Transparent conductive film and manufacturing method of transparent conductive film

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 manufacturing the same.

Background Art

[0002] 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 having a film substrate and a polycrystalline layer of indium tin oxide formed on the film substrate has been proposed (see, for example, Patent Document 1).

[0004] Further, such a transparent conductive film can be obtained by disposing an amorphous layer of indium tin oxide on the surface of a film substrate in the presence of argon gas by sputtering, and then heating this amorphous layer to crystallize the amorphous layer of indium tin oxide.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] On the one hand, such a polycrystalline layer (crystalline) may be reheated. For example, when forming members required for creating a touch sensor, a photoelectric conversion element, etc. on a transparent conductive film, a heating process may be necessary. As a more specific example, when creating a touch sensor, there is, for example, a process of applying a metal-containing paste on the polycrystalline layer and heating it to form the routing wiring of the touch sensor. In such cases, it is required to suppress the change in the resistance value of the polycrystalline layer (excellent in heating stability) before and after heating.

[0007] A polycrystalline layer excellent in heating stability can be realized, for example, by applying an inorganic substrate such as a glass substrate and setting the substrate temperature high (for example, 230 °C or higher) when forming an indium tin oxide layer (transparent conductive layer) by sputtering. However, since a film substrate (polymer film) is inferior in heat resistance and has a large dimensional deformation due to heat, the substrate temperature cannot be set high (the substrate temperature is usually set to less than 200 °C, preferably 180 °C or less). For this reason, in the prior art including Patent Document 1, a transparent conductive film sufficiently excellent in heating stability has not been realized.

[0008] The present invention aims to provide a transparent conductive film excellent in heating stability and a method for manufacturing the transparent conductive film.

Means for Solving the Problems

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

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

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

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

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

[0014] The manufacturing method of the transparent conductive film of the present invention [6] is characterized in that in the presence of krypton and / or xenon, a light-transmissive conductive layer is disposed on a base material layer by a sputtering method targeting a material constituting the light-transmissive conductive layer, and the base material layer includes a resin layer.

Advantages of the Invention

[0015] In the manufacturing method of the transparent conductive film of the present invention, in the presence of krypton and / or xenon, a light-transmissive conductive layer is disposed on a base material layer by a sputtering method targeting a material constituting the light-transmissive conductive layer.

[0016] When disposing the light-transmissive conductive layer by the sputtering method, the sputtering gas is incorporated into the light-transmissive conductive layer.

[0017] In this method, since krypton atoms and / or xenon atoms having an atomic weight larger than that of argon are used as the sputtering gas instead of argon, it is possible to suppress the incorporation of the sputtering gas (krypton atoms and / or xenon atoms) into the light-transmissive conductive layer.

[0018] Thereby, a transparent conductive film excellent in heat stability can be manufactured.

[0019] Therefore, the transparent conductive film of the present invention is excellent in heat stability.

Brief Description of the Drawings

[0020]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Embodiments for Carrying Out 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 orthogonal to the thickness direction, and has a flat upper surface and a flat lower surface.

[0022] The transparent conductive film 1 is a member provided in a touch sensor, a dimming element, a photoelectric conversion element, a heat ray control member, an antenna, an electromagnetic wave shielding member, an image display device, a heater member (light-transmissive heater), and lighting, etc., which will be described later. The transparent conductive film 1 is an intermediate member for manufacturing them. The transparent conductive film 1 is circulated alone and is an industrially available device.

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

[0024] The thickness of the transparent conductive film 1 is, 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 is, for example, 1 μm or more, preferably 10 μm or more.

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

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

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

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

[0029] The transparent base material 4 has a film shape.

[0030] The transparent base material 4 is made of, for example, a polymer film. Thereby, the transparent conductive film 1 is excellent in production efficiency.

[0031] Further, when the transparent substrate 4 is made of a polymer film, the transparent conductive film 1 (crystalline light-transmissive conductive layer 3) may be reheated from the viewpoint of imparting dimensional stability to the transparent conductive film 1. However, this transparent conductive film 1 is excellent in heat stability.

