KR102695635B1 - Transparent conductive film - Google Patents

Abstract

The transparent conductive film (X) of the present invention comprises a transparent resin substrate (10) and a crystalline transparent conductive layer (20) in this order in the thickness direction (D). The transparent conductive layer (20) contains a rare gas atom having an atomic number greater than argon. The transparent conductive layer (20) has a first resistance value R1 (Ω/□) and, after heat treatment under heating conditions at 160° C. for 30 minutes, has a second resistance value R2 (Ω/□). The ratio of the second resistance value R2 to the first resistance value R1 is 0.650 or more and 0.990 or less.

Description

Transparent conductive film

The present invention relates to a transparent conductive film.

Conventionally, a transparent conductive film is known that includes a transparent base film made of resin and a transparent conductive layer (transparent conductive layer) in that order in the thickness direction. The transparent conductive layer is used as a conductive film for forming a transparent electrode in various devices such as a liquid crystal display, a touch panel, and a solar cell, for example. The transparent conductive layer is formed by forming a film of a conductive oxide on a base film by, for example, a sputtering method. A technology related to such a transparent conductive film is described, for example, in the following Patent Document 1.

Japanese Patent Publication No. 2017-71850

Conventional transparent conductive films are manufactured, for example, as follows. First, an amorphous transparent conductive layer is formed on a substrate film in a deposition chamber of a sputter deposition device. Next, the transparent conductive layer on the substrate film is heated in a hot-air heating oven. By this heating, the transparent conductive layer is converted from an amorphous state to a crystalline state (crystallization process). The higher the heating temperature, the higher the crystallinity of the formed crystalline transparent conductive layer, and the lower the resistance value of the same layer.

If the heating temperature in the crystallization process is too high, problems such as dimensional change and deformation occur in the resin base film. Therefore, in the crystallization process, it is necessary to heat the transparent conductive layer at a temperature that does not cause such problems (a temperature that is not too high).

However, in the case of a conventional transparent conductive film having a transparent conductive layer crystallized in the crystallization process described above, when a relatively high-temperature heating process is performed during the manufacturing process of a device including the copper film, the resistance value of the transparent conductive layer may increase. An increase in the resistance value of the transparent conductive layer in the transparent conductive film after manufacturing is undesirable because it affects the performance of the device.

The present invention provides a transparent conductive film suitable for suppressing an increase in the resistance value of a transparent conductive layer due to heating during a device manufacturing process.

The present invention [1] includes a transparent conductive film comprising a transparent resin substrate and a crystalline transparent conductive layer in this order in the thickness direction, wherein the transparent conductive layer contains a rare gas atom having an atomic number greater than argon, the transparent conductive layer has a first resistance value R1 (Ω/□), and after heat treatment under heating conditions of 160°C and 30 minutes, has a second resistance value R2 (Ω/□), and the ratio of the second resistance value R2 to the first resistance value R1 is 0.650 or more and 0.990 or less.

The present invention [2] includes a transparent conductive film as described in [1], wherein the transparent conductive layer includes an indium tin composite oxide layer having a tin oxide content of less than 10 mass%.

The present invention [3] includes a transparent conductive film as described in [1] or [2], wherein the transparent conductive layer has a thickness of 150 nm or less.

The present invention [4] includes a transparent conductive film according to any one of [1] to [3], wherein the first resistance value R1 is 220Ω/□ or less.

The transparent conductive film of the present invention, as described above, has a crystalline transparent conductive layer containing a rare gas atom having an atomic number larger than argon, and in the transparent conductive layer, a ratio (R2/R1) of the second resistance value R2 after heat treatment under heating conditions of 160°C and 30 minutes to the first resistance value R1 (before heat treatment) is 0.650 or more and 0.990 or less. In the transparent conductive film, the second resistance value R2 after heat treatment (160°C, 30 minutes) is suitably smaller than the first resistance value R1 before heat treatment. Such a transparent conductive film is suitable for suppressing an increase in the resistance value of a transparent conductive layer due to heating in a device manufacturing process.

Figure 1 is a cross-sectional schematic diagram of one embodiment of the transparent conductive film of the present invention.
Figure 2 shows a case where the transparent conductive layer includes multiple layers.
Fig. 3 shows a method for manufacturing a transparent conductive film shown in Fig. 1. Fig. 3A shows a process for preparing a resin film, Fig. 3B shows a process for forming a functional layer on a resin film, Fig. 3C shows a process for forming a transparent conductive layer on a functional layer, and Fig. 3D shows a process for crystallizing the transparent conductive layer.
FIG. 4 shows a case where a transparent conductive layer is patterned in the transparent conductive film shown in FIG. 1.

As one embodiment of the transparent conductive film of the present invention, a transparent conductive film (X) comprises a transparent resin substrate (10) and a transparent conductive layer (20) in this order in the thickness direction D. The transparent conductive film (X) has a sheet shape extending in a direction (plane direction) orthogonal to the thickness direction D. The transparent conductive film (X) is an element provided in a touch sensor device, a light control element, a photoelectric conversion element, a heat ray control element, an antenna element, an electromagnetic shield element, a heater element, a lighting device, an image display device, and the like.

In this embodiment, the transparent resin substrate (10) comprises a resin film (11) and a functional layer (12) in this order in the thickness direction D.

The resin film (11) is a substrate that secures the strength of the transparent conductive film (X). In addition, the resin film (11) is a transparent resin film having flexibility. Examples of the material for the resin film (11) include polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyethersulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, and polystyrene resin. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin resin include polyethylene, polypropylene, and cycloolefin polymer. Examples of the acrylic resin include polymethacrylate. Examples of the material for the resin film (11) include, for example, from the viewpoint of transparency and strength, a polyester resin is preferably used, and more preferably PET is used.

The surface of the functional layer (12) side of the resin film (11) may be surface modified. Examples of the surface modified treatment include corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.

The thickness of the resin film (11) is preferably 1 µm or more, more preferably 10 µm or more, and even more preferably 30 µm or more, from the viewpoint of securing the strength of the transparent conductive film (X). The thickness of the resin film (11) is preferably 500 µm or less, more preferably 300 µm or less, even more preferably 200 µm or less, still more preferably 100 µm or less, and particularly preferably 75 µm or less, from the viewpoint of securing the handleability of the resin film (11) in a roll-to-roll method.

