Light-transmissive conductive layer and light-transmissive conductive film

Abstract

To provide a light-transmissive electroconductive layer and a light-transmissive electroconductive film with low resistivity.SOLUTION: A light-transmissive electroconductive layer 1 has a first main surface 2, and a second main surface 3 positioned with a space in between so as to face one side of the first main surface 2 in the thickness direction. The light-transmissive electroconductive layer 1 has a single layer extending in the planar direction. The light-transmissive electroconductive layer 1 contains an electroconductive oxide. The electroconductive oxide contains an indium-tin composite oxide, argon, and krypton.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a light-transmitting conductive layer and a light-transmitting conductive film. [Background technology]

[0002] Conventionally, a transparent conductive film made of ITO has been known.

[0003] Transparent conductive films are required to have low resistivity. As a method for producing a transparent conductive film made of ITO with low resistivity, a method has been proposed in which a horizontal magnetic field above a target material is set to 50 mT and sputtering is performed with a mixed gas containing argon gas (for example, Patent Document 1). Also, a transparent conductive film made of ITO mixed with xenon or krypton instead of argon gas has been proposed (for example, see Patent Document 2 below). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Re-tabled publication 2013 / 080995 [Patent Document 2] Japanese Patent Application Publication No. 7-262829 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, transparent conductive films are required to have lower resistivity. Patent Document 1 does not realize a transparent conductive film having a sufficiently low resistivity. Even the transparent conductive film described in Patent Document 2 has a limit to how low the resistivity can be achieved. In addition, xenon and krypton are very expensive compared to argon due to their rarity, and it is preferable to use them in small amounts.

[0006] The present invention provides a light-transmitting conductive layer and a light-transmitting conductive film having low resistivity. [Means for solving the problem]

[0007] The present invention (1) provides a light-transmitting conductive layer having a first main surface and a second main surface arranged opposite to and spaced apart from the first main surface on one side in a thickness direction, the light-transmitting conductive layer having a single layer extending in a plane direction perpendicular to the thickness direction, the light-transmitting conductive layer including a conductive oxide, the conductive oxide containing argon and a rare gas having an atomic number greater than that of argon.

[0008] The present invention (2) includes the light-transmitting conductive layer according to (1), which is crystalline.

[0009] The present invention (3) includes the light-transmitting conductive layer according to (1) or (2), which has, in the thickness direction, the first region containing the rare gas and the second region containing argon in that order.

[0010] The present invention (4) includes the light-transmitting conductive layer according to any one of (1) to (3), in which the rare gas is krypton.

[0011] The present invention (5) includes the light-transmitting conductive layer according to any one of (1) to (4), in which the conductive oxide further contains indium and tin.

[0012] The present invention (6) includes a light-transmitting conductive film comprising the light-transmitting conductive layer according to any one of (1) to (5) and a substrate in contact with the first main surface of the light-transmitting conductive layer, wherein the first region includes the first main surface. Effect of the Invention

[0013] The light-transmitting conductive layer of the present invention has a low specific resistance.

[0014] The light-transmitting conductive film of the present invention has excellent reliability since it includes the light-transmitting conductive layer described above. [Brief description of the drawings]

[0015] [Figure 1]FIG. 1 is an enlarged cross-sectional view of one embodiment of the light-transmitting conductive layer of the present invention. [Diagram 2] FIG. 2 is a cross-sectional view of a light-transmitting conductive film including the light-transmitting conductive layer shown in FIG. [Diagram 3] FIG. 3 is a schematic diagram of a sputtering apparatus for producing the light-transmitting conductive film shown in FIG. [Figure 4] FIG. 4 is a cross-sectional view of a modified example of the light-transmitting conductive film shown in FIG. [Diagram 5] 5A to 5D are enlarged cross-sectional views of modified examples of the optically transparent conductive layer shown in FIG. 1. FIG. 5A shows a modified example in which the second region includes the first main surface and the first region includes the second main surface. FIGS. 5B and 5C show modified examples in which the first region and the second region are arranged alternately. FIG. 5D shows a modified example in which argon and a rare gas having an atomic number higher than that of argon are mixed. [Figure 6] FIG. 6 is a graph showing the relationship between the amount of oxygen introduced when forming an amorphous light-transmitting conductive layer by sputtering and the surface resistance of the amorphous light-transmitting conductive layer. [Figure 7] 7A and 7B are cross-sectional views of other examples of laminates including a light-transmitting conductive layer, with FIG. 7A showing a light-transmitting conductive layer laminate in which a light-transmitting conductive layer is laminated on a functional layer, and FIG. 7B showing a light-transmitting conductive film in which a light-transmitting conductive layer is laminated on a transparent substrate film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] [One embodiment of the light-transmitting conductive layer] The light-transmitting conductive layer 1 shown in Fig. 1 is a component included in a light-transmitting conductive film 10 (see Fig. 2) described later, a touch sensor, a light control 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-transmitting heater), and lighting, and is an intermediate member for producing these. The light-transmitting conductive layer 1 is a layer that is distributed alone and can be used industrially.

