Transparent conductive film and method for producing the same

Abstract

To provide a transparent conductive film excellent in heat stability, and a manufacturing method of the transparent conductive film.SOLUTION: A transparent conductive film 1 sequentially includes a substrate layer 2 and a light transmissive conductive layer 3. The substrate layer 2 includes a resin layer. The light transmissive conductive layer 3 includes a krypton atom and no argon atom. The light transmissive conductive layer 3 is 40 nm thick or more. The light transmissive conductive layer 3 has a peak in a vicinity of 28.2° in X-ray spectrums measured by a scanning fluorescence X-ray spectrometer. The light transmissive conductive layer 3 is crystalline and includes a crystal grain of 200 nm or larger grain diameter.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a transparent conductive film and a method for producing the transparent conductive film. [Background technology]

[0002] BACKGROUND ART In recent years, optical films such as transparent conductive films have been known to be used in optical applications such as touch panels.

[0003] As such a transparent conductive film, a transparent conductive film has been proposed that has a film substrate and a polycrystalline layer of indium tin oxide formed on the film substrate (see, for example, Patent Document 1).

[0004] Such a transparent conductive film can be obtained by forming an amorphous layer of indium tin oxide on the surface of a film substrate by sputtering in the presence of argon gas, and then heating the amorphous layer to crystallize it. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-103067 Summary of the Invention [Problem to be solved by the invention]

[0006] On the other hand, such a polycrystalline layer (crystalline) may be heated again. For example, a heating process may be required when forming components required for producing a touch sensor, a photoelectric conversion element, or the like on a transparent conductive film. A more specific example is a process for forming wiring for the touch sensor by applying a metal-containing paste to the polycrystalline layer and heating it when producing a touch sensor. In such cases, it is required to suppress changes in the resistance value of the polycrystalline layer before and after heating (excellent thermal stability).

[0007] A polycrystalline layer with excellent thermal stability can be achieved, for example, by using an inorganic substrate such as a glass substrate and setting the substrate temperature at a high temperature (e.g., 230°C or higher) when forming an indium tin oxide layer (transparent conductive layer) by sputtering. However, film substrates (polymer films) have poor heat resistance and are subject to significant dimensional deformation due to heat, so the substrate temperature cannot be set at a high temperature (the substrate temperature is usually set to less than 200°C, preferably 180°C or lower). For this reason, conventional techniques, including Patent Document 1, have not been able to achieve a transparent conductive film with sufficiently excellent thermal stability.

[0008] The present invention provides a transparent conductive film having excellent heat stability and a method for producing the transparent conductive film. [Means for solving the problem]

[0009] The present invention [1] is a transparent conductive film comprising, in order, a substrate layer and a light-transmitting conductive layer, the substrate layer including a resin layer, and the light-transmitting conductive layer including krypton atoms and / or xenon atoms.

[0010] The present invention [2] includes the transparent conductive film according to the above [1], wherein the thickness of the light-transmitting conductive layer is 60 nm or more and 100 nm or less.

[0011] The present invention [3] includes the transparent conductive film according to the above [1] or [2], in which the light-transmitting conductive layer is crystalline and contains crystal grains having a grain size of 35 nm or more.

[0012] The present invention [4] includes the transparent conductive film according to any one of the above [1] to [3], wherein the light-transmitting conductive layer contains an indium tin composite oxide.

[0013] The present invention [5] includes the transparent conductive film according to any one of the above [1] to [4], wherein the light-transmitting conductive layer has a patterned shape.

[0014] The present invention [6] is a method for producing a transparent conductive film, characterized in that a light-transmitting conductive layer is disposed on a substrate layer by a sputtering method in the presence of krypton and / or xenon, using a material constituting the light-transmitting conductive layer as a target, and the substrate layer includes a resin layer. [Effects of the Invention]

[0015] In the method for producing a transparent conductive film of the present invention, a light-transmitting conductive layer is disposed on a substrate layer by a sputtering method in the presence of krypton and / or xenon, using a material constituting the light-transmitting conductive layer as a target.

[0016] When the light-transmitting conductive layer is disposed by sputtering, a sputtering gas is taken into the light-transmitting conductive layer.

[0017] In this method, krypton atoms and / or xenon atoms, which have a larger atomic weight than argon, are used as the sputtering gas instead of argon, which makes it possible to prevent the sputtering gas (krypton atoms and / or xenon atoms) from being incorporated into the light-transmitting conductive layer.

[0018] This makes it possible to produce a transparent conductive film with excellent heat stability.

[0019] Therefore, the transparent conductive film of the present invention has excellent heat stability. [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 is a schematic diagram showing one embodiment of the transparent conductive film of the present invention. [Figure 2] FIG. 2 is a schematic diagram showing one embodiment of the method for producing a transparent conductive film of the present invention, in which FIG. 2A shows the first step of preparing a substrate layer, FIG. 2B shows the first step of arranging an amorphous light-transmitting conductive layer on one surface of the substrate layer in the thickness direction by sputtering, and FIG. 2C shows the step of heating the amorphous light-transmitting conductive layer to form a crystalline light-transmitting conductive layer. [Figure 3] FIG. 3 is a graph showing the relationship between the amount of oxygen gas introduced when disposing the amorphous light-transmitting conductive layer in the first step and the resistance value of the amorphous light-transmitting conductive layer. [Figure 4] FIG. 4 is a schematic diagram showing an embodiment in which the light-transmitting conductive layer of the transparent conductive film shown in FIG. 1 is patterned. [Figure 5] FIG. 5 is a schematic diagram showing a modified example of the transparent conductive film (wherein the substrate layer does not include a transparent substrate and is made of only a functional layer). DETAILED DESCRIPTION OF THE INVENTION

[0021] 1. Transparent conductive film The transparent conductive film 1 has a film shape (including a sheet shape) with a predetermined thickness, extends in a plane direction perpendicular to the thickness direction, and has a flat upper surface and a flat lower surface.

[0022] The transparent conductive film 1 is a component included in touch sensors, light control elements, photoelectric conversion elements, heat ray control members, antennas, electromagnetic wave shielding members, image display devices, heater members (light-transmitting heaters), lighting, and the like, which will be described later, and is an intermediate component for producing these products. The transparent conductive film 1 is a device that can be distributed independently and is industrially applicable.