[0032] Examples of the material of the transparent substrate 4 include olefin resins such as polyethylene, polypropylene, and cycloolefin polymers; 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, polystyrene resins, etc. Preferably, olefin resins, polyester resins, (meth)acrylic resins, polycarbonate resins, and melamine resins are mentioned. More preferably, polyester resins are mentioned. Even more preferably, polyethylene terephthalate (PET) is mentioned. Since the transparent substrate 4 made of the above materials has low heat resistance, it cannot be applied to a heating step of 200 °C or higher (specifically, the second step described later). However, according to such a transparent substrate 4, a transparent conductive film 1 excellent in smoothness and having heat stability can be obtained.

[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, 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 also, for example, 300 μm or less, preferably 200 μm or less, more preferably 100 μm or less, even more preferably 60 μm or less.

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

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

[0037] Examples of the functional layer 5 include a hard coat layer.

[0038] In such a case, the base material layer 2 includes a transparent base material 4 and a 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 a scratch protection layer for making it difficult for the transparent conductive film 1 to be scratched.

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

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

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

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

[0045] Examples of the material of the light-transmissive 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. The metal oxide may be further doped with the metal atoms shown in the above group as necessary.

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

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

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

[0049] When the content ratio of tin oxide is not less than the above-described lower limit, the reduction of resistance is promoted. When the content ratio of tin oxide is not more than the above-described upper limit, the light-transmissive conductive layer 3 is excellent in heat stability.

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

[0051] For example, the light-transmissive conductive layer 3 includes a first region 11 as an example of a region where the ratio of tin oxide is 8% by mass or more, and a second region 12 where the ratio of tin oxide is lower than that in the first region 11. Specifically, the light-transmissive conductive layer 3 sequentially includes a layered first region 11 and a layered second region 12 disposed on one side in the thickness direction of the first region 11. Note that the boundary between the first region 11 and the second region 12 is not confirmed by observation with a measuring device and may be unclear. In addition, the light-transmissive conductive layer 3 may have a concentration gradient in which the tin oxide concentration gradually increases from one side to the other side in the thickness direction. When the light-transmissive conductive layer 3 includes the second region 12 in addition to the first region 11 described above, a desired crystallization rate can be obtained by adjusting the ratio of the regions.

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

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

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

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

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

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

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

[0059] Further, as will be described in detail later, the light-transmissive conductive layer 3 contains a trace amount of sputtering gas (krypton atoms and / or xenon atoms).

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

[0061] The lower limit of the above content is the ratio 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] Further, the light-transmissive conductive layer 3 is crystalline or amorphous.

[0063] If the light-transmissive conductive layer 3 is crystalline, the specific resistance can be reduced.

[0064] The crystallinity of the light-transmissive 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 washing with water and drying, and then measuring the resistance between terminals within about 15 mm on the surface on the side of the light-transmissive conductive layer 3. In the transparent conductive film 1 after the above immersion, washing with water, and drying, when the resistance between terminals within 15 mm is 10 kΩ or less, the light-transmissive conductive layer 3 is crystalline; on the other hand, when the resistance exceeds 10 kΩ, the light-transmissive conductive layer 3 is amorphous.

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

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

[0067] If the thickness of the light-transmissive conductive layer 3 is at least the above lower limit, the heat stability of the transparent conductive film 1 can be further improved.

[0068] Also, if the thickness of the light-transmissive conductive layer 3 is at most the above upper limit, the heat stability of the transparent conductive film 1 can be further improved.

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

[0070] The specific resistance of the light-transmissive conductive layer 3 is, for example, 5.0×10 -4Less than -4 Ω·cm, preferably less than 2.5×10 -4 Ω·cm, more preferably less than 2.4×10 -4 Ω·cm, even more preferably less than 2.2×10 -4 Ω·cm, particularly preferably less than 2.0×10 -4 Ω·cm, and for example, more than 0.1×10 -4 Ω·cm, preferably more than 0.5×10 -4 Ω·cm, more preferably more than 1.0×10 -4 Ω·cm, even more preferably more than 1.01×10 -4 Ω·cm.