The total light transmittance (JIS K 7375-2008) of the resin film (11) is preferably 60% or more, more preferably 80% or more, and even more preferably 85% or more. This configuration is suitable for securing the transparency required for the transparent conductive film (X) when the transparent conductive film (X) is provided in a touch sensor device, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic shield member, a heater member, a lighting device, an image display device, and the like. The total light transmittance of the resin film (11) is, for example, 100% or less.

The functional layer (12) is arranged on one side of the thickness direction D of the resin film (11). In the present embodiment, the functional layer (12) is in contact with the resin film (11). In addition, in the present embodiment, the functional layer (12) is a hard coat layer for making it difficult for scratches to form on the exposed surface (the upper surface in FIG. 1) of the transparent conductive layer (20).

The hard coat layer is a cured product of a curable resin composition. The curable resin composition contains a curable resin. Examples of the curable resin include polyester resin, acrylic urethane resin, acrylic resin (excluding acrylic urethane resin), urethane resin (excluding acrylic urethane resin), amide resin, silicone resin, epoxy resin, and melamine resin. These curable resins may be used alone, or two or more types may be used in combination. From the viewpoint of securing high hardness of the hard coat layer, at least one selected from the group consisting of acrylic urethane resin and acrylic resin is preferably used as the curable resin.

In addition, as the curable resin, examples thereof include ultraviolet-curable resins and thermosetting resins. From the viewpoint that it is helpful in improving the manufacturing efficiency of the transparent conductive film (X) because it can be cured without high-temperature heating, ultraviolet-curable resins are preferable as the curable resin.

The curable resin composition may contain particles. Examples of the particles include inorganic oxide particles and organic particles. Examples of the inorganic oxide particle material include silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. Examples of the organic particle material include polymethyl methacrylate, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate.

The surface of the transparent conductive layer (20) side of the functional layer (12) may be surface modified. Examples of the surface modified treatment include corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.

The thickness of the functional layer (12) as a hard coat layer is preferably 0.1 µm or more, more preferably 0.5 µm or more, and even more preferably 1 µm or more, from the viewpoint of exhibiting sufficient abrasion resistance in the transparent conductive layer (20). The thickness of the functional layer (12) as a hard coat layer is preferably 20 µm or less, more preferably 10 µm or less, even more preferably 5 µm or less, and especially preferably 3 µm or less, from the viewpoint of ensuring transparency of the functional layer (12).

The thickness of the transparent resin substrate (10) is preferably 1 µm or more, more preferably 10 µm or more, even more preferably 15 µm or more, and particularly preferably 30 µm or more. The thickness of the transparent resin substrate (10) is preferably 520 µm or less, more preferably 320 µm or less, even more preferably 220 µm or less, still more preferably 120 µm or less, and particularly preferably 80 µm or less. These configurations regarding the thickness of the transparent resin substrate (10) are suitable for ensuring the handleability of the transparent conductive film (X).

The total light transmittance (JIS K 7375-2008) of the transparent resin substrate (10) is preferably 60% or more, more preferably 80% or more, and even more preferably 85% or more. This configuration is suitable for securing the transparency required for the transparent conductive film (X) when the transparent conductive film (X) is provided in a touch sensor device, a light control element, a photoelectric conversion element, a heat ray control element, an antenna element, an electromagnetic shield element, a heater element, a lighting device, an image display device, and the like. The total light transmittance of the transparent resin substrate (10) is, for example, 100% or less.

The transparent conductive layer (20) is arranged on one side of the thickness direction D of the transparent resin substrate (10). In the present embodiment, the transparent conductive layer (20) is in contact with the transparent resin substrate (10). The transparent conductive layer (20) is a crystalline film having both light transmittance and conductivity. This transparent conductive layer (20) is formed of, for example, a conductive oxide. The fact that the transparent conductive layer (20) is a crystalline film is suitable for suppressing a large change in the resistance value due to subsequent heating in the transparent conductive layer (20).

Whether the transparent conductive layer (the transparent conductive layer (20) on the transparent resin substrate (10) in the transparent conductive film (X)) is a crystalline film can be judged by observation of the transparent conductive layer in the plane using a transmission electron microscope (TEM). In the observation of the transparent conductive layer in the plane using a TEM, if no amorphous region is confirmed and crystal grains are confirmed, it can be judged that the transparent conductive layer is a crystalline film. In the production of a sample for observation in the plane of the transparent conductive layer in the transparent conductive film, after fixing the transparent conductive film to a sample holder of an ultramicrotome, a microtome knife is installed at an extremely acute angle with respect to the transparent conductive layer, and the transparent conductive layer is cut by the knife so as to be approximately parallel to the exposed surface of the transparent conductive layer. Thereby, a transparent conductive layer sample as a sample for observation in the plane can be obtained.

Whether the transparent conductive layer is a crystalline film can also be determined by cross-sectional observation of the transparent conductive layer using a field emission transmission electron microscope (FE-TEM). In cross-sectional observation of the transparent conductive layer using FE-TEM, if no amorphous region is confirmed but crystal grains are confirmed, it can be determined that the transparent conductive layer is a crystalline film. A method for confirming that the transparent conductive layer is a crystalline film using FE-TEM is as specifically described later with respect to the examples.

Whether the transparent conductive layer is a crystalline film can also be determined by, for example, the following method. First, the transparent conductive layer is immersed in 5 mass% hydrochloric acid at 20°C for 15 minutes. Next, the transparent conductive layer is washed with water and then dried. Next, on the exposed plane of the transparent conductive layer (in the transparent conductive film (X), the surface opposite to the transparent resin substrate (10) in the transparent conductive layer (20)), the resistance (terminal-to-terminal resistance) between a pair of terminals with a separation distance of 15 mm is measured. In this measurement, if the terminal-to-terminal resistance is 10 kΩ or less, it can be determined that the transparent conductive layer is a crystalline film.

As the conductive oxide, examples thereof include indium-containing conductive oxides and antimony-containing conductive oxides. Examples thereof include indium-tin composite oxide (ITO), indium-zinc composite oxide (IZO), indium-gallium composite oxide (IGO), and indium-gallium-zinc composite oxide (IGZO). Examples thereof include antimony-tin composite oxide (ATO). From the viewpoint of realizing high transparency and good electrical conductivity, an indium-containing conductive oxide is preferably used as the conductive oxide, and ITO is more preferably used. This ITO may contain a metal or metalloid other than In and Sn in an amount less than the respective contents of In and Sn.