[0023] 1, the transparent conductive film 1 includes a base layer 2 and a light-transmitting conductive layer 3, arranged in this order toward one side in the thickness direction. More specifically, the transparent conductive film 1 includes a base layer 2 and a light-transmitting conductive layer 3 disposed on the upper surface (one side in the thickness direction) of the base layer 2. Preferably, the transparent conductive film 1 includes only the base layer 2 and the light-transmitting conductive layer 3.

[0024] The transparent conductive film 1 has a thickness of, for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less, and for example, 1 μm or more, preferably 10 μm or more.

[0025] 2.Base material layer The substrate layer 2 is a transparent substrate for ensuring the mechanical strength of the transparent conductive film 1 .

[0026] The base layer 2 has a film shape and is disposed on the entire lower surface of the light-transmitting conductive layer 3 so as to be in contact with the lower surface of the light-transmitting conductive layer 3.

[0027] The substrate layer 2 includes a transparent substrate 4 as a resin layer and a functional layer 5 .

[0028] Specifically, the base layer 2 includes a transparent base material 4 and a functional layer 5, which are arranged in this order toward one side in the thickness direction. Specifically, the base layer 2 includes a transparent base material 4 and a functional layer 5 that is disposed on one surface of the transparent base material 4 in the thickness direction.

[0029] The transparent substrate 4 has a film shape.

[0030] The transparent substrate 4 is made of, for example, a polymer film, which allows the transparent conductive film 1 to be produced with excellent production efficiency.

[0031] Furthermore, when the transparent substrate 4 is made of a polymer film, the transparent conductive film 1 (crystalline light-transmitting conductive layer 3) may be reheated in order to provide dimensional stability to the transparent conductive film 1, but this transparent conductive film 1 has excellent heat stability.

[0032] Examples of materials for the transparent substrate 4 include olefin resins such as polyethylene, polypropylene, and cycloolefin polymer; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; (meth)acrylic resins (acrylic resins and / or methacrylic resins) such as polymethacrylate; and polycarbonate resins, melamine resins, and polystyrene resins. Preferred examples include olefin resins, polyester resins, (meth)acrylic resins, polycarbonate resins, and melamine resins. More preferred examples include polyester resins, and even more preferred examples include polyethylene terephthalate (PET). Transparent substrates 4 made of the above materials have low heat resistance and cannot be used in heating processes at temperatures above 200°C (specifically, the second process described below). However, such transparent substrates 4 can provide transparent conductive films 1 that are smooth and have excellent heat stability.

[0033] The transparent substrate 4 has transparency. Specifically, the total light transmittance (JIS K 7375-2008) of the transparent substrate 4 is, for example, 60% or more, preferably 80% or more, and more preferably 85% or more.

[0034] The thickness of the transparent substrate 4 is, for example, 1 μm or more, preferably 10 μm or more, preferably 30 μm or more, and for example, 300 μm or less, preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 60 μm or less.

[0035] The functional layer 5 is disposed on one surface of the transparent substrate 4 in the thickness direction.

[0036] The functional layer 5 has a film shape.

[0037] The functional layer 5 may be, for example, a hard coat layer.

[0038] In such a case, the substrate layer 2 includes the transparent substrate 4 and the hard coat layer in this order toward one side in the thickness direction.

[0039] In the following description, the case where the functional layer 5 is a hard coat layer will be described.

[0040] The hard coat layer is an abrasion protection layer that makes the transparent conductive film 1 less susceptible to scratches.

[0041] The material of the hard coat layer is, for example, a hard coat composition, such as the mixture described in JP-A-2016-179686. The mixture contains, for example, a resin (binder resin) such as an acrylic resin or a urethane resin.

[0042] The hard coat layer has a thickness of, for example, 0.1 μm or more, and for example, 10 μm or less, preferably 5 μm or less.

[0043] The number of base layers 2 in the transparent conductive film 1 is not particularly limited, but is preferably one. 3.Light transparent conductive layer The light-transmitting conductive layer 3 is a transparent layer that exhibits excellent conductivity.

[0044] The light-transmitting conductive layer 3 has a film shape and is disposed on the entire upper surface (one surface in the thickness direction) of the base layer 2 (hard coat layer) so as to be in contact with the one surface in the thickness direction of the base layer 2.

[0045] Examples of materials for the light-transmitting conductive layer 3 include metal oxides containing at least one metal and / or metalloid selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. If necessary, the metal oxides may be further doped with metal atoms listed in the above group.

[0046] Specific examples of the light-transmitting conductive layer 3 include indium-containing oxides such as indium tin oxide (ITO), indium gallium oxide (IGO), indium zinc oxide (IZO), and indium gallium zinc oxide (IGZO), and antimony-containing oxides such as antimony tin oxide (ATO), and preferably indium-containing oxides, and more preferably indium tin oxide (ITO).

[0047] When the light-transmitting conductive layer 3 contains an indium tin composite oxide, the specific resistance can be reduced.

[0048] When ITO is used as the material for the light-transmitting conductive layer 3, the tin oxide content is, relative to the total amount of tin oxide and indium oxide, for example, 0.5 mass% or more, preferably 3 mass% or more, more preferably 5 mass% or more, even more preferably 8 mass% or more, particularly preferably 9 mass% or more, and for example, 20 mass% or less, preferably 15 mass% or less, more preferably 12 mass% or less.

[0049] When the content of tin oxide is equal to or greater than the above-mentioned lower limit, the resistance is reduced. When the content of tin oxide is equal to or less than the above-mentioned upper limit, the light-transmitting conductive layer 3 has excellent heat stability.

[0050] Furthermore, the light-transmitting conductive layer 3 may include a region where the proportion of tin oxide is 8% by mass or more. When the light-transmitting conductive layer 3 includes a region where the proportion of tin oxide is 8% by mass or more, the surface resistance value can be reduced.

[0051] For example, the light-transmitting conductive layer 3 includes a first region 11, which is an example of a region having a tin oxide content of 8% by mass or more, and a second region 12, which has a tin oxide content lower than that of the first region 11. Specifically, the light-transmitting conductive layer 3 includes, in order, a layered first region 11 and a layered second region 12 disposed on one surface of the first region 11 in the thickness direction. The boundary between the first region 11 and the second region 12 is not observed by observation with a measuring device and is therefore allowed to be unclear. The light-transmitting conductive layer 3 may have a concentration gradient in which the tin oxide concentration gradually increases from one surface to the other surface in the thickness direction. When the light-transmitting conductive layer 3 includes the second region 12 in addition to the first region 11, a desired crystallization rate can be obtained by adjusting the ratio of the regions.