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

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

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

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

[0075] The manufacturing method of the transparent conductive film 1 (when the optically transparent conductive layer 3 is amorphous) comprises a first step of disposing an amorphous optically transparent conductive layer 3 on one surface in the thickness direction of the base material layer 2 by a sputtering method using as a target the material constituting the optically transparent conductive layer 3 in the presence of krypton and / or xenon. In this manufacturing 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, the base material layer 2 is prepared.

[0077] Specifically, a diluted solution of a hard coat composition is applied on one surface in the thickness direction of the transparent base material 4, and after drying, the hard coat composition is cured by ultraviolet irradiation. Thereby, a hard coat layer (functional layer 5) is formed on one surface in the thickness direction of the transparent base material 4.

[0078] Thereby, the base material layer 2 is prepared.

[0079] Next, as shown in Fig. 2B, an amorphous optically transparent conductive layer 3 is disposed on one surface in the thickness direction of the base material layer 2 by sputtering.

[0080] Specifically, in a sputtering apparatus, while facing one surface in the thickness direction of the base material layer 2 to a target made of the material of the optically transparent conductive layer 3, 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 side opposite to the base material layer 2 with respect to the target. The horizontal magnetic field intensity 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 intensity on the target surface within the above range, the amount of impurities in the optically transparent conductive layer 3 can be reduced, and an optically transparent conductive layer 3 excellent in low specific resistance and heat stability can be manufactured.

[0082] When forming the optically transparent conductive layer 3 by sputtering, the temperature of the base material layer 2 is not particularly limited, but preferably, the base material layer 2 is cooled. Specifically, the temperature of the base material layer 2 is, for example, 15°C or lower, more preferably 10°C or lower, still more preferably 5°C or lower, particularly preferably 0°C or lower, and also, for example, -50°C or higher, preferably -30°C, more preferably -20°C or higher. If it is below the above temperature, the base material layer 2 can be cooled during sputtering, outgassing (water or organic solvent) from the base material layer 2 is less likely to occur, and impurity components in the optically transparent conductive layer 3 can be reduced. Therefore, an optically transparent conductive layer 3 having excellent low specific resistance and heat stability can be obtained. If it is above the above temperature, deterioration of the physical properties of the base material layer 2 can be suppressed.

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

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

[0085] As shown in FIG. 3, the introduction amount of the reactive gas can be estimated from the surface resistance of the amorphous optically transparent conductive layer 3. Specifically, since the film quality (surface resistance) of the amorphous optically transparent conductive layer 3 changes depending on the introduction amount of the reactive gas introduced into the amorphous optically transparent conductive layer 3, the introduction amount of the reactive gas can be adjusted according to the target surface resistance of the amorphous optically transparent conductive layer 3. In order to obtain a crystalline film optically transparent conductive layer 3 by heating the amorphous optically transparent conductive layer 3, it is preferable to adjust the introduction amount of the reactive gas within the range of region X in FIG. 3 to obtain the amorphous optically transparent conductive layer 3.

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

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

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

[0089] In addition, when using ITO as the material of the light-transmissive conductive layer 3, a first target and a second target with different tin oxide concentrations can also be arranged in order along the conveyance direction of the base material layer 2 in the sputtering apparatus. The material of the first target is, for example, ITO (tin oxide concentration: 8 mass % or more) in the first region 11 described above. The material of the second target is, for example, ITO (tin oxide concentration: less than 8 mass %) in the second region 12 described above.

[0090] By the above sputtering, the amorphous light-transmissive conductive layer 3 is arranged on one side in the thickness direction of the base material layer 2.

[0091] In addition, when the amorphous light-transmissive conductive layer 3 is formed by sputtering using the above-described first target and second target, the amorphous light-transmissive conductive layer 3 includes a first amorphous layer and a second amorphous layer having different tin oxide concentrations in order toward one side in the thickness direction. The materials of the first amorphous layer and the second amorphous layer are the same as the materials of the first target and the second target. 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 in the thickness of the amorphous light-transmissive conductive layer 3 is, for example, more than 50%, preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and is also, for example, 99% or less, preferably 97% or less.

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

[0094] Thereby, a transparent conductive film 1 (which may be referred to as an amorphous laminated film) composed of the base material layer 2 and the amorphous light-transmissive conductive layer 3 is obtained.