[0017] This light-transmitting conductive layer 1 has a first main surface 2 and a second main surface 3 disposed opposite to and spaced apart in the thickness direction from the first main surface 2. The light-transmitting conductive layer 1 is a single layer extending in a planar direction perpendicular to the thickness direction.

[0018] [material] The light-transmitting conductive layer 1 is made of a composition containing a conductive oxide, and is preferably made of a conductive oxide. The conductive oxide is the main component of the light-transmitting conductive layer 1, and contains a small amount of argon and a rare gas having an atomic number larger than that of argon. Specifically, the conductive oxide contains a small amount of argon and a rare gas having an atomic number larger than that of argon.

[0019] [argon] The argon is contained in the sputtering gas in the manufacturing method described below, and is mixed into the conductive oxide. In Fig. 1, the argon is depicted as a white circle.

[0020] [Noble gases with atomic numbers higher than argon] Examples of rare gases with atomic numbers larger than that of argon include krypton, xenon, and radon. These can be used alone or in combination. Krypton and xenon are preferred, and krypton (specifically, krypton used alone) is more preferred from the viewpoint of low cost and excellent electrical conductivity. The rare gas with an atomic number larger than that of argon is derived from the rare gas contained in the sputtering gas in the manufacturing method described below, and is mixed into the conductive oxide. In FIG. 1, the rare gas with an atomic number larger than that of argon is depicted as a black circle.

[0021] [Conductive oxide] The conductive oxide is a matrix in which the above-mentioned argon and a rare gas having an atomic number larger than that of argon are dispersed. Examples of the conductive oxide include metal oxides containing at least one metal 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 doped with metal atoms and / or metalloid atoms shown in the above group, as necessary.

[0022] Specific examples of the conductive oxide include metal oxides such as indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), indium gallium oxide (IGO), indium tin oxide (ITO), and antimony tin oxide (ATO). As the conductive oxide, indium tin oxide (ITO), which contains both indium and tin, is preferably used from the viewpoint of improving transparency and electrical conductivity. If the conductive oxide is ITO, it has even better transparency and electrical conductivity.

[0023] When the conductive oxide is ITO, the ratio of the content of tin oxide to the total content of indium oxide (In2O3) and tin oxide (SnO2) in the ITO is, for example, 0.1 mass% or more, preferably 3 mass% or more, more preferably 5 mass% or more, even more preferably 7 mass% or more, and even more preferably 10 mass% or more. The ratio of the number of tin atoms to the number of indium atoms in the ITO used (number of tin atoms / number of indium atoms) is, for example, 0.001 or more, preferably 0.03 or more, more preferably 0.05 or more, even more preferably 0.07 or more, and even more preferably 0.10 or more. If the ratio of the content of tin oxide to the number of indium atoms is the above-mentioned lower limit or more and / or the ratio of the number of tin atoms is the above-mentioned lower limit or more, the durability of the light-transmitting conductive layer 1 can be ensured.

[0024] The ratio of the content of tin oxide to the total content of indium oxide (In2O3) and tin oxide (SnO2) in the ITO used is, for example, 20 mass% or less, preferably 15 mass% or less, more preferably 13 mass% or less, and even more preferably 12 mass% or less. The ratio of the number of tin atoms to the number of indium atoms in the ITO used (number of tin atoms / number of indium atoms) is, for example, 0.23 or less, preferably 0.16 or less, more preferably 0.14 or less, and even more preferably 0.13 or less. If the ratio of the content of tin oxide is below the above-mentioned upper limit and / or the ratio of the number of tin atoms to the number of indium atoms is below the above-mentioned upper limit, a light-transmitting conductive layer 1 that is easily crystallized by heating can be obtained.

[0025] The ratio of the number of tin atoms to the number of indium atoms in ITO is determined, for example, by determining the abundance ratio of indium atoms and tin atoms for the measurement object by X-ray photoelectron spectroscopy. The above-mentioned content ratio of tin oxide in ITO is determined, for example, from the abundance ratio of indium atoms and tin atoms thus determined. The abundance ratio of indium atoms and tin atoms in ITO and the above-mentioned content ratio of tin oxide may be determined from the abundance ratio of indium oxide (In2O3) and tin oxide (SnO2) in the ITO target used during sputtering film formation.