[0052] The proportion of tin oxide in the first region 11 is preferably 9% by mass or more, and more preferably 10% by mass or more and 20% by mass or less.

[0053] The ratio of the thickness of the first region 11 to the thickness of the light-transmitting conductive layer 3 is, for example, more than 50%, preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, and is, for example, 99% or less, preferably 97% or less.

[0054] If the thickness ratio of the first region 11 is equal to or greater than the above-mentioned lower limit, the ratio of tin oxide in the light-transmitting conductive layer 3 can be increased, and therefore the surface resistance value can be sufficiently reduced.

[0055] The proportion of tin oxide in the second region 12 is, for example, less than 8 mass%, preferably 7 mass% or less, more preferably 5 mass% or less, and even more preferably 4 mass% or less, and for example, 1 mass% or more, preferably 2 mass% or more, and more preferably 3 mass% or more.

[0056] The ratio of the thickness of the second region 12 to the thickness of the light-transmitting conductive layer 3 is, for example, 1% or more, preferably 3% or more, and for example, 50% or less, preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less.

[0057] The ratio of the proportion of tin oxide in the first region 11 to the proportion of tin oxide in the second region 12 (proportion of tin oxide in the first region 11 / proportion of tin oxide in the second region 12) is, for example, 1.5 or more, preferably 2 or more, more preferably 2.5 or more, and for example, 5 or less, preferably 4 or less.

[0058] The tin oxide concentrations in the light-transmitting conductive layer 3, the first region 11, and the second region 12 are measured by X-ray photoelectron spectroscopy. Alternatively, the tin oxide content can be estimated from the (known) components of the target used when forming the amorphous light-transmitting conductive layer 3 by sputtering.

[0059] Furthermore, the light-transmitting conductive layer 3 contains a small amount of sputtering gas (krypton atoms and / or xenon atoms), which will be described in detail later.

[0060] The content of sputtering gas (krypton atoms and / or xenon atoms) in the light-transmitting conductive layer 3 is, for example, 1.0 atomic % or less, preferably 0.5 atomic % or less, more preferably 0.2 atomic % or less, even more preferably 0.1 atomic % or less, and particularly preferably less than 0.1 atomic %.

[0061] The lower limit of the content is the proportion corresponding to when the presence of krypton atoms and / or xenon atoms can be confirmed by a fluorescent X-ray analyzer, and is at least 0.0001 atomic % or more.

[0062] The light-transmitting conductive layer 3 is crystalline or amorphous.

[0063] If the light-transmitting conductive layer 3 is crystalline, the resistivity can be reduced.

[0064] The crystallinity of the light-transmitting conductive layer 3 can be determined, for example, by immersing the transparent conductive film 1 in hydrochloric acid (20°C, concentration 5% by mass) for 15 minutes, followed by rinsing with water and drying, and then measuring the resistance between terminals about 15 mm from the surface on the side of the light-transmitting conductive layer 3. If the resistance between terminals 15 mm in the transparent conductive film 1 after immersion, rinsing with water, and drying is 10 kΩ or less, the light-transmitting conductive layer 3 is crystalline, and if the resistance exceeds 10 kΩ, the light-transmitting conductive layer 3 is amorphous.

[0065] The light-transmitting conductive layer 3 is transparent. Specifically, the total light transmittance (JIS K 7375-2008) of the light-transmitting conductive layer 3 is, for example, 60% or more, preferably 80% or more, and more preferably 85% or more.

[0066] The thickness of the light-transmitting conductive layer 3 is, for example, 10 nm or more, preferably 20 nm or more, more preferably 40 nm or more, even more preferably 50 nm or more, and particularly preferably 60 nm or more, and for example, 1000 nm or less, preferably less than 300 nm, more preferably 250 nm or less, even more preferably 180 nm or less, particularly preferably less than 150 nm, and particularly preferably 140 nm or less.

[0067] When the thickness of the light-transmitting conductive layer 3 is equal to or greater than the above lower limit, the heat stability of the transparent conductive film 1 can be further improved.

[0068] Furthermore, when the thickness of the light-transmitting conductive layer 3 is equal to or less than the above upper limit, the heat stability of the transparent conductive film 1 can be further improved.

[0069] The thickness of the light-transmitting conductive layer 3 can be measured by observing the cross section of the transparent conductive film 1 using, for example, a transmission electron microscope.

[0070] The resistivity of the light-transmitting conductive layer 3 is, for example, 5.0×10 -4Ω·cm or less, preferably 2.5×10 -4 Ω·cm or less, preferably 2.4×10 -4 Ω·cm or less, more preferably 2.2×10 -4 Ω·cm or less, particularly preferably 2.0×10 -4 Ω·cm or less, particularly preferably 1.8×10 -4 Ω cm or less, and for example, 0.1×10 -4 Ω·cm or more, preferably 0.5×10 -4 Ω·cm or more, more preferably 1.0×10 -4 Ω·cm or more, more preferably 1.01×10 -4 Ω·cm or more.

[0071] The resistivity can be measured by the four-terminal method in accordance with JIS K7194.

[0072] The surface resistance of the light-transmitting conductive layer 3 is, for example, 200 Ω / □ or less, preferably 80 Ω / □ or less, more preferably 60 Ω / □ or less, even more preferably 50 Ω / □ or less, particularly preferably 30 Ω / □ or less, and most preferably 20 Ω / □ or less, and is usually greater than 0 Ω / □ and greater than 1 Ω / □.

[0073] The surface resistance value can be measured by a four-terminal method in accordance with JIS K7194.

[0074] The number of light-transmitting conductive layers 3 in the transparent conductive film 1 is not particularly limited, and is preferably 1. Specifically, the number of light-transmitting conductive layers 3 per base layer 2 is preferably 1. 4. Transparent conductive film manufacturing method Next, a method for producing the transparent conductive film 1, particularly a method for producing the transparent conductive film 1 in which the light-transmitting conductive layer 3 is amorphous, will be described with reference to FIG.

[0075] The method for producing the transparent conductive film 1 (when the light-transmitting conductive layer 3 is amorphous) includes a first step of disposing the amorphous light-transmitting conductive layer 3 on one surface in the thickness direction of the substrate layer 2 by sputtering in the presence of krypton and / or xenon using a material that constitutes the light-transmitting conductive layer 3 as a target. In this production method, each layer is disposed in order, for example, by a roll-to-roll method.