[0095] In addition, when manufacturing the transparent conductive film 1 in which the light-transmissive conductive layer 3 is crystalline, after the above-described first step, a second step of heating the amorphous light-transmissive conductive layer 3 to form a crystalline light-transmissive conductive layer 3 is performed.

[0096] That is, the manufacturing method of the transparent conductive film 1 (when the light-transmissive conductive layer 3 is crystalline) is a sputtering method targeting the material constituting the light-transmissive conductive layer 3 in the presence of krypton and / or xenon. In a first step, an amorphous light-transmissive conductive layer 3 is disposed on one surface in the thickness direction of the base material layer 2. In a second step, the amorphous light-transmissive conductive layer 3 is heated to form a crystalline light-transmissive conductive layer 3.

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

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

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

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

[0101] When the amorphous light-transmissive conductive layer 3 includes a first amorphous layer and a second amorphous layer, the crystalline light-transmissive 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. [[ID=,21]]

[0102] Thereby, the transparent conductive film 1 including the base material layer 2 and the crystalline light-transmissive conductive layer 3 in this order is manufactured.

[0103]

[0104] ​ In a transparent conductive film 1 provided with a crystalline light-transmissive conductive layer 3, the light-transmissive 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, still more preferably 250 nm or more, particularly preferably 300 nm or more, most preferably 400 nm or more, further 480 nm or more, and further 550 nm or more, and also, for example, 2000 nm or less, preferably 1000 nm or less, more preferably 600 nm or less.

[0105] If the particle size is within the above range (particularly, if it is 35 nm or more), the specific resistance of the light-transmissive conductive layer 3 can be reduced, and the heat stability of the transparent conductive film 1 can be further improved.

[0106] Note that the method for measuring the particle size of the crystal grains will be described in detail in the examples described later.

[0107] There is no particular limitation on the carrier density of the crystalline light-transmissive conductive layer 3, but for example, it is 30×10 19 cm -3 or more, preferably 70×10 19 cm -3 or more, more preferably 90×10 19 cm -3 or more, still more preferably 100×10 19 cm -3 or more, and also 300×10 19 cm -3 or less, preferably 200×10 19 cm -3 or less, more preferably 190×10 19 cm -3 or less. If the carrier density is within the above range, a light-transmissive conductive layer 3 excellent in low specific resistance can be obtained.

[0108] There is no particular limitation on the mobility of the crystalline light-transmissive conductive layer 3, but for example, it is 15 cm 2 / V·s or more, preferably 20 cm 2 / V·s or more, more preferably 25 cm 2Above / V·s, more preferably 27 cm 2 Above / V·s, particularly preferably 28 cm 2 Above / V·s and also 50 cm 2 Below / V·s, preferably 40 cm 2 Below / V·s. If the mobility is within the above range, a light-transmissive conductive layer 3 excellent in low specific resistance can be obtained.

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

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

[0111] When an amorphous light-transmissive conductive layer 3 is disposed by a sputtering method, the sputtering gas is incorporated into the amorphous light-transmissive conductive layer 3.

[0112] However, in this method, since krypton atoms and / or xenon atoms having a larger atomic weight than argon are used as the sputtering gas instead of the commonly used argon, it is possible to suppress the incorporation of the sputtering gas (krypton atoms and / or xenon atoms) into the amorphous light-transmissive conductive layer 3.

[0113] And such an amorphous light-transmissive conductive layer 3 becomes a crystalline light-transmissive conductive layer 3 in the second step.

[0114] Therefore, although the crystalline light-transmissive 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. Therefore, this transparent conductive film 1 is excellent in heat stability.

[0115] Also, as shown in FIG. 4, in the transparent conductive film 1, the light-transmissive conductive layer 3 can also be patterned. That is, the light-transmissive conductive layer 3 has a pattern shape.

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

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

[0118] Also, after obtaining the crystalline light-transmissive conductive layer 3 by the second step, the light-transmissive conductive layer 3 can be patterned.