The transparent conductive layer (20) (crystalline) preferably includes an indium-tin composite oxide layer (first ITO layer) having a tin oxide ratio of less than 10 mass%. The tin oxide ratio in the ITO layer is specifically the ratio of the tin oxide content to the total content of indium oxide (In ₂ O ₃ ) and tin oxide (SnO ₂ ) in the ITO forming the same layer. The transparent conductive layer (20) including the first ITO layer is formed by crystallization by heating of the transparent conductive layer (20') after an amorphous transparent conductive layer (20') including the first ITO layer is formed, as described later. The transparent conductive layer (20) including the first ITO layer is suitable for forming an amorphous transparent conductive layer (later transparent conductive layer (20')) in which an increase in resistance value due to heating is suppressed after heat crystallization.

The tin oxide ratio of the first ITO layer is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, even more preferably 1 mass% or more, still more preferably 1.5 mass% or more, and particularly preferably 2 mass% or more, from the viewpoint of ensuring the durability of the transparent conductive layer (20). The tin oxide ratio of the first ITO layer is preferably 9.9 mass% or less, more preferably 9 mass% or less, even more preferably 8 mass% or less, still more preferably 6 mass% or less, still more preferably 5 mass% or less, and particularly preferably 4 mass% or less, from the viewpoint of facilitating the formation of an amorphous transparent conductive layer in the sputtering film formation described later and of suppressing an increase in the resistance value of the transparent conductive layer (20) due to heating after heat crystallization.

The tin oxide ratio in ITO can be identified, for example, as follows. First, the existence ratio of indium atoms (In) and tin atoms (Sn) in ITO as a measurement target is obtained by X-ray photoelectron spectroscopy. From the respective existence ratios of In and Sn in the ITO, the ratio of the number of Sn atoms to the number of In atoms in the ITO is obtained. Thereby, the tin oxide ratio in the ITO is obtained. In addition, the tin oxide ratio in ITO can also be specified from the tin oxide (SnO ₂ ) content ratio of the ITO target used during sputtering deposition.

The transparent conductive layer (20) may include other layers than the first ITO layer (tin oxide ratio less than 10 mass%). The other layers may include, for example, an ITO layer (second ITO layer) having a tin oxide ratio of 10 mass% or more, and a layer formed of a conductive oxide other than ITO. From the viewpoint of achieving both high transparency and good electrical conductivity of the transparent conductive layer (20), the other layer is preferably the second ITO layer.

The tin oxide ratio of the second ITO layer (tin oxide ratio of 10 mass% or more) is preferably 11 mass% or more, more preferably 12 mass% or more, and even more preferably 13 mass% or more, from the viewpoint of reducing the resistance value of the transparent conductive layer (20) after heat crystallization. The tin oxide ratio of the second ITO layer is preferably 30 mass% or less, more preferably 20 mass% or less, and even more preferably 15 mass% or less, from the viewpoint of ensuring the crystallinity of the transparent conductive layer (20) after heating.

FIG. 2 is an example of a case where the transparent conductive layer (20) is formed of a plurality of layers including a first ITO layer, and exemplarily shows a case where the transparent conductive layer (20) is formed of two layers, a first layer (21) and a second layer (22). In FIG. 2, the first layer (21) or the second layer (22) is the first ITO layer. From the viewpoint of suppressing an increase in the resistance value due to heating of the transparent conductive layer (20) after heat crystallization, it is preferable that the second layer (22) is the first ITO layer.

The thickness of the transparent conductive layer (20) is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more, from the viewpoint of reducing the resistance of the transparent conductive layer (20). In addition, the thickness of the transparent conductive layer (20) is preferably 300 nm or less, more preferably 150 nm or less, even more preferably 120 nm or less, still more preferably 100 nm or less, and especially preferably 80 nm or less, from the viewpoint of suppressing cracking due to heating in the transparent conductive layer (20).

When the transparent conductive layer (20) includes a first layer (21) and a second layer (22), the ratio of the thickness of the second layer (22) to the total thickness of the first layer (21) and the second layer (22) is, from the viewpoint of lowering the resistance of the transparent conductive layer (20), preferably 1% or more, more preferably 5% or more, and even more preferably 7% or more. In addition, the ratio of the thickness of the second layer (22) to the total thickness of the first layer (21) and the second layer (22) is, from the viewpoint of ensuring high crystallinity in the transparent conductive layer (20) after heating, preferably 99% or less, more preferably 95% or less, even more preferably 90% or less, still more preferably 60% or less, and particularly preferably 50% or less.

The transparent conductive layer (20) contains a noble gas atom (atom E) having an atomic number higher than argon. Examples of such noble gas atoms include krypton (Kr) and xenon (Xe), and Kr is preferably used. In addition, the transparent conductive layer (20) may contain argon (Ar). The noble gas atoms in the transparent conductive layer (20), in this embodiment, are derived from noble gas atoms used as sputtering gas in the sputtering method described later for forming the transparent conductive layer (20). In this embodiment, the transparent conductive layer (20) is a film (sputtered film) formed by the sputtering method. The transparent conductive layer (20) containing the atom E is formed by crystallization by heating of the transparent conductive layer (20') after an amorphous transparent conductive layer (20') containing the atom E is formed, as described later. The transparent conductive layer (20) containing the atom E is suitable for forming an amorphous transparent conductive layer (transparent conductive layer (20') described later) in which an increase in resistance value due to heating after thermal crystallization is suppressed. Specific methods for determining whether the transparent conductive layer (20) contains the atom E include, for example, fluorescence X-ray analysis and Rutherford backscattering spectrometry (RBS).

The content ratio of atoms E such as Kr in the transparent conductive layer (20) is preferably 1 atomic% or less, more preferably 0.5 atomic% or less, even more preferably 0.3 atomic% or less, and particularly preferably 0.2 atomic% or less in the entire thickness direction D. This configuration is suitable for realizing good crystal growth when crystallizing the amorphous transparent conductive layer (20') by heating, and therefore is suitable for obtaining a low-resistance transparent conductive layer (20). The content ratio of atoms E in the transparent conductive layer (20) is preferably 0.0001 atomic% or more in the entire thickness direction D. Examples of methods for identifying the content ratio of noble gas atoms in the transparent conductive layer (20) include fluorescence X-ray analysis and Rutherford backscattering spectrometry (RBS).