[0076] In the first step, as shown in FIG. 2A, first, a base layer 2 is prepared.

[0077] Specifically, a diluted solution of the hard coat composition is applied to one surface in the thickness direction of the transparent substrate 4, dried, and then cured by ultraviolet light, thereby forming a hard coat layer (functional layer 5) on one surface in the thickness direction of the transparent substrate 4.

[0078] In this way, the base material layer 2 is prepared.

[0079] Next, as shown in FIG. 2B, an amorphous light-transmitting conductive layer 3 is disposed on one surface of the base layer 2 in the thickness direction by sputtering.

[0080] Specifically, in a sputtering device, one thickness-wise surface of the substrate layer 2 is placed facing a target made of the material of the light-transmitting conductive layer 3, and the target material is sputtered in the presence of krypton gas and / or xenon gas (preferably, krypton gas alone or xenon gas alone).

[0081] A magnet is disposed on the opposite side of the target from the substrate layer 2. The horizontal magnetic field strength on the target surface is, for example, 10 mT or more, preferably 60 mT or more, and is, for example, 300 mT or less. By disposing the magnet and setting the horizontal magnetic field strength on the target surface within the above range, the amount of impurities in the light-transmitting conductive layer 3 can be reduced, and a light-transmitting conductive layer 3 with low resistivity and excellent thermal stability can be produced.

[0082] The temperature of the substrate layer 2 when forming the light-transmitting conductive layer 3 by sputtering is not particularly limited, but the substrate layer 2 is preferably cooled. Specifically, the temperature of the substrate layer 2 is, for example, 15°C or lower, more preferably 10°C or lower, even more preferably 5°C or lower, and particularly preferably 0°C or lower, and is, for example, −50°C or higher, preferably −30°C or higher, and more preferably −20°C or higher. If the temperature is below the above range, the substrate layer 2 can be cooled during sputtering, which reduces outgassing (water and organic solvents) from the substrate layer 2 and reduces impurity components in the light-transmitting conductive layer 3. This allows for a light-transmitting conductive layer 3 with low resistivity and excellent thermal stability to be obtained. If the temperature is above the above range, deterioration of the physical properties of the substrate layer 2 can be suppressed.

[0083] The partial pressure of the krypton gas and / or xenon gas in the sputtering apparatus is, for example, 0.1 Pa or more, preferably 0.3 Pa or more, and for example, 10 Pa or less, preferably 5 Pa or less, more preferably 1 Pa or less.

[0084] Furthermore, when sputtering the target material, a reactive gas such as oxygen may be present in addition to the krypton gas and / or xenon gas.

[0085] As shown in Fig. 3, the amount of reactive gas introduced can be estimated based on the surface resistance of the amorphous light-transmitting conductive layer 3. More specifically, the film quality (surface resistance) of the amorphous light-transmitting conductive layer 3 changes depending on the amount of reactive gas introduced into the amorphous light-transmitting conductive layer 3, and therefore the amount of reactive gas introduced can be adjusted depending on the target surface resistance of the amorphous light-transmitting conductive layer 3. In order to obtain a crystalline light-transmitting conductive layer 3 by heating the amorphous light-transmitting conductive layer 3, it is preferable to obtain an amorphous light-transmitting conductive layer 3 by adjusting the amount of reactive gas introduced within the range of region X in Fig. 3.

[0086] Although there is no limitation on the amount of reactive gas introduced, when the reactive gas is oxygen, the ratio of the amount of oxygen introduced to the total amount of krypton gas and / or xenon gas and oxygen introduced is, for example, 0.01% by flow rate or more, and, for example, less than 5% by mass, preferably less than 4.5% by mass. If the amount of oxygen introduced is within the above range, it can be reliably set within the range of region X in FIG. 3.

[0087] Specifically, the reactive gas is introduced so that the surface resistance of the amorphous light-transmitting conductive layer 3 is, for example, 300 Ω / □ or less, preferably 200 Ω / □ or less, more preferably 150 Ω / □ or less, and for example, 30 Ω / □ or more, preferably 70 Ω / □ or more.

[0088] The pressure in the sputtering apparatus is the total pressure of the partial pressure of the krypton gas and / or xenon gas and the partial pressure of the reactive gas.

[0089] When ITO is used as the material for the light-transmitting conductive layer 3, a first target and a second target having different tin oxide concentrations can be arranged in this order in the sputtering device along the transport direction of the base layer 2. The material for the first target is, for example, the ITO (tin oxide concentration: 8% by mass or more) in the first region 11 described above. The material for the second target is, for example, the ITO (tin oxide concentration: less than 8% by mass) in the second region 12 described above.

[0090] By the above sputtering, an amorphous light-transmitting conductive layer 3 is disposed on one surface of the base layer 2 in the thickness direction.

[0091] When the amorphous light-transmitting conductive layer 3 is formed by sputtering using the first and second targets described above, the amorphous light-transmitting conductive layer 3 includes a first amorphous layer and a second amorphous layer having different tin oxide concentrations, arranged in this order toward one side in the thickness direction. The materials of the first and second amorphous layers are the same as the materials of the first and second targets. Specifically, the tin oxide concentration in the ITO of the first amorphous layer is, for example, 8% by mass or more. The tin oxide concentration in the ITO of the second amorphous layer is, for example, less than 8% by mass.

[0092] The ratio of the thickness of the first amorphous layer to the thickness of the amorphous light-transmitting conductive layer 3 is, for example, more than 50%, preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, and is, for example, 99% or less, preferably 97% or less.

[0093] The ratio of the thickness of the second amorphous layer to the thickness of the light-transmitting conductive layer 3 is, for example, 1% or more, preferably 3% or more, and for example, 50% or less, preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less.

[0094] As a result, a transparent conductive film 1 (sometimes referred to as an amorphous laminate film) consisting of the base layer 2 and the amorphous light-transmitting conductive layer 3 is obtained.

[0095] Furthermore, when producing a transparent conductive film 1 in which the light-transmitting conductive layer 3 is crystalline, after the first step described above, a second step is carried out in which the amorphous light-transmitting conductive layer 3 is heated to form a crystalline light-transmitting conductive layer 3.

