness direction D.
  • the transparent conductive film X is used in a state where it is fixed to an article and the transparent conductive layer 20 is patterned as necessary.
  • the transparent conductive film X is attached to an article via, for example, an adhesive functional layer.
  • Articles include, for example, elements, members, and devices. That is, examples of articles with a transparent conductive film include elements with a transparent conductive film, members with a transparent conductive film, and devices with a transparent conductive film.
  • Devices include, for example, light control devices and photoelectric conversion devices.
  • Examples of the light control device include a current-driven light control device and an electric field drive light control device.
  • Current-driven light control devices include, for example, electrochromic (EC) light control devices.
  • Examples of electric field-driven light control devices include PDLC (polymer dispersed liquid crystal) light control devices, PNLC (polymer network liquid crystal) light control devices, and SPD (suspended particle device) light control devices.
  • Examples of photoelectric conversion elements include solar cells. Solar cells include, for example, organic thin-film solar cells and dye-sensitized solar cells.
  • Examples of the member include an electromagnetic wave shield member, a heat ray control member, a heater member, and an antenna member.
  • Devices include, for example, touch sensor devices, lighting devices, and image display devices.
  • fixation functional layer examples include an adhesive layer and an adhesive layer.
  • a material for the fixing function layer any material can be used without particular limitation as long as it is transparent and exhibits a fixing function.
  • the fixation functional layer is preferably made of resin.
  • resins include acrylic resins, silicone resins, polyester resins, polyurethane resins, polyamide resins, polyvinyl ether resins, vinyl acetate/vinyl chloride copolymers, modified polyolefin resins, epoxy resins, fluorine resins, natural rubbers, and synthetic rubbers. be done.
  • an acrylic resin is preferable because it exhibits adhesive properties such as cohesiveness, adhesiveness, and moderate wettability, is excellent in transparency, and is excellent in weather resistance and heat resistance.
  • the fixing functional layer may contain a corrosion inhibitor to suppress corrosion of the transparent conductive layer 20 .
  • the fixing functional layer may contain a migration inhibitor (for example, the material disclosed in JP-A-2015-022397) in order to suppress migration of the transparent conductive layer 20 .
  • the fixing functional layer may contain an ultraviolet absorber in order to suppress deterioration of the article when it is used outdoors. Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxalic acid anilide compounds, cyanoacrylate compounds, and triazine compounds.
  • the transparent conductive layer 20 (including the transparent conductive layer 20 after patterning) in the transparent conductive film X is exposed.
  • a cover layer may be arranged on the exposed surface of the transparent conductive layer 20 .
  • the cover layer is a layer that covers the transparent conductive layer 20 , and can improve the reliability of the transparent conductive layer 20 and suppress functional deterioration due to damage to the transparent conductive layer 20 .
  • Such a cover layer is preferably made of a dielectric material, more preferably a composite material of a resin and an inorganic material. Examples of the resin include the resins described above for the fixing functional layer.
  • Inorganic materials include, for example, inorganic oxides and fluorides.
  • Inorganic oxides include, for example, silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide, and calcium oxide.
  • fluorides include magnesium fluoride.
  • the cover layer may contain the above-described corrosion inhibitor, migration inhibitor, and ultraviolet absorber.
  • Example 1 An ultraviolet curable resin containing an acrylic resin was applied to one surface of a long polyethylene terephthalate (PET) film (thickness: 50 ⁇ m, manufactured by Toray Industries, Inc.) as a transparent resin film to form a coating film. Next, the coating film was cured by ultraviolet irradiation to form a hard coat layer (thickness: 2 ⁇ m). In this manner, a transparent resin base material including a resin film and a hard coat (HC) layer as a functional layer was produced.
  • PET polyethylene terephthalate
  • HC hard coat
  • an amorphous transparent conductive layer was formed on the HC layer of the transparent resin substrate by a reactive sputtering method (transparent conductive layer forming step).
  • a roll-to-roll type sputtering deposition apparatus DC magnetron sputtering deposition apparatus
  • the apparatus includes a first film-forming chamber and a second film-forming chamber in which the film-forming process can be performed while the work film is run in a roll-to-roll manner.
  • the first sputtering film formation in the first film formation chamber and the second sputtering film formation in the second film formation chamber were sequentially performed.
  • a first layer (thickness: 11 nm) was formed on the transparent resin substrate.
  • a second layer (thickness 11 nm) was formed on the first layer.
  • the conditions for each sputtering film formation in this example are as follows.
  • the sputtering deposition apparatus (first deposition chamber, second deposition chamber) is evacuated until the ultimate vacuum in the first deposition chamber reaches 0.9 ⁇ 10 -4 Pa.
  • krypton as a sputtering gas and oxygen as a reactive gas were introduced into the first film forming chamber, and the pressure inside the first film forming chamber was set to 0.2 Pa.
  • the ratio of the introduced amount of oxygen to the total introduced amount of krypton and oxygen introduced into the first deposition chamber was about 1.8 flow rate %.