When the transparent conductive layer (20) includes a plurality of layers, the transparent conductive layer (20) may include a layer containing the atom E (the atom E-containing layer) and a layer not containing the atom E (the atom E-free layer). The atom E-free layer is, for example, a layer formed by sputtering film formation using argon as a sputtering gas. In the transparent conductive layer (20) shown in Fig. 2, the first layer (21) or the second layer (22) contains the atom E. From the viewpoint of securing the crystallinity of the transparent conductive layer (20) after heating, it is preferable that the first layer (21) contains the atom E.

When the transparent conductive layer (20) includes an atomic E-containing layer and an atomic E-free layer, the ratio of the thickness of the atomic E-containing layer to the total thickness of the atomic E-containing layer and the atomic E-free layer is, from the viewpoint of increasing the crystallinity of the transparent conductive layer (20) after heating and thus improving the transmittance, preferably 5% or more, more preferably 10% or more, even more preferably 20% or more, still more preferably 30% or more, and particularly preferably 40% or more. This ratio is, from the viewpoint of reducing the dimensional shrinkage rate of the transparent conductive layer (20) after heating, preferably 99% or less, more preferably 90% or less, still more preferably 80% or less, still more preferably 70% or less, and particularly preferably 60% or less.

The transparent conductive layer (20) has a first resistance value R1 (Ω/□), and after heat treatment under heating conditions of 160°C and 30 minutes, has a second resistance value R2 (Ω/□). The resistance values R1 and R2 are each expressed as surface resistivity. The surface resistivity can be measured by a four-terminal method based on JIS K 7194 (1994). The method for measuring the resistance values R1 and R2 is as specifically described later with respect to the examples.

The ratio R2/R1 of the second resistance value R2 to the first resistance value R1 is, from the viewpoint of suppressing an increase in the resistance value due to subsequent heating of the transparent conductive layer (20), 0.990 or less, preferably 0.950 or less, more preferably 0.900 or less, and even more preferably 0.880 or less. Furthermore, from the viewpoint of suppressing a change in the resistance value due to subsequent heating of the transparent conductive layer (20), the ratio R2/R1 is 0.650 or more, preferably 0.700 or more, and more preferably 0.800 or more.

The difference R1-R2 between the first resistance value R1 and the second resistance value R2 is, from the viewpoint of suppressing an increase in the resistance value due to subsequent heating in the transparent conductive layer (20), preferably 1.5Ω/□ or more, more preferably 3Ω/□ or more, even more preferably 4Ω/□ or more, still more preferably 5Ω/□ or more, and particularly preferably 6Ω/□ or more. Furthermore, from the viewpoint of suppressing a change in the resistance value due to subsequent heating of the transparent conductive layer (20), the difference R1-R2 is preferably 10Ω/□ or less, more preferably 9.5Ω/□ or less, even more preferably 9Ω/□ or less, and particularly preferably 8Ω/□ or less.

From the viewpoint of lowering the resistance of the transparent conductive layer (20), the first resistance value R1 is preferably 240Ω/□ or less, more preferably 220Ω/□ or less, even more preferably 200Ω/□ or less, still more preferably 180Ω/□ or less, still more preferably 160Ω/□ or less, and particularly preferably 150Ω/□ or less. The first resistance value R1 is, for example, 1Ω/□ or more. The first resistance value R1 can be controlled, for example, by adjusting various conditions when sputtering to form the transparent conductive layer (20) (the same applies to the second resistance value R2). Examples of the conditions include the temperature of the substrate (the transparent resin substrate (10) in the present embodiment) on which the transparent conductive layer (20) is formed, the amount of oxygen introduced into the formation room, the air pressure in the formation room, and the horizontal magnetic field strength on the target.

From the viewpoint of lowering the resistance of the transparent conductive layer (20), the second resistance value R2 is preferably 240Ω/□ or less, more preferably 220Ω/□ or less, even more preferably 200Ω/□ or less, still more preferably 180Ω/□ or less, still more preferably 160Ω/□ or less, and particularly preferably 150Ω/□ or less. The second resistance value R2 is, for example, 1Ω/□ or more.

The total light transmittance (JIS K 7375-2008) of the transparent conductive layer (20) is preferably 60% or more, more preferably 80% or more, and even more preferably 85% or more. This configuration is suitable for securing transparency in the transparent conductive layer (20). In addition, the total light transmittance of the transparent conductive layer (20) is, for example, 100% or less.

A transparent conductive film (X) is manufactured, for example, as follows.

First, as shown in Fig. 3A, a resin film (11) is prepared.

Next, as shown in Fig. 3B, a functional layer (12) is formed on one side of the thickness direction D of the resin film (11). A transparent resin substrate (10) is produced by forming the functional layer (12) on the resin film (11).

The above-described functional layer (12) as a hard coat layer can be formed by applying a curable resin composition on a resin film (11) to form a coating film, and then curing the coating film. When the curable resin composition contains an ultraviolet-curable resin, the coating film is cured by ultraviolet irradiation. When the curable resin composition contains a thermosetting resin, the coating film is cured by heating.

The exposed surface of the functional layer (12) formed on the resin film (11) is subjected to surface modification treatment as needed. In the case of plasma treatment as the surface modification treatment, an inert gas, for example, argon gas, is used. In addition, the discharge power in the plasma treatment is, for example, 10 W or more, and further, for example, 5000 W or less.

Next, as shown in Fig. 3C, an amorphous transparent conductive layer (20') is formed on a transparent resin substrate (10) (transparent conductive layer forming process). Specifically, a material is deposited as a film on a functional layer (12) in a transparent resin substrate (10) by a sputtering method to form an amorphous transparent conductive layer (20'). The transparent conductive layer (20') is an amorphous film having both light transmittance and conductivity (the transparent conductive layer (20') is converted into a crystalline transparent conductive layer (20) by heating in a crystallization process described later).

In the sputtering method, it is preferable to use a sputtering film-forming apparatus capable of performing a film-forming process in a roll-to-roll manner. In the case of using a roll-to-roll sputtering film-forming apparatus in the manufacture of a transparent conductive film (X), a material is formed as a film on a transparent resin substrate (10) while a long transparent resin substrate (10) is moved from an unwinding roll provided by the apparatus to a winding roll, thereby forming a transparent conductive layer (20'). Furthermore, in the sputtering method, a sputtering film-forming apparatus having one film-forming chamber may be used, or a sputtering film-forming apparatus having a plurality of film-forming chambers sequentially arranged along the travel path of the transparent resin substrate (10) may be used (in the case of forming a transparent conductive layer (20') including the first layer (21) and the second layer (22) described above, a sputtering film-forming apparatus having two or more film-forming chambers is used).