[0096] In other words, the method for producing the transparent conductive film 1 (when the light-transmitting conductive layer 3 is crystalline) comprises a first step of disposing an amorphous light-transmitting conductive layer 3 on one thickness-wise surface of the substrate layer 2 by a sputtering method in the presence of krypton and / or xenon, targeting the material that constitutes the light-transmitting conductive layer 3; and a second step of heating the amorphous light-transmitting conductive layer 3 to form a crystalline light-transmitting conductive layer 3.

[0097] In this method, the second step is carried out after the first step described above.

[0098] In the second step, the amorphous laminate film is heated. For example, the amorphous light-transmitting conductive layer 3 is heated by a heating device such as an infrared heater or an oven.

[0099] Regarding heating conditions, the heating temperature is, for example, 80°C or higher, preferably 110°C or higher, and, for example, lower than 200°C, preferably 180°C or lower, more preferably 160°C or lower; the heating time is, for example, 1 minute or longer, preferably 10 minutes or longer, even more preferably 30 minutes or longer, and, for example, 5 hours or shorter, preferably 3 hours or shorter.

[0100] As a result, the amorphous light-transmitting conductive layer 3 is crystallized to form a crystalline light-transmitting conductive layer 3, as shown in FIG. 2C.

[0101] In addition, when the amorphous light-transmitting conductive layer 3 includes a first amorphous layer and a second amorphous layer, the crystalline light-transmitting conductive layer 3 includes a first region 11 and a second region 12 corresponding to the first amorphous layer and the second amorphous layer, respectively.

[0102] In this way, a transparent conductive film 1 is produced which is provided with the substrate layer 2 and the crystalline light-transmitting conductive layer 3 in this order.

[0103] As a result of the above, a transparent conductive film 1 is produced which includes the base layer 2 and the amorphous or crystalline light-transmitting conductive layer 3 in that order.

[0104] In the transparent conductive film 1 having a crystalline light-transmitting conductive layer 3, the light-transmitting conductive layer 3 contains crystal grains having a particle size of, for example, 35 nm or more, preferably 100 nm or more, more preferably 200 nm or more, even more preferably 250 nm or more, particularly preferably 300 nm or more, most preferably 400 nm or more, even 480 nm or more, or even 550 nm or more, and for example, 2000 nm or less, preferably 1000 nm or less, more preferably 600 nm or less.

[0105] When the particle size is within the above range (especially when it is 35 nm or more), the resistivity of the light-transmitting conductive layer 3 can be reduced, and the heat stability of the transparent conductive film 1 can be further improved.

[0106] The method for measuring the grain size of the crystal grains will be described in detail in the examples below.

[0107] The carrier density of the crystalline light-transmitting conductive layer 3 is not particularly limited. For example, 19 cm -3 More than 70 × 10 19 cm -3 More preferably, 90×10 19 cm -3 More preferably, 100×10 19 cm -3 That's it, and 300 x 10 19 cm -3 Less than 200 × 10, preferably 19 cm -3 or less, more preferably 190×10 19 cm -3 If the carrier density is within the above range, a light-transmitting conductive layer 3 having excellent low resistivity can be obtained.

[0108] The mobility of the crystalline light-transmitting conductive layer 3 is not particularly limited, but may be, for example, 15 cm 2 / V·s or more, preferably 20cm 2 / V·s or more, preferably 25cm 2 / V·s or more, more preferably 27cm 2 / V·s or more, especially preferably 28cm 2 / V·s or more and 50cm 2 / V·s or less, preferably 40cm 2 When the mobility is within the above range, a light-transmitting conductive layer 3 having excellent low resistivity can be obtained.

[0109] The carrier density and mobility can be measured using a Hall effect measuring device (for example, trade name "HL5500PC", manufactured by Bio-Rad).

[0110] As described above, in the first step of this method, the amorphous light-transmitting conductive layer 3 is disposed by sputtering in the presence of krypton gas and / or xenon gas.

[0111] When the amorphous light-transmitting conductive layer 3 is disposed by sputtering, a sputtering gas is taken into the amorphous light-transmitting conductive layer 3 .

[0112] However, in this method, instead of the commonly used argon, krypton atoms and / or xenon atoms, which have a larger atomic weight than argon, are used as the sputtering gas, and therefore, the incorporation of the sputtering gas (krypton atoms and / or xenon atoms) into the amorphous light-transmitting conductive layer 3 can be suppressed.

[0113] Then, such an amorphous light-transmitting conductive layer 3 becomes a crystalline light-transmitting conductive layer 3 in the second step.

[0114] Therefore, although the crystalline light-transmitting conductive layer 3 contains krypton atoms and / or xenon atoms, as described above, the amount of krypton atoms and / or xenon atoms incorporated is suppressed, and therefore the transparent conductive film 1 has excellent heat stability.

[0115] 4, the light-transmitting conductive layer 3 of the transparent conductive film 1 can also be patterned. That is, the light-transmitting conductive layer 3 has a pattern shape.

[0116] To pattern the light-transmitting conductive layer 3, for example, after the first step, the amorphous light-transmitting conductive layer 3 is etched. As a result, the transparent conductive film 1 has a patterned portion 7 having the light-transmitting conductive layer 3 and a non-patterned portion 8 not having the light-transmitting conductive layer 3.

[0117] Thereafter, in the second step, the light-transmitting conductive layer 3 is crystallized.

[0118] Alternatively, after the crystalline light-transmitting conductive layer 3 is obtained in the second step, the light-transmitting conductive layer 3 can be patterned.

[0119] This transparent conductive film 1 is used in a variety of products, such as touch sensors, dimming elements (voltage-driven dimming elements such as PDLC, PNLC, and SPD, and current-driven dimming elements such as electrochromic (EC)), photoelectric conversion elements (electrodes of solar cell elements such as organic thin-film solar cells and dye-sensitized solar cells), heat ray control members (near-infrared reflective and / or absorbing members and far-infrared reflective and / or absorbing members), antennas (light-transmitting antennas), electromagnetic wave shielding members, image display devices, heater members (light-transmitting heaters), and lighting.

[0120] The article comprises the transparent conductive film 1 and a member corresponding to each article.

[0121] Such articles can be obtained by fixing the transparent conductive film 1 to a member corresponding to each article.

[0122] Specifically, the light-transmitting conductive layer 3 (including the light-transmitting conductive layer 3 having a pattern shape) in the transparent conductive film 1 and a member corresponding to each article are fixed via an adhesive layer.