  • a first sintered body of indium oxide and tin oxide (with a tin oxide concentration of 10% by mass) was used as a target.
  • a DC power supply was used as a power supply for applying voltage to the target.
  • the horizontal magnetic field strength on the target was set to 90 mT.
  • the film formation temperature (the temperature of the transparent resin base material on which the transparent conductive layer is laminated) was -5°C.
  • krypton as a sputtering gas and oxygen as a reactive gas are introduced into the second film forming chamber.
  • the ratio of the introduced amount of oxygen to the total introduced amount of krypton and oxygen introduced into the second film forming chamber was about 1.8 flow rate %.
  • a second sintered body of indium oxide and tin oxide (with a tin oxide concentration of 3% by mass) was used as a target.
  • a DC power supply was used as a power supply for applying voltage to the target.
  • the horizontal magnetic field strength on the target was set to 90 mT.
  • the film formation temperature was -5°C.
  • the transparent conductive layer on the transparent resin substrate was heated by being brought into contact with a heating roll in a vacuum heating device and crystallized (crystallization process).
  • the heating temperature was set to 160° C.
  • the heating time was set to 1 minute
  • the transparent conductive layer was heated and crystallized under vacuum.
  • the transparent conductive film of Example 1 was produced as described above.
  • the transparent conductive layer (thickness: 22 nm) of the transparent conductive film of Example 1 consisted of a first layer of ITO (percentage of tin oxide: 10% by mass, thickness: 11 nm) and a second layer of ITO (percentage of tin oxide: 3% by mass). , thickness 11 nm) in order from the transparent resin substrate side and is crystalline (the ratio of the thickness of the first layer to the thickness of the transparent conductive layer is 50%, and the thickness of the second layer is The thickness percentage is 50%).
  • Example 2 A transparent conductive film of Example 2 was produced in the same manner as the transparent conductive film of Example 1, except for the following.
  • a first layer (amorphous) with a thickness of 22 nm is formed in the first sputtering film formation in the transparent conductive layer forming step, and a second sintered body (tin oxide concentration is 10% by mass) is used as a target in the second sputtering film formation. ) was used to form a second layer (amorphous) with a thickness of 22 nm.
  • the transparent conductive layer of the transparent conductive film of Example 2 is made of an ITO film (tin oxide concentration: 10% by mass, thickness: 44 nm) and is crystalline.
  • Example 3 A transparent conductive film of Example 3 was produced in the same manner as the transparent conductive film of Example 1, except for the following.
  • a first layer (amorphous) having a thickness of 22 nm is formed in the first sputtering film formation in the transparent conductive layer forming step, and in the second sputtering film formation, argon is used as the sputtering gas, and the second sintered body ( A tin oxide concentration of 10% by mass) was used to form a second layer (amorphous) with a thickness of 22 nm.
  • the transparent conductive layer of the transparent conductive film of Example 3 consisted of a krypton-containing first layer (tin oxide concentration: 10% by mass, thickness: 22 nm) and an argon-containing second layer (tin oxide concentration: 10% by mass, thickness: 22 nm) and is crystalline.
  • Comparative Example 1 A transparent conductive film of Comparative Example 1 was produced in the same manner as the transparent conductive film of Example 1, except for the following. Argon was used as a sputtering gas in the first sputtering film formation and the second sputtering film formation in the transparent conductive layer forming step. In the crystallization process, the transparent conductive layer on the transparent resin substrate was heated in a hot air heating oven. The heating temperature was 160° C., and the heating time was 1 hour. In this step, the transparent conductive layer was heated and crystallized in the atmosphere.
  • Comparative Example 2 A transparent conductive film of Comparative Example 2 was produced in the same manner as the transparent conductive film of Example 1, except for the following. Argon was used as a sputtering gas in the first sputtering film formation and the second sputtering film formation in the transparent conductive layer forming step.
  • Comparative Example 3 A transparent conductive film of Comparative Example 3 was produced in the same manner as the transparent conductive film of Example 1 except for the following. In the crystallization process, the transparent conductive layer on the transparent resin substrate was heated in a hot air heating oven. The heating temperature was 160° C., and the heating time was 1 hour. In this step, the transparent conductive layer was heated and crystallized in the atmosphere.
  • Comparative Example 4 A transparent conductive film of Comparative Example 4 was produced in the same manner as the transparent conductive film of Example 1 except for the following. Argon was used as a sputtering gas in the first sputtering film formation and the second sputtering film formation in the transparent conductive layer forming step. A first layer (amorphous) with a thickness of 22 nm is formed in the first sputtering film formation, and a second sintered body (tin oxide concentration is 10% by mass) is used as a target in the second sputtering film formation, and the thickness A second layer (amorphous) of 22 nm was formed.
  • Argon was used as a sputtering gas in the first sputtering film formation and the second sputtering film formation in the transparent conductive layer forming step.