In the sputtering method, specifically, a sputtering gas (inert gas) is introduced into a deposition chamber equipped with a sputtering deposition device under vacuum conditions, while a negative voltage is applied to a target placed on a cathode in the deposition chamber. Thereby, a glow discharge is generated to ionize gas atoms, and the gas ions are collided with the target surface at high speed to bounce the target material from the target surface, and the bounced target material is deposited on a transparent resin substrate (10). As a material of the target, for example, a sintered body of a conductive oxide described above with respect to the transparent conductive layer (20) is used. As the sputtering gas, for example, a noble gas can be mentioned. As the noble gas, for example, argon and krypton can be mentioned. The sputtering gas may be a mixed gas of a plurality of noble gases.

The sputtering method is preferably a reactive sputtering method. In the reactive sputtering method, for example, in addition to the sputtering gas, oxygen as a reactive gas is introduced into the deposition chamber. In the reactive sputtering method, the ratio of the amount of oxygen introduced to the total amount of sputtering gas and oxygen introduced into the deposition chamber is, for example, 0.01% by volume or more, and further, for example, 15% by volume or less.

When forming a transparent conductive layer (20) containing a noble gas atom (atom E) having an atomic number higher than argon (Ar) over the entire thickness direction D (first case), the gas introduced into one or more deposition chambers equipped with a sputtering deposition device contains atom E as a sputtering gas and oxygen as a reactive gas. As the atom E, Kr and Xe can be exemplified as described above, and Kr is preferably used. The sputtering gas may contain an inert gas other than atom E. As the inert gas other than atom E, Ar can be exemplified, for example. When the sputtering gas contains an inert gas other than atom E, the content ratio is preferably 80 vol% or less, and more preferably 50 vol% or less.

When forming a transparent conductive layer (20) including the above-described atomic E-containing layer and atomic E-free layer (second case), the gas introduced into the deposition chamber for forming the atomic E-containing layer contains atomic E as a sputtering gas and oxygen as a reactive gas. The sputtering gas may contain an inert gas other than atomic E. The type and content ratio of the inert gas other than atomic E are the same as the type and content ratio described above for the inert gas other than atomic E in the first case. In addition, the gas introduced into the deposition chamber for forming the atomic E-free layer contains an inert gas other than atomic E as a sputtering gas and oxygen as a reactive gas. As the inert gas other than atomic E, Ar can be exemplified.

The air pressure inside the deposition room during deposition by the sputtering method (sputter deposition) is, for example, 0.02 Pa or more, and further, for example, 1 Pa or less.

The temperature of the transparent resin substrate (10) during sputtering film formation is, for example, 180°C or less. The temperature of the transparent resin substrate (10) during sputtering film formation is, from the viewpoint of suppressing outgassing from the transparent resin substrate (10) during sputtering film formation and appropriately forming an amorphous transparent conductive layer (20'), preferably 20°C or less, more preferably 10°C or less, even more preferably 5°C or less, still more preferably 0°C or less, and particularly preferably -5°C or less. The temperature is, for example, -50°C or more, -20°C or more, or -10°C or more.

Power sources for applying voltage to the target include, for example, a DC power source, an AC power source, an MF power source, and an RF power source. As the power source, a DC power source and an RF power source may be used together. The absolute value of the discharge voltage during sputtering is, for example, 50 V or more, and also, for example, 500 V or less.

In the present manufacturing method, as shown in Fig. 3D, the amorphous transparent conductive layer (20') is then converted into a crystalline transparent conductive layer (20) by heating under vacuum (crystallization process). In the present process, a vacuum heating device having a contact heating unit is used. As the contact heating unit, for example, a heating roll and a heating block can be mentioned. In order to perform the crystallization process in a roll-to-roll manner, a vacuum heating device having a heating roll is preferable. That is, in the present process, it is preferable to heat the transparent conductive layer (20') on the transparent resin substrate (10) by bringing it into contact with the heating roll in the vacuum heating device. Contact heating by the heating roll is suitable for efficiently crystallizing the transparent conductive layer (20') under vacuum.

In this process, the heating temperature is preferably 120°C or higher, more preferably 140°C or higher, and even more preferably 160°C or higher from the viewpoint of securing a high crystallization speed. The heating temperature is preferably less than 200°C, more preferably 180°C or lower, and even more preferably 170°C or lower, from the viewpoint of suppressing the influence of heating on the transparent resin substrate (10). The heating time is preferably 10 seconds or higher, preferably 30 seconds or higher, and even more preferably 45 seconds or higher, from the viewpoint of sufficient crystallization of the transparent conductive layer (20). The heating time is preferably 60 minutes or lower, more preferably 30 minutes or lower, even more preferably 10 minutes or lower, and especially preferably 5 minutes or lower, from the viewpoint of shortening the tact time in this process.

Preferably, a series of processes from the transparent conductive layer forming process described above to the crystallization process are performed on a single continuous line while running the work film in a roll-to-roll manner. More preferably, during the process on a single continuous line, the work film is never released into the atmosphere.

In this manner, a transparent conductive film (X) is manufactured.

The transparent conductive layer (20) in the transparent conductive film (X) may be patterned as schematically shown in Fig. 4. The transparent conductive layer (20) can be patterned by etching the transparent conductive layer (20) through a predetermined etching mask. The patterning of the transparent conductive layer (20) may be performed before the crystallization process described above or after the crystallization process. The patterned transparent conductive layer (20) functions as a wiring pattern, for example.

The transparent conductive film (X), as described above, has a crystalline transparent conductive layer (20) containing noble gas atoms having an atomic number larger than argon. The transparent conductive layer (20) being a crystalline film is suitable for suppressing a large change in resistance value due to subsequent heating in the transparent conductive layer (20). The transparent conductive layer (20) containing noble gas atoms having an atomic number larger than argon is suitable for forming an amorphous transparent conductive layer (20') in which an increase in resistance value due to heating after heat crystallization is suppressed. And, the transparent conductive film (X) has a ratio (R2/R1) of the second resistance value R2 after heat treatment under heating conditions of 160°C and 30 minutes to the first resistance value R1 (before heat treatment) of 0.650 or more, preferably 0.70 or more, more preferably 0.80 or more, and further preferably 0.990 or less, more preferably 0.950 or less, even more preferably 0.900 or less, and particularly preferably 0.880 or less. That is, in the transparent conductive film, the second resistance value R2 after heat treatment (160°C, 30 minutes) is suitably smaller than the first resistance value R1 before heat treatment. The transparent conductive film as described above is suitable for suppressing an increase in the resistance value of a transparent conductive layer due to heating during a device manufacturing process.