[0119] And this transparent conductive film 1 is used for various articles. Examples of the articles include a touch sensor, a light control element (voltage-driven light control elements such as PDLC, PNLC, and SPD, and current-driven light control elements such as electrochromic (EC)), a photoelectric conversion element (electrodes of solar cell elements typified by organic thin-film solar cells and dye-sensitized solar cells), a heat ray control member (near-infrared reflection and / or absorption member and far-infrared reflection and / or absorption member), an antenna (light-transmissive antenna), an electromagnetic wave shielding member, an image display device, a heater member (light-transmissive heater), and lighting.

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

[0121] Such an article is obtained by fixing the transparent conductive film 1 and a member corresponding to each article.

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

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

[0124] As the fixing functional layer, any material can be used without particular limitation as long as it has transparency. The fixing functional layer is preferably formed of a resin. Examples of the resin include acrylic resin, silicone resin, polyester resin, polyurethane resin, polyamide resin, polyvinyl ether resin, vinyl acetate / vinyl chloride copolymer, modified polyolefin resin, epoxy resin, fluororesin, natural rubber, and synthetic rubber. In particular, from the viewpoints of excellent optical transparency, exhibiting adhesive properties such as appropriate wettability, cohesiveness, and adhesiveness, and also excellent weather resistance and heat resistance, acrylic resin is preferably selected as the resin.

[0125] Known corrosion inhibitors and migration inhibitors (for example, the materials disclosed in JP-A-2015-022397) can also be added to the fixing functional layer (the resin forming the fixing functional layer) to suppress corrosion and migration of the optically transparent conductive layer 3. Further, a known ultraviolet absorber may be added to the fixing functional layer (the resin forming the fixing functional layer) to suppress deterioration during outdoor use of the article. Examples of the ultraviolet absorber include benzophenone-based compounds, benzotriazole-based compounds, salicylic acid-based compounds, oxalic acid anilide-based compounds, cyanoacrylate-based compounds, and triazine-based compounds.

[0126] Further, the base material layer 2 in the transparent conductive film 1 and the member corresponding to each article can also be fixed via the fixing functional layer. In such a case, in the transparent conductive film 1, the optically transparent conductive layer 3 (including the optically transparent conductive layer 3 having a pattern shape) is exposed. Therefore, a cover layer can also be disposed on the upper surface of the optically transparent conductive layer 3.

[0127] The cover layer is a layer that covers the optically transparent conductive layer 3, and can improve the reliability of the optically transparent conductive layer 3 and suppress functional deterioration due to scratches.

[0128] The cover layer is preferably a dielectric. 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 fixing functional layer. Examples of the inorganic material include the materials exemplified for the material of the intermediate layer described later.

[0129] Also, for the cover layer (a mixture of a resin and an inorganic material), from the same viewpoints as those of the above-described fixing functional layer, a corrosion inhibitor, a migration inhibitor, and an ultraviolet absorber can be added.

[0130] Since such articles (touch sensors, dimming elements, photoelectric conversion elements, heat ray control members, antennas, electromagnetic wave shielding members, image display devices, heater members, and illuminations) are provided with the transparent conductive film 1 of the present invention, they are excellent in heat stability. 5. Modification In the modification, for members and steps similar to those in one embodiment, the same reference numerals are given, and detailed descriptions thereof are omitted. Further, the modification can exhibit the same operational effects as those of one embodiment unless otherwise specified. Furthermore, one embodiment and its modification can be appropriately combined.

[0131] The light-transmissive conductive layer 3 may include only the first region 11 in which the ratio of tin oxide is 8% by mass or more, without including a second region in which the ratio of tin oxide is less than 8% by mass.

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

[0133] In such a case, the base material layer 2 includes a transparent base material 4 and an 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-transmissive conductive layer 3 and adjusts the optical physical 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 mixture described in JP-A-2016-179686.

[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] Further, 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, and after drying, the optical adjustment composition is cured by ultraviolet irradiation.

[0138] Thereby, the optical adjustment layer is formed.

[0139] Also, as the functional layer 5, a peeling functional layer can be disposed.

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

[0141] The peeling functional layer is a layer (easy peeling layer) that is easily peeled from the light transmissive conductive layer 3.

[0142] If the base material layer 2 includes the peeling functional layer, the light transmissive conductive layer 3 can be peeled from the transparent conductive film 1. The peeled light transmissive conductive layer 3 can be used, for example, by transferring and laminating it to other members constituting a touch sensor.