  • a first layer (amorphous) with a thickness of 22 nm is formed in the first sputtering film formation
  • a second sintered body titanium oxide concentration is 10% by mass
  • ⁇ Thickness of transparent conductive layer> The thickness of the transparent conductive layer of each transparent conductive film in Examples 1-3 and Comparative Examples 1-4 was measured by observation with a field emission transmission electron microscope (FE-TEM). Specifically, first, samples for cross-sectional observation of each transparent conductive layer in Examples 1 to 3 and Comparative Examples 1 to 4 were prepared by the FIB microsampling method. In the FIB microsampling method, an FIB device (product name "FB2200", manufactured by Hitachi) was used with an acceleration voltage of 10 kV. Next, the cross section of the transparent conductive layer in the sample for cross section observation was observed by FE-TEM, and the thickness of the transparent conductive layer was measured in the observed image. In the same observation, an FE-TEM apparatus (product name "JEM-2800", manufactured by JEOL) was used, and the acceleration voltage was set to 200 kV.
  • FE-TEM apparatus product name "JEM-2800", manufactured by JEOL
  • the thickness of the first layer of the transparent conductive layer in Examples 1 and 3 and Comparative Examples 1 to 3 was obtained by preparing a sample for cross-sectional observation from the intermediate product before forming the second layer on the first layer. , was measured by FE-TEM observation of the sample.
  • the thickness of the second layer of each transparent conductive layer in Examples 1 and 3 and Comparative Examples 1 to 3 was the total thickness of each transparent conductive layer in Examples 1 and 3 and Comparative Examples 1 to 3 to the thickness of the first layer. I asked for it after subtracting it.
  • an FE-TEM device product name “JEM-2800”, manufactured by JEOL
  • JEM-2800 manufactured by JEOL
  • the accelerating voltage was 200 kV.
  • the transparent conductive layers in Examples 1 to 3 and Comparative Examples 1 to 4 it was confirmed that crystal grains grew over the entire region in the plane direction and thickness direction of the same layer (plane direction/thickness direction confirmed to be crystalline across all directions).
  • the transparent conductive layers in Comparative Examples 2 and 4 it was confirmed that there were regions in which crystal grains did not grow in the plane direction and thickness direction of the same layer (in the plane direction and thickness direction).
  • the first resistance value R1 surface resistivity before heat treatment
  • the transparent conductive film was heat-treated in a hot air heating oven. In the heat treatment, the heating temperature was 160° C. and the heating time was 30 minutes.
  • the second resistance value R2 surface resistivity after heat treatment
  • the ratio (R2/R1) of the second resistance value R2 to the first resistance value R1 was obtained. The values are shown in Table 1. Table 1 also shows the difference R1-R2 between the first resistance value R1 and the second resistance value R2.
  • each transparent conductive layer in Examples 1 to 3 and Comparative Example 3 contained Kr atoms.
  • a scanning fluorescent X-ray analyzer (trade name "ZSX PrimusIV", manufactured by Rigaku)
  • the fluorescent X-ray analysis measurement was repeated five times under the following measurement conditions, and the average value of each scanning angle was calculated. and an X-ray spectrum was created.
  • Kr atoms were contained in the transparent conductive layer by confirming that a peak appeared in the vicinity of the scanning angle of 28.2° in the prepared X-ray spectrum.
  • each transparent conductive layer in Examples 1 to 3 and Comparative Example 3 contained Kr atoms, and that each transparent conductive layer in Comparative Examples 1, 2, and 4 did not contain Kr. bottom.
  • the transparent conductive film of the present invention can be used, for example, as a supply material for transparent conductive films for transparent electrodes in various devices such as liquid crystal displays, touch panels, and solar cells.

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JPH05334924A (ja) * 1992-05-29 1993-12-17 Tonen Corp 透明導電薄膜の製造法
WO2014112535A1 (ja) * 2013-01-16 2014-07-24 日東電工株式会社 透明導電フィルムおよびその製造方法
JP2018078090A (ja) * 2016-10-31 2018-05-17 日東電工株式会社 透明導電性フィルム及びそれを用いたタッチパネル

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JPH01100260A (ja) * 1987-10-14 1989-04-18 Daicel Chem Ind Ltd 透明導電性フイルム積層体の製造方法
JPWO2015072321A1 (ja) * 2013-11-14 2017-03-16 旭硝子株式会社 透明導電性積層体およびタッチパネル
JP6066154B2 (ja) 2014-05-20 2017-01-25 日東電工株式会社 透明導電性フィルムの製造方法

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Publication number Priority date Publication date Assignee Title
JPH05334924A (ja) * 1992-05-29 1993-12-17 Tonen Corp 透明導電薄膜の製造法
WO2014112535A1 (ja) * 2013-01-16 2014-07-24 日東電工株式会社 透明導電フィルムおよびその製造方法
JP2018078090A (ja) * 2016-10-31 2018-05-17 日東電工株式会社 透明導電性フィルム及びそれを用いたタッチパネル

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