[0123] Examples of the adhesive layer include an adhesive layer and an adhesive layer.

[0124] The adhesive layer can be made of any material without particular limitations as long as it is transparent. The adhesive layer is preferably made of a resin. Examples of resins 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. In particular, acrylic resin is preferably selected as the resin from the viewpoints of excellent optical transparency, adhesive properties such as moderate wettability, cohesiveness, and adhesiveness, and excellent weather resistance and heat resistance.

[0125] To inhibit corrosion and migration of the light-transmitting conductive layer 3, known corrosion inhibitors and migration inhibitors (such as those disclosed in JP 2015-022397 A) may be added to the adhesive layer (the resin forming the adhesive layer). To inhibit deterioration of the article during outdoor use, known ultraviolet absorbers may be added to the adhesive layer (the resin forming the adhesive layer). Examples of ultraviolet absorbers include benzophenone-based compounds, benzotriazole-based compounds, salicylic acid-based compounds, oxalic acid anilide-based compounds, cyanoacrylate-based compounds, and triazine-based compounds.

[0126] Furthermore, the base layer 2 of the transparent conductive film 1 can be fixed to a member corresponding to each article via an adhesive layer. In such a case, the light-transmitting conductive layer 3 (including the light-transmitting conductive layer 3 having a patterned shape) is exposed in the transparent conductive film 1. Therefore, a cover layer can be disposed on the upper surface of the light-transmitting conductive layer 3.

[0127] The cover layer is a layer that covers the light-transmitting conductive layer 3, and can improve the reliability of the light-transmitting conductive layer 3 and prevent deterioration of its function due to scratches.

[0128] The cover layer is preferably a dielectric material. The cover layer is formed from a mixture of a resin and an inorganic material. Examples of the resin include the resins exemplified for the adhesive layer. Examples of the inorganic material include the materials exemplified for the intermediate layer described below.

[0129] Furthermore, from the same viewpoint as in the adhesive layer, a corrosion inhibitor, a migration inhibitor, and an ultraviolet absorber may also be added to the cover layer (a mixture of resin and inorganic material).

[0130] Such products (touch sensors, light control elements, photoelectric conversion elements, heat ray control members, antennas, electromagnetic wave shielding members, image display devices, heater members, and lighting) have excellent heat stability because they include the transparent conductive film 1 of the present invention. 5. Variations In the modified example, the same components and steps as those in the first embodiment are denoted by the same reference numerals, and detailed descriptions thereof will be omitted. Furthermore, the modified example can achieve the same effects as those in the first embodiment unless otherwise specified. Furthermore, the first embodiment and its modified example can be combined as appropriate.

[0131] The light-transmitting conductive layer 3 may not include the second region in which the proportion of tin oxide is less than 8 mass %, but may include only the first region 11 in which the proportion of tin oxide is 8 mass % or more.

[0132] In the above description, the functional layer 5 is a hard coat layer, but an optical adjustment layer can also be disposed as the functional layer 5.

[0133] In such a case, the substrate layer 2 includes the transparent substrate 4 and the optical adjustment layer in this order toward one side in the thickness direction.

[0134] The optical adjustment layer is a layer that suppresses the visibility of the pattern formed from the light-transmitting conductive layer 3 and adjusts the optical properties (specifically, the refractive index) of the transparent conductive film 1.

[0135] The material of the optical adjustment layer is, for example, an optical adjustment composition. Examples of the optical adjustment composition include the mixtures described in JP 2016-179686 A.

[0136] The mixture contains, for example, a resin (binder resin) such as an acrylic resin, and inorganic and / or organic particles (preferably inorganic particles such as zirconia). The thickness of the optical adjustment layer 8 is, for example, 0.05 μm or more and, for example, 1 μm or less.

[0137] To form the optical adjustment layer, a diluted solution of the optical adjustment composition is applied to one surface in the thickness direction of the transparent substrate 4, dried, and then cured by ultraviolet irradiation.

[0138] In this way, an optical adjustment layer is formed.

[0139] Furthermore, a release functional layer can also be disposed as the functional layer 5.

[0140] In such a case, the base layer 2 includes the transparent base 4 and the release functional layer in this order toward one side in the thickness direction.

[0141] The peelable functional layer is a layer that can be easily peeled from the light-transmitting conductive layer 3 (easy peelable layer).

[0142] If the base layer 2 has a peelable functional layer, the light-transmitting conductive layer 3 can be peeled off from the transparent conductive film 1. The peeled light-transmitting conductive layer 3 can be used, for example, by being transferred and attached to another member constituting a touch sensor.

[0143] Furthermore, an easy-adhesion layer can also be disposed as the functional layer 5 .

[0144] In such a case, the base layer 2 includes the transparent base material 4 and the easy-adhesion layer in this order toward one side in the thickness direction.

[0145] The easy-adhesion layer is a layer for ensuring adhesion between the transparent substrate 4 and a layer formed on the easy-adhesion layer, and can improve the adhesion between the transparent substrate 4 and the light-transmitting conductive layer 3, for example.

[0146] The functional layer 5 may be a multi-layer layer.

[0147] That is, the base layer 2 can optionally include, as the functional layer 5, two or more layers selected from the group consisting of a hard coat layer, an optical adjustment layer, a release functional layer, and an easy-adhesion layer.

[0148] In detail, the substrate layer 2 may have a transparent substrate 4, an easy-adhesion layer, a hard coat layer, and an optical adjustment layer, in that order toward one side in the thickness direction, or the substrate layer 2 may have a transparent substrate 4, a release functional layer, and a hard coat layer and / or an optical adjustment layer, in that order toward one side in the thickness direction.

[0149] When the substrate layer 2 has a transparent substrate 4, a release functional layer, and a hard coat layer and / or an optical adjustment layer, in that order toward one side in the thickness direction, a laminate having a hard coat layer and / or an optical adjustment layer and a light-transmitting conductive layer 3 can be peeled off from the transparent conductive film 1.

[0150] The substrate layer 2 may also be composed of only the transparent substrate 4 without including the functional layer 5 .

[0151] Furthermore, the substrate layer 2 may not include the transparent substrate 4 and may be composed of only the functional layer 5 .

[0152] An example of the transparent conductive film 1 having such a substrate layer 2 is the above-mentioned laminate (a laminate having a hard coat layer and / or an optical adjustment layer and a light-transmitting conductive layer 3).