In the transparent conductive film (X), the functional layer (12) may be an adhesion-improving layer for realizing high adhesion of the transparent conductive layer (20) to the transparent resin substrate (10). A configuration in which the functional layer (12) is an adhesion-improving layer is suitable for securing adhesion between the transparent resin substrate (10) and the transparent conductive layer (20).

The functional layer (12) may be an index-matching layer for adjusting the reflectivity of the surface (one side in the thickness direction D) of the transparent resin substrate (10). A configuration in which the functional layer (12) is an index-matching layer is suitable for making it difficult to recognize the pattern shape of the transparent conductive layer (20) when the transparent conductive layer (20) on the transparent resin substrate (10) is patterned.

The functional layer (12) may be a peeling functional layer for practically enabling peeling of the transparent conductive layer (20) from the transparent resin substrate (10). A configuration in which the functional layer (12) is a peeling functional layer is suitable for peeling the transparent conductive layer (20) from the transparent resin substrate (10) and transferring the transparent conductive layer (20) to another member.

The functional layer (12) may be a composite layer in which a plurality of layers are connected in the thickness direction D. The composite layer preferably includes two or more layers selected from the group consisting of a hard coat layer, an adhesion improving layer, a refractive index adjusting layer, and a peeling functional layer. This configuration is suitable for compositely expressing the above-described functions of each of the selected layers in the functional layer (12). In one preferred embodiment, the functional layer (12) is provided with an adhesion improving layer, a hard coat layer, and a refractive index adjusting layer in this order toward one side of the thickness direction D on a resin film (11). In another preferred embodiment, the functional layer (12) is provided with a peeling functional layer, a hard coat layer, and a refractive index adjusting layer in this order toward one side of the thickness direction D on a resin film (11).

The transparent conductive film (X) is fixed to the article, and is also used in a state where the transparent conductive layer (20) is patterned, as needed. The transparent conductive film (X) is bonded to the article, for example, via a fixing functional layer.

As articles, examples thereof include elements, members, and devices. That is, as articles to which a transparent conductive film is attached, examples thereof include transparent conductive film attachment elements, transparent conductive film attachment members, and transparent conductive film attachment devices.

As the components, examples thereof include dimming elements and photoelectric conversion elements. As the dimming elements, examples thereof include current-driven dimming elements and field-driven dimming elements. As the current-driven dimming elements, examples thereof include electrochromic (EC) dimming elements. As the electric field-driven dimming elements, examples thereof include PDLC (polymer dispersed liquid crystal) dimming elements, PNLC (polymer network liquid crystal) dimming elements, and SPD (suspended particle device) dimming elements. As the photoelectric conversion elements, examples thereof include solar cells and the like. As the solar cells, examples thereof include organic thin-film solar cells and dye-sensitized solar cells. As the members, examples thereof include electromagnetic shield members, heat control members, heater members, and antenna members. As the devices, examples thereof include touch sensor devices, lighting devices, and image display devices.

As the above-mentioned fixing functional layer, for example, an adhesive layer and an adhesive layer can be mentioned. As a material of the fixing functional layer, as long as it is transparent and exhibits a fixing function, it can be used without particular limitation. The fixing functional layer is preferably formed of a resin. As the resin, for example, an acrylic resin, a silicone resin, a polyester resin, a polyurethane resin, a polyamide resin, a polyvinyl ether resin, a vinyl acetate/vinyl chloride copolymer, a modified polyolefin resin, an epoxy resin, a fluororesin, natural rubber, and a synthetic rubber can be mentioned. In view of exhibiting adhesive properties such as cohesiveness, adhesiveness, and appropriate wettability, having excellent transparency, and having excellent weather resistance and heat resistance, an acrylic resin is preferable as the resin.

A corrosion inhibitor may be mixed into the fixing functional layer (resin forming the fixing functional layer) to suppress corrosion of the transparent conductive layer (20). A migration inhibitor (for example, a material disclosed in Japanese Patent Application Laid-Open No. 2015-022397) may be mixed into the fixing functional layer (resin forming the fixing functional layer) to suppress migration of the transparent conductive layer (20). In addition, an ultraviolet absorber may be mixed into the fixing functional layer (resin forming the fixing functional layer) to suppress deterioration of the product during outdoor use. Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxalic acid anilide compounds, cyanoacrylate compounds, and triazine compounds.

In addition, when the transparent resin substrate (10) of the transparent conductive film (X) is fixed to the article via a fixing functional layer, the transparent conductive layer (20) (including the transparent conductive layer (20) after patterning) in the transparent conductive film (X) is exposed. In this case, a cover layer may be disposed on the exposed surface of the transparent conductive layer (20). The cover layer is a layer that covers the transparent conductive layer (20), and can improve the reliability of the transparent conductive layer (20) and also suppress functional deterioration due to scratches on the transparent conductive layer (20). Such a cover layer is preferably formed of a dielectric material, and more preferably formed of a composite material of a resin and an inorganic material. As the resin, for example, the resin described above with respect to the fixing functional layer can be exemplified. As the inorganic material, for example, inorganic oxides and fluorides can be exemplified. Examples of inorganic oxides include silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide, and calcium oxide. Examples of fluorides include magnesium fluoride. In addition, the cover layer (a mixture of resin and inorganic material) may contain the above-described corrosion inhibitor, migration inhibitor, and ultraviolet absorber.

Example

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples. In addition, the specific numerical values of the mixing amount (content), physical property values, parameters, etc. described below can be replaced with the upper limit (a numerical value defined as “not more than” or “less than”) or lower limit (a numerical value defined as “not less than” or “exceeds”) of the mixing amount (content), physical property values, parameters, etc. corresponding to them described in the above-described “Specific Description for Carrying Out the Invention.”

〔Example 1〕

An ultraviolet-curable resin containing an acrylic resin was applied to one side of a long polyethylene terephthalate (PET) film (thickness: 50 μm, manufactured by Toray Industries, Inc.) as a transparent resin film to form a coating film. Next, the coating film was cured by ultraviolet irradiation to form a hard coat layer (thickness: 2 μm). In this way, a transparent resin substrate comprising a resin film and a hard coat (HC) layer as a functional layer was manufactured.