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

[0144] In such a case, the base material layer 2 includes the transparent substrate 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 the adhesion between the transparent substrate 4 and the layer formed on the easy - adhesion layer. For example, it can improve the adhesion between the transparent substrate 4 and the light - transmissive conductive layer 3.

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

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

[0148] Specifically, the substrate layer 2 can also be provided with a transparent substrate 4, an easy - adhesion layer, a hard - coat layer, and an optical adjustment layer in this order toward one side in the thickness direction. Also, the substrate layer 2 can be provided with a transparent substrate 4, a peeling - function layer, a hard - coat layer and / or an optical adjustment layer in this order toward one side in the thickness direction.

[0149] When the substrate layer 2 is provided with a transparent substrate 4, a peeling - function layer, a hard - coat layer and / or an optical adjustment layer in this order toward one side in the thickness direction, a laminate including the hard - coat layer and / or the optical adjustment layer and the light - transmissive conductive layer 3 can be peeled from the transparent conductive film 1.

[0150] Also, the substrate layer 2 can consist of only the transparent substrate 4 without the functional layer 5.

[0151] Also, the substrate layer 2 can consist of only the functional layer 5 without the transparent substrate 4.

[0152] Examples of the transparent conductive film 1 having such a substrate layer 2 include the above - described laminate (a laminate including the hard - coat layer and / or the optical adjustment layer and the light - transmissive conductive layer 3).

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

[0154] Further, the base material layer 2 can also be composed of a transparent base material 4 containing glass and a functional layer 5.

[0155] In addition, the base material layer 2 can also be provided with an anti-blocking layer (not shown) on the other surface of the transparent base material 4.

[0156] In such a case, the base material layer 2 includes an anti-blocking layer, a transparent base material 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 plurality of transparent conductive films 1 that come into contact with each other when the transparent conductive film 1 is laminated in the thickness direction.

[0158] The anti-blocking layer has a film shape.

[0159] The material of the anti-blocking layer is, for example, an anti-blocking composition.

[0160] Examples of the anti-blocking composition include the mixture 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 anti-blocking layer is, for example, 0.1 μm or more and, for example, 10 μm or less.

[0163] Further, to form the anti-blocking layer, a diluted solution of the anti-blocking composition is applied to the other surface of the transparent base material 4 in the thickness direction, and after drying, the anti-blocking composition is cured by ultraviolet irradiation.

[0164] Thereby, the anti-blocking layer is formed.

[0165] Further, a functional layer 5 such as an easy adhesion layer can also be provided between the antiblocking layer and the transparent substrate 4.

[0166] Further, the base material layer 2 can also include 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 material layer 2 and relieving the stress received by the optically transparent conductive layer 3 from the base material layer 2 at an intermediate point.

[0168] The intermediate layer can be provided at an arbitrary position on one side in the thickness direction of the transparent conductive film with respect to the transparent substrate 4, the functional layer 5, and the antiblocking layer, and may include a plurality of layers.

[0169] For example, the base material layer 2 includes the transparent substrate 4, the functional layer 5, and the intermediate layer in this order toward one side in the thickness direction. Further, the base material layer 2 includes, for example, the intermediate layer, the antiblocking layer, the transparent substrate 4, and the functional layer 5 in this order toward one side in the thickness direction.

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

[0171] The material of the intermediate layer is composed of a composition containing inorganic oxides such as silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide, calcium oxide, and fluorides such as magnesium fluoride. Note that the composition of the inorganic functional layer may or may not be a stoichiometric composition.

[0172] In one embodiment, the preferred number of the optically transparent conductive layers 3 in the transparent conductive film 1 is exemplified as 1. However, for example, although not shown, it may be 2. In this case, each of the two optically transparent conductive layers 3 is disposed on each of both sides in the thickness direction of the base material layer 2. That is, in a preferred example of this modification, the number of the optically transparent conductive layers 3 with respect to one base material layer 2 is preferably 2.