[0153] Specifically, as shown in FIG. 5, the transparent conductive film 1 includes a base layer 2 (functional layer 5) and a light-transmitting conductive layer 3 in this order toward one side in the thickness direction.

[0154] The substrate layer 2 can also be composed of a transparent substrate 4 containing glass and a functional layer 5 .

[0155] The substrate layer 2 may also be provided with an anti-blocking layer (not shown) on the other side of the transparent substrate 4.

[0156] In such a case, the substrate layer 2 includes an anti-blocking layer, a transparent substrate 4, and a functional layer 5 in this order toward one side in the thickness direction.

[0157] The anti-blocking layer imparts anti-blocking properties to the surfaces of the transparent conductive films 1 that are in contact with each other when the transparent conductive films 1 are stacked in the thickness direction, for example.

[0158] The antiblocking layer has a film shape.

[0159] The material of the antiblocking layer is, for example, an antiblocking composition.

[0160] Examples of anti-blocking compositions include the mixtures described in JP-A-2016-179686.

[0161] The mixture contains, for example, a resin (binder resin) such as an acrylic resin, and inorganic and / or organic particles (preferably organic particles such as polystyrene).

[0162] The thickness of the antiblocking layer is, for example, 0.1 μm or more and, for example, 10 μm or less.

[0163] To form the antiblocking layer, a diluted solution of the antiblocking composition is applied to the other surface of the transparent substrate 4 in the thickness direction, dried, and then cured by irradiating with ultraviolet light.

[0164] This forms an anti-blocking layer.

[0165] Furthermore, a functional layer 5 such as an easy-adhesion layer may be further provided between the anti-blocking layer and the transparent substrate 4 .

[0166] The substrate layer 2 may also be provided with an intermediate layer (not shown) made of an inorganic layer on one side of the transparent substrate 4.

[0167] The intermediate layer has the function of improving the surface hardness of the base layer 2 and alleviating the stress that the light-transmitting conductive layer 3 receives from the base layer 2 at an intermediate point.

[0168] The intermediate layer can be provided at any position on one side of the transparent conductive film in the thickness direction relative to the transparent substrate 4, the functional layer 5, and the anti-blocking layer, and multiple layers may be provided.

[0169] For example, the base layer 2 includes a transparent base material 4, a functional layer 5, and an intermediate layer, in that order toward one side in the thickness direction. Also, the base layer 2 includes, for example, an intermediate layer, an anti-blocking layer, the transparent base material 4, and a functional layer 5, in that order toward one side in the thickness direction.

[0170] The intermediate layer is preferably an inorganic dielectric material, and its surface resistance is, for example, 1×10 6 Ω / □ or more, preferably 1×10 8 It is Ω / □ or more.

[0171] The material of the intermediate layer is, for example, a composition containing an inorganic oxide such as silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide, or calcium oxide, or a fluoride such as magnesium fluoride. The composition of the inorganic functional layer may or may not be a stoichiometric composition.

[0172] In one embodiment, one is illustrated as a suitable number of light-transmitting conductive layers 3 in the transparent conductive film 1, but it may also be two, for example, although not shown. In this case, two light-transmitting conductive layers 3 are disposed on both sides of the base layer 2 in the thickness direction. That is, in a suitable example of this modification, the number of light-transmitting conductive layers 3 for one base layer 2 is preferably two. [Example]

[0173] Specific numerical values ​​of blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the corresponding upper limit values ​​(numeric values ​​defined as "not more than" or "less than") or lower limit values ​​(numeric values ​​defined as "not less than" or "exceeding") of blending ratios (content ratios), physical property values, parameters, etc. described in the above "Description of the Invention." Furthermore, unless otherwise specified in the following description, "parts" and "%" are based on mass. 1. Manufacturing of transparent conductive film Example 1 (1st step) A UV-curable acrylic resin was applied to one side of a transparent film substrate made of a PET film roll (manufactured by Toray Industries, Inc., thickness 50 μm) and cured by UV irradiation. This formed a hard coat layer with a thickness of 2 μm. This gave a substrate layer.

[0174] Next, the base layer was placed in a vacuum sputtering device, and the ultimate vacuum was 0.9×10 -4 The chamber was fully evacuated to 0.4 Pa, and the substrate layer was degassed. Then, while the substrate layer was conveyed along the film-forming roll, a first target consisting of ITO, a sintered body of indium oxide and tin oxide with a tin oxide concentration of 10% by mass, was sputtered under reduced pressure (0.4 Pa) with krypton as the sputtering gas and oxygen as the reactive gas, using the equipment and conditions described below to form a 150 nm-thick amorphous light-transmitting conductive layer (first amorphous layer with a tin oxide concentration of 10% by mass) on one side of the substrate layer (hard coat layer). The amount of oxygen introduced was adjusted so that it was within region X of the resistance-oxygen curve shown in Figure 3 and the surface resistance of the amorphous light-transmitting conductive layer was 45 Ω / □ (the ratio of the oxygen introduction amount to the total amount of krypton and oxygen introduced was approximately 1.4% by mass). This resulted in an amorphous laminate film consisting of the substrate layer and the amorphous light-transmitting conductive layer. (2nd process) The obtained amorphous laminate film was heated for 1 hour in a hot air oven at 155°C, thereby converting the amorphous light-transmitting conductive layer into a crystalline light-transmitting conductive layer, and obtaining a transparent conductive film consisting of a substrate layer and a crystalline light-transmitting conductive layer. <Film formation equipment and conditions> Power supply: DC power supply Horizontal magnetic field strength of the first target: 90mT Film formation pressure: 0.4Pa Film forming roll temperature (temperature of substrate layer): -8°C Example 2, Comparative Example 7, Comparative Example 1 and Comparative Example 5 A transparent conductive film was obtained in the same manner as in Example 1, except that the sputtering gas, the thickness of the first region, the temperature of the film-forming roll, and the surface resistance of the amorphous light-transmitting conductive layer were changed according to the description in Table 1.

[0175] Example 3 A second target consisting of ITO with a tin oxide concentration of 3% by mass was further placed in the vacuum sputtering apparatus of Example 1, and a first amorphous layer with a thickness of 60 nm (tin oxide concentration of 10% by mass) was formed. Then, a second amorphous layer with a thickness of 3 nm (tin oxide concentration of 3% by mass) was successively formed on one side of the first amorphous layer. A transparent conductive film was obtained in the same manner as in Example 1, except that the amount of oxygen introduced was adjusted so that the surface resistance of the amorphous light-transmitting conductive layer was 120 Ω / □.