Next, an amorphous transparent conductive layer was formed on the HC layer in the transparent resin substrate by a reactive sputtering method (transparent conductive layer forming process). In this process, a roll-to-roll type sputtering film forming device (DC magnetron sputtering film forming device) was used. The device has a first film forming room and a second film forming room capable of performing a film forming process while running a work film in a roll-to-roll manner. In this process, specifically, the first sputtering film forming in the first film forming room and the second sputtering film forming in the second film forming room were sequentially performed. In the first sputtering film forming, a first layer (thickness 11 nm) was formed on the transparent resin substrate. In the subsequent second sputtering film forming, a second layer (thickness 11 nm) was formed on the first layer. The conditions for each sputtering film forming in this example are as follows.

In the first sputter deposition, the inside of the sputter deposition apparatus (the first deposition chamber, the second deposition chamber) was evacuated until the ultimate vacuum inside the first deposition chamber reached 0.9×10 ^-4 Pa, and then krypton as a sputtering gas and oxygen as a reactive gas were introduced into the first deposition chamber, and the atmospheric pressure inside the first deposition chamber was set to 0.2 Pa. The ratio of the amount of oxygen introduced to the total amount of krypton and oxygen introduced into the first deposition chamber was set to approximately 1.8% by mass. In addition, as a target, a first sintered body of indium oxide and tin oxide (tin oxide concentration: 10 mass%) was used. A DC power supply was used as a power supply for applying voltage to the target. The horizontal magnetic field strength on the target was set to 90 mT. The deposition temperature (temperature of the transparent resin substrate on which the transparent conductive layer is laminated) was set to -5°C.

In the second sputtering deposition, after the sputtering deposition apparatus was vacuum-evacuated, krypton as a sputtering gas and oxygen as a reactive gas were introduced into the second deposition chamber, and the atmospheric pressure in the second deposition chamber was set to 0.2 Pa. The ratio of the amount of oxygen introduced to the total amount of krypton and oxygen introduced into the second deposition chamber was set to approximately 1.8% by mass. In addition, as a target, a second sintered body of indium oxide and tin oxide (tin oxide concentration of 3 mass%) was used. A DC power supply was used as a power source for applying voltage to the target. The horizontal magnetic field strength on the target was set to 90 mT. The deposition temperature was set to -5°C.

Next, the transparent conductive layer on the transparent resin substrate was heated by contacting it with a heating roll in a vacuum heating device and crystallized (crystallization process). In this process, the heating temperature was 160°C, the heating time was 1 minute, and the transparent conductive layer was heated and crystallized under vacuum.

A series of processes from the transparent conductive layer formation process described above to the crystallization process were carried out on a single continuous line while running the work film in a roll-to-roll manner. During this process, the work film never comes out into the air.

In this manner, the transparent conductive film of Example 1 was produced. The transparent conductive layer (thickness 22 nm) of the transparent conductive film of Example 1 has a first layer of ITO (tin oxide ratio of 10 mass%, thickness 11 nm) and a second layer of ITO (tin oxide ratio of 3 mass%, thickness 11 nm), in that order from the transparent resin substrate side, and is crystalline (with respect to the thickness of the transparent conductive layer, the ratio of the thickness of the first layer is 50%, and the ratio of the thickness of the second layer is 50%).

〔Example 2〕

A transparent conductive film of Example 2 was produced in the same manner as the transparent conductive film of Example 1, except for the following. In the first sputtering deposition of the transparent conductive layer forming process, a first layer (amorphous) having a thickness of 22 nm was formed, and in the second sputtering deposition, a second sintered body (having a tin oxide concentration of 10 mass%) was used as a target to form a second layer (amorphous) having a thickness of 22 nm.

The transparent conductive layer of the transparent conductive film of Example 2 is made of an ITO film (tin oxide concentration 10 mass%, thickness 44 nm) and is crystalline.

〔Example 3〕

A transparent conductive film of Example 3 was produced in the same manner as the transparent conductive film of Example 1, except for the following. In the first sputtering deposition of the transparent conductive layer forming process, a first layer (amorphous) having a thickness of 22 nm was formed, and in the second sputtering deposition, argon was used as a sputtering gas and a second sintered body (having a tin oxide concentration of 10 mass%) was used as a target, thereby forming a second layer (amorphous) having a thickness of 22 nm.

The transparent conductive layer of the transparent conductive film of Example 3 is composed of a first layer containing krypton (tin oxide concentration of 10 mass%, thickness of 22 nm) and a second layer containing argon (tin oxide concentration of 10 mass%, thickness of 22 nm), and is crystalline.

〔Comparative Example 1〕

A transparent conductive film of Comparative Example 1 was produced in the same manner as the transparent conductive film of Example 1, except for the following. In the first sputtering deposition and the second sputtering deposition of the transparent conductive layer forming process, argon was used as a sputtering gas. In the crystallization process, the transparent conductive layer on the transparent resin substrate was heated in a hot air-type heating oven. The heating temperature was 160°C, and the heating time was 1 hour. In this process, the transparent conductive layer was heated and crystallized in the atmosphere.

〔Comparative Example 2〕

A transparent conductive film of Comparative Example 2 was produced in the same manner as the transparent conductive film of Example 1, except for the following. In the first sputtering film formation and the second sputtering film formation of the transparent conductive layer formation process, argon was used as a sputtering gas.

〔Comparative Example 3〕

A transparent conductive film of Comparative Example 3 was produced in the same manner as the transparent conductive film of Example 1, except for the following. In the crystallization process, the transparent conductive layer on the transparent resin substrate was heated in a hot air-type heating oven. The heating temperature was 160°C, and the heating time was 1 hour. In this process, the transparent conductive layer was heated and crystallized in the air.

〔Comparative Example 4〕

A transparent conductive film of Comparative Example 4 was produced in the same manner as the transparent conductive film of Example 1, except for the following. In the first sputtering deposition and the second sputtering deposition of the transparent conductive layer forming process, argon was used as a sputtering gas. In the first sputtering deposition, a first layer (amorphous) having a thickness of 22 nm was formed, and in the second sputtering deposition, a second sintered body (having a tin oxide concentration of 10 mass%) was used as a target to form a second layer (amorphous) having a thickness of 22 nm.