Example

[0173] In the following description, specific numerical values such as the mixing ratio (content ratio), physical property values, parameters, etc. used can be replaced with the upper limit values (numerical values defined as "below" and "less than") or lower limit values (numerical values defined as "above" and "exceeding") of the corresponding mixing ratio (content ratio), physical property values, parameters, etc. described in the above "Mode for Carrying Out the Invention". Also, unless otherwise specified in the following description, "parts" and "%" are based on mass. 1. Manufacture of Transparent Conductive Film Example 1 (First Step) An ultraviolet curable resin made of an acrylic resin was applied to one surface of a film substrate made of a PET film roll (manufactured by Toray Industries, Inc., thickness 50 μm) as a transparent substrate, and cured by ultraviolet irradiation. As a result, a hard coat layer with a thickness of 2 μm was formed. Thus, a substrate layer was obtained.

[0174] Next, the substrate layer was installed in a vacuum sputtering apparatus, and sufficient evacuation was performed so that the ultimate vacuum degree reached 0.9×10 -4 Pa, and degassing treatment of the substrate layer was carried out. Then, while transporting the substrate layer along the film forming roll, under reduced pressure (0.4 Pa), krypton as a sputtering gas and oxygen as a reactive gas were introduced, and a first target made of a sintered body of indium oxide and tin oxide with a tin oxide concentration of 10% by mass was sputtered under the following equipment and conditions to form an amorphous light-transmissive conductive layer with a thickness of 150 nm (a first amorphous layer with a tin oxide concentration of 10% by mass) on one surface of the substrate layer (hard coat layer). The oxygen introduction amount was adjusted so that it was in region X of the resistance-oxygen curve shown in Figure 3 and the surface resistance of the amorphous light-transmissive conductive layer became 45 Ω / □ (the ratio of the oxygen introduction amount to the total introduction amount of krypton and oxygen was about 1.4% by mass). As a result, an amorphous laminated film composed of a substrate layer and an amorphous light-transmissive conductive layer was obtained. (Second Step) The obtained amorphous laminated film was heated in a hot air oven at 155 °C for 1 hour. As a result, the amorphous light-transmissive conductive layer was changed to a crystalline light-transmissive conductive layer, and a transparent conductive film composed of a base material layer and the crystalline light-transmissive conductive layer was obtained. <Film forming equipment and conditions> Power supply: DC power supply Horizontal magnetic field strength of the first target: 90 mT Film forming pressure: 0.4 Pa Film forming roll temperature (temperature of the base material layer): -8 °C Example 2, Comparative Example 7, Comparative Example 1, and Comparative Example 5 According to the description in Table 1, 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 film forming roll temperature, and the surface resistance of the amorphous light-transmissive conductive layer were changed.

[0175] Example 3 A second target made of ITO with a tin oxide concentration of 3% by mass was further installed in the vacuum sputtering apparatus of Example 1. After forming a first amorphous layer with a thickness of 60 nm (tin oxide concentration of 10% by mass), a second amorphous layer with a thickness of 3 nm (tin oxide concentration of 3% by mass) was continuously formed on one surface of the first amorphous layer. A transparent conductive film was obtained in the same manner as in Example 1, except that the oxygen introduction amount was adjusted so that the surface resistance of the amorphous light-transmissive conductive layer was 120 Ω / sq.

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

[0177] (Thickness of the light-transmissive conductive layer) Cross-sections of the transparent conductive films of each example and each comparative example were prepared by the FIB micro-sampling method. Next, the cross-section of the optically transparent conductive layer was observed by FE-TEM, and the thicknesses of the optically transparent conductive layer (first region and second region) were measured. Here, 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 sample for cross-sectional observation in which only the first region was formed in one aspect in the thickness direction of the first region before arranging the second region, and subjecting the sample to FE-TEM observation. Also, the thickness of the second region was calculated by subtracting the thickness of the first region from the thickness of the optically transparent conductive layer. The results are shown in Table 1.

[0178] The apparatus and measurement conditions are shown below. FIB apparatus: FB2200 manufactured by Hitachi, acceleration voltage: 10 kV FE-TEM apparatus: JEM-2800 manufactured by JEOL, acceleration voltage: 200 kV <Evaluation of resistance value> For the transparent conductive films of each example and each comparative example, the surface resistance (R1) and specific resistance (R1') of the optically transparent conductive layer were measured by the four-terminal method in accordance with JIS K7194 (1994). The results are shown in Table 1.