[0176] Comparative Examples 2 to 4 and 6 A transparent conductive film was obtained in the same manner as in Example 3, except that the sputtering gas, the thickness of the first and second regions, and the surface resistance of the amorphous light-transmitting conductive layer were changed according to the description in Table 1. 2. Evaluation <Thickness measurement> (Thickness of transparent substrate and hard coat layer) The thickness of the transparent substrate and the thickness of the hard coat layer were measured using a film thickness meter (Digital Dial Gauge DG-205 manufactured by Peacock Co., Ltd.). The results are shown in Table 1.

[0177] (Thickness of light-transmitting conductive layer) Cross sections of the transparent conductive films of each example and comparative example were prepared using the FIB microsampling method. The cross sections of the light-transmitting conductive layer were then observed using FE-TEM, and the thicknesses of the light-transmitting conductive layer (first and second regions) were measured. In Example 3, Comparative Example 6, Comparative Example 2, Comparative Example 3, and Comparative Example 4, the thickness of the first region was measured by preparing a cross-sectional observation sample in which only the first region was formed on one side of the first region in the thickness direction before the second region was disposed, and then observing the sample using FE-TEM. The thickness of the second region was calculated by subtracting the thickness of the first region from the thickness of the light-transmitting conductive layer. The results are shown in Table 1.

[0178] The equipment and measurement conditions are as follows: FIB equipment: Hitachi FB2200, Acceleration voltage: 10 kV FE-TEM equipment: JEOL JEM-2800, accelerating voltage: 200 kV <Evaluation of resistance value> For the transparent conductive films of each Example and Comparative Example, the surface resistance (R1) and specific resistance (R1') of the light-transmitting conductive layer were measured by the four-terminal method in accordance with JIS K7194 (1994). The results are shown in Table 1.

[0179] <Heating stability> The transparent conductive films of each Example and Comparative Example were further heated in a hot air oven at 155°C for 1 hour, and then the surface resistance (R2) and specific resistance (R2') of the light-transmitting conductive layer were measured. The results are shown in Table 1.

[0180] The heat stability was then evaluated as the ratio (R2 / R1) of the surface resistance (R2) to the surface resistance (R1).

[0181] In other words, the thermal stability (R2 / R1) is an evaluation of the amount of change in resistance when a crystalline light-transmitting conductive layer is reheated, and a value closer to 1 indicates better thermal stability. The results are shown in Table 1.

[0182] <Appearance> The transparent conductive films of each example and comparative example were placed on a horizontal table to check for the occurrence of wrinkles or streaks, and evaluated for the presence or absence of practical problems (uneven coating when forming a functional layer required for the product on the ITO film, or uneven appearance on the touch panel) when processing and incorporating the film into the product. ◯: Appearance was at a level that presented no practical problems. ×: Appearance was at a level that was problematic for practical use.

[0183] <Measurement of grain size> The transparent conductive films of the examples and comparative examples were cut out and fixed to a sample holder of an ultramicrotome. Next, a microtome knife was placed at an extremely acute angle to the ITO film surface, and the cut surface was cut so that it was approximately parallel to the ITO film surface to obtain an observation sample. This observation sample was observed using a transmission electron microscope (magnification: 50,000x). A 1.5 μm square area was arbitrarily selected from the TEM observation photograph, and the largest crystal grain observed in this 1.5 μm area was selected. Two arbitrary measurement points were placed on the grain boundary of this largest crystal grain, and the linear distance between the measurement points was calculated. In this measurement, the distance between the measurement points where the distance between the measurement points was the longest was taken as the particle size. The results are shown in Table 1.

[0184] <Identification of krypton atoms> Using a scanning X-ray fluorescence analyzer (ZSX PrimusIV, manufactured by Rigaku Corporation), it was confirmed that krypton atoms were present in the light-transmitting conductive layers of Examples 1 to 3 and Comparative Example 6. Specifically, measurements were repeated five times under the following conditions, and the average value for each scanning angle was calculated to create an X-ray spectrum. The presence of krypton atoms was identified by confirming that a peak appeared near 28.2° in the created X-ray spectrum. <Measurement conditions> Spectrum: Kr-KA Measuring diameter: 30 mm Atmosphere: Vacuum Target: Rh Tube voltage: 50kV Tube current: 60mA Primary filter: Ni40 Scanning angle (deg): 27.0~29.5 Step (deg): 0.020 Speed ​​(Deg / min):0.75 Attenuator: 1 / 1 Slit: S2 Spectroscopic crystal: LiF(200) Detector: SC PHA:100-300

[0185] [Table 1]

[0186] The above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be interpreted as limiting. Modifications of the present invention that are obvious to those skilled in the art are intended to be included in the scope of the following claims. [Industrial Applicability]

[0187] The transparent conductive film and the method for producing the transparent conductive film of the present invention are suitably used in touch sensors, light control elements, photoelectric conversion elements, heat ray control members, antennas, electromagnetic wave shielding members, image display devices, heater members (light-transmitting heaters), and lighting. [Explanation of symbols]

[0188] 1. Transparent conductive film 2 Base material layer 3 Light-transparent conductive layer 4 Transparent base material

Claims

1. A transparent conductive film having a base layer and a light-transmitting conductive layer in this order, the substrate layer includes a resin layer, the light-transmitting conductive layer contains krypton atoms and does not contain argon atoms; the thickness of the light-transmitting conductive layer is 40 nm or more; the light-transmitting conductive layer has a peak at about 28.2° in an X-ray spectrum measured with a scanning X-ray fluorescence analyzer; A transparent conductive film, wherein the light-transmitting conductive layer is crystalline and contains crystal grains having a grain size of 200 nm or more.

2. 2. The transparent conductive film according to claim 1, wherein the thickness of the light-transmitting conductive layer is 60 nm or more and 100 nm or less.

3. The transparent conductive film according to claim 1 , wherein the light-transmitting conductive layer contains an indium tin composite oxide.

4. 4. The transparent conductive film according to claim 1, wherein the light-transmitting conductive layer has a pattern shape.

5. A photoelectric conversion element comprising the transparent conductive film according to any one of claims 1 to 4.

6. A light-controlling element comprising the transparent conductive film according to any one of claims 1 to 4.

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