<Thickness of transparent challenge layer>

The thickness of the transparent conductive layer of each transparent conductive film in Examples 1 to 3 and Comparative Examples 1 to 4 was measured by observation using a field emission transmission electron microscope (FE-TEM). Specifically, first, a cross-sectional observation sample of each transparent conductive layer in Examples 1 to 3 and Comparative Examples 1 to 4 was produced by the FIB microsampling method. In the FIB microsampling method, a FIB device (product name "FB2200", manufactured by Hitachi) was used, and the acceleration voltage was set to 10 kV. Next, the cross-section of the transparent conductive layer in the cross-sectional observation sample was observed by FE-TEM, and the thickness of the transparent conductive layer was measured in the observation image. In the observation, an FE-TEM device (product name "JEM-2800", manufactured by JEOL) was used, and the acceleration voltage was set to 200 kV.

The thickness of the first layer of the transparent conductive layer in Examples 1 and 3 and Comparative Examples 1 to 3 was measured by producing a cross-sectional observation sample from an intermediate product before forming a second layer on the first layer and observing the sample using FE-TEM. The thickness of the second layer of each transparent conductive layer in Examples 1 and 3 and Comparative Examples 1 to 3 was obtained by subtracting the thickness of the first layer from the total thickness of each transparent conductive layer in Examples 1 and 3 and Comparative Examples 1 to 3.

<Decision>

For each transparent conductive layer in Examples 1 to 3 and Comparative Examples 1 to 4, the crystallinity was investigated by cross-sectional observation using FE-TEM. Specifically, first, cross-sectional observation samples of each transparent conductive layer in Examples 1 to 3 and Comparative Examples 1 to 4 were produced by the FIB microsampling method. In the FIB microsampling method, a FIB device (product name "FB2200", manufactured by Hitachi) was used, and the acceleration voltage was set to 10 kV. Next, the cross-section of the transparent conductive layer in the cross-sectional observation sample was photographed at a magnification that allowed clear confirmation of the crystal grains by the FE-TEM device (product name "JEM-2800", manufactured by JEOL) at a magnification that allowed clear confirmation of the crystal grains (the acceleration voltage was set to 200 kV). In each transparent conductive layer in Examples 1 to 3 and Comparative Examples 1 to 4, it was confirmed that crystal grains had grown over the entire area in the plane direction and thickness direction of the same layer (it was confirmed that it was crystalline over the entire area in the plane direction and thickness direction). In this regard, in each of the transparent conductive layers in Comparative Examples 2 and 4, it was confirmed that there was a region in which crystal grains had not grown in the plane direction and thickness direction of the same layer (it was not confirmed that the entire area in the plane direction and thickness direction was crystalline). From these results, the crystallinity of each of the transparent conductive layers in Examples 1 to 3 and Comparative Examples 1 and 3 was evaluated as “good”, and the crystallinity of each of the transparent conductive layers in Comparative Examples 2 and 4 was evaluated as “poor”. The evaluation results are shown in Table 1.

<Transmittance>

For each transparent conductive film of Examples 1 to 3 and Comparative Examples 1 to 4, the total light transmittance (JIS K 7375-2008) was measured using a transmittance measuring device (product name “HM-150”, manufactured by Murakami Color Technology Laboratory). The measurement results are shown in Table 1 as transmittance (%).

<Resistance change due to heating>

For each transparent conductive film of Examples 1 to 3 and Comparative Examples 1 to 4, the change in resistance value due to post-heating was investigated. Specifically, it is as follows.

First, the first resistance value R1 (surface resistivity before heat treatment) of the transparent conductive layer of the transparent conductive film was measured by the four-terminal method according to JIS K 7194 (1994). Next, the transparent conductive film was heat-treated in a hot-air heating oven. In the heat treatment, the heating temperature was 160°C, and the heating time was 30 minutes. Next, the second resistance value R2 (surface resistivity after heat treatment) of the transparent conductive layer of the transparent conductive film was measured by the four-terminal method according to JIS K 7194 (1994). Then, the ratio of the second resistance value R2 to the first resistance value R1 (R2/R1) was obtained. The values are shown in Table 1. In addition, the difference R1-R2 between the first resistance value R1 and the second resistance value R2 is also shown in Table 1.

<Confirmation of Kr atoms within the transparent challenge layer>

It was confirmed as follows that each transparent conductive layer in Examples 1 to 3 and Comparative Example 3 contained Kr atoms. First, using a scanning type X-ray fluorescence spectrometer (trade name "ZSX PrimusIV", manufactured by Rigaku Corporation), fluorescence X-ray analysis measurement was repeated five times under the following measurement conditions, and the average value for each scanning angle was calculated to create an X-ray spectrum. Then, by confirming that a peak appeared in the vicinity of a scanning angle of 28.2° in the created X-ray spectrum, it was confirmed that the transparent conductive layer contained Kr atoms. In this way, it was confirmed that each transparent conductive layer in Examples 1 to 3 and Comparative Example 3 contained Kr atoms, and that each transparent conductive layer in Comparative Examples 1, 2, and 4 did not contain Kr.

<Measurement Conditions>

Spectrum; Kr-KA

Measurement diameter: 30mm

Atmosphere: Vacuum

Target: Rh

Tube voltage: 50kV

Tube current: 60mA

1st filter: Ni40

Injection angle (deg): 27.0~29.5

Step(deg): 0.020

Speed (deg/min): 0.75

Attenuator: 1/1

Slit: S2

Spectroscopic determination: LiF(200)

Detector: SC

PHA: 100~300

Industrial applicability

The transparent conductive film of the present invention can be used as a supply material for a transparent conductive film for transparent electrodes in various devices such as liquid crystal displays, touch panels, and solar cells.

X: Transparent conductive film D: Thickness direction
10: Transparent resin substrate 11: Resin film
12: Functional layer 20: Transparent conductive layer
21: 1st floor 22: 2nd floor

Claims (4)

A transparent conductive film comprising a transparent resin substrate and a crystalline transparent conductive layer in this order in the thickness direction,
The above transparent conductive layer contains a noble gas atom having an atomic number greater than argon,
The above transparent conductive layer has a first resistance value R1 (Ω/□), and after heat treatment under heating conditions of 160°C and 30 minutes, has a second resistance value R2 (Ω/□),
A transparent conductive film having a ratio of a second resistance value R2 to a first resistance value R1 of 0.650 or more and 0.990 or less. In paragraph 1,
A transparent conductive film, wherein the transparent conductive layer includes an indium tin composite oxide layer having a tin oxide content of less than 10 mass%. In claim 1 or 2,
A transparent conductive film, wherein the transparent conductive layer has a thickness of 150 nm or less. In claim 1 or 2,
A transparent conductive film having a first resistance value R1 of 220Ω/□ or less.