[0179] <Heat stability> The transparent conductive films of each example and each 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 optically transparent conductive layer were measured. The results are shown in Table 1.

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

[0181] That is, the heat stability (R2 / R1) is an evaluation of the amount of change in the resistance value when the crystalline optically transparent conductive layer is reheated, and the closer the value is to 1, the better the heat stability. The results are shown in Table 1.

[0182] <Appearance> The transparent conductive films of each example and each comparative example were left standing on a horizontal table, and the occurrence of wrinkles and streaks was checked. When processing and incorporating the products, they were evaluated based on the presence or absence of practical problems (coating unevenness when forming a layer with the necessary functions of the product on the ITO film and appearance unevenness in the touch panel). 〇: It was at a level where there were no appearance problems in practical use. ×: It was at a level where the appearance was a problem in practical use.

[0183] <Measurement of the grain size of crystal grains> The transparent conductive films of the examples and comparative examples were cut out and fixed to the sample holder of an ultramicrotome. Next, a microtome knife was installed at an extremely acute angle with respect to the ITO film surface, and cutting was performed so that the cut surface was substantially parallel to the ITO film surface to obtain an observation sample. This observation sample was observed using a transmission electron microscope (magnification: 50,000 times). In the TEM observation photograph, an area of 1.5 μm□ was arbitrarily selected, and among the crystal grains observed in this 1.5 μm area, the largest crystal grain was selected. On the grain boundary of this largest crystal grain, two arbitrary measurement points were arranged, and the distance between the measurement points was obtained as the straight-line distance. In this measurement, among the distances between the measurement points, the distance between the measurement points with the maximum distance between the measurement points was taken as the grain size. The results are shown in Table 1.

[0184] <Identification of krypton atoms> Using a scanning fluorescent X-ray analyzer (manufactured by Rigaku Corporation, ZSX PrimusIV), it was confirmed that the light-transmissive conductive layers of Examples 1 to 3 and Comparative Example 6 contained krypton atoms. Specifically, under the following conditions, repeated measurements were performed 5 times to calculate the average value of each scanning angle, and an X-ray spectrum was created. The mixing of krypton atoms was identified by confirming that a peak appeared in the vicinity of 28.2° in the created X-ray spectrum. <Measurement conditions> Spectrum: Kr-KA Measurement diameter: 30 mm Atmosphere: Vacuum Target: Rh Tube voltage: 50 kV Tube current: 60 mA Primary filter: Ni40 Scanning Angle (deg): 27.0 - 29.5 Step (deg): 0.020 Speed (Deg / min): 0.75 Attenuator: 1 / 1 Slit: S2 Diffraction Crystal: LiF(200) Detector: SC PHA: 100 - 300

[0185] [Table 1]

[0186] Note that the above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be construed in a limiting sense. Modifications of the present invention that are obvious to those skilled in the art are 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 preferably 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 transmissive heaters), and lighting.

Explanation of Reference Numerals

[0188] 1 Transparent Conductive Film 2 Substrate Layer 3 Light Transmissive Conductive Layer 4 Transparent Substrate

Claims

1. A transparent conductive film comprising a base material layer and a light-transmissive conductive layer in this order, wherein the base material layer includes a resin layer, the light-transmissive conductive layer contains krypton atoms and does not contain argon atoms, the thickness of the light-transmissive conductive layer is 40 nm or more, the light-transmissive conductive layer has a peak in the X-ray spectrum measured by a scanning fluorescent X-ray analyzer in the vicinity of 28.2°, and the light-transmissive conductive layer is crystalline and contains crystal grains having a particle size of 200 nm or more. A transparent conductive film characterized by the above.

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

3. The transparent conductive film according to Claim 1 or 2, wherein the light-transmissive conductive layer contains indium tin composite oxide.

4. The transparent conductive film according to any one of Claims 1 to 3, wherein the light-transmissive 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 control element comprising the transparent conductive film according to any one of Claims 1 to 4.

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