[0026] [First area, second area] In this embodiment, as shown in FIG. 1, a light transmissive conductive layer 1 includes a first region 4 containing a rare gas having an atomic number greater than that of argon, and a second region 5 containing argon, in that order in the thickness direction.

[0027] [First area] The first region 4 includes, for example, the first main surface 2. In the first region 4, a rare gas having an atomic number larger than that of argon is dispersed in the thickness direction and the surface direction relative to the conductive oxide.

[0028] In the first region 4, the content of the rare gas having an atomic number larger than that of argon is, for example, 0.0001 atom% or more, preferably 0.001 atom% or more, and for example, 1.0 atom% or less, more preferably 0.7 atom% or less, even more preferably 0.5 atom% or less, particularly preferably 0.3 atom% or less, particularly preferably 0.2 atom% or less, and most preferably 0.15 atom% or less. If the content of the rare gas having an atomic number larger than that of argon is within the above range, the light-transmitting conductive layer 1 has excellent resistivity and transparency.

[0029] Although not shown in FIG. 1, argon is permitted to be mixed into the first region 4. In this case, however, the content ratio R of the rare gas having an atomic number larger than that of argon in the first region 4 is rg1 is the content ratio R of the rare gas having an atomic number larger than that of argon in the second region 5 rg2 Higher. Specifically, R rg1 / R rg2 is, for example, more than 1, preferably 1.2 or more, more preferably 1.5 or more, and for example, 10,000 or less. The rare gas having an atomic number larger than that of argon in the first region 4 is identified (presence or absence is determined) by, for example, Rutherford backscattering spectrometry, secondary ion mass spectrometry, laser resonance ionization mass spectrometry, and / or X-ray fluorescence analysis, but is preferably identified by X-ray fluorescence analysis from the viewpoint of analytical simplicity. Details of X-ray fluorescence analysis will be described in the Examples. In the first region 4 and the light-transmitting conductive layer 1 including the first region 4, when Rutherford backscattering analysis is performed and the rare gas atom content is not equal to or greater than the detection limit (lower limit), it is impossible to quantify, while when X-ray fluorescence analysis is performed and the presence of rare gas atoms is identified, it is determined that the light-transmitting conductive layer 1 includes a region in which the Kr content is 0.0001 atom% or more.

[0030] In the thickness direction, the ratio R1 (thickness ratio) of the first region 4 in the light-transmitting conductive layer 1 is, for example, 0.99 or less, preferably 0.95 or less, more preferably 0.9 or less, even more preferably 0.8 or less, particularly preferably 0.7 or less, and for example, 0.01 or more, preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.2 or more, particularly preferably 0.3 or more. When the ratio R1 of the first region 4 is equal to or less than the above upper limit, the resistivity of the light-transmitting conductive layer 1 can be reduced, and a large gain in resistivity (described later) can be obtained.

[0031] [Second area] The second region 5 includes the second main surface 3. In the second region 5, argon is dispersed in the conductive oxide in the thickness direction and the surface direction. In the light-transmitting conductive layer 1, the content of the rare gas having an atomic number larger than that of argon is, for example, 0.001 atom% or more, and, for example, 0.5 atom% or less. In the light-transmitting conductive layer 1, the content of argon is, for example, 0.001 atom% or more, preferably 0.01 atom% or more, and, for example, 0.5 atom% or less, preferably 0.4 atom% or less, more preferably 0.3 atom% or less, and further preferably 0.2 atom% or less. Even if the light-transmitting conductive layer 1 cannot be formed under high temperature conditions (for example, 200°C), if the content of argon is within the above range, a light-transmitting conductive layer 1 having excellent resistivity and / or resistivity gain (described later) can be obtained.

[0032] Although not shown in FIG. 1, the second region 5 is permitted to contain a rare gas having an atomic number larger than that of argon. In this case, the content ratio R of argon in the second region 5 is Ar2 is the argon content ratio R in the first region 4 Ar1 Higher. Specifically, R Ar2 / R Ar1is, for example, more than 1, preferably 1.2 or more, more preferably 1.5 or more, and is, for example, 10,000 or less. Argon in the light-transmitting conductive layer 1 is identified (presence or absence is determined) and quantified, for example, by Rutherford Backscattering Spectrometry (RBS). Details of Rutherford Backscattering Spectrometry will be described in the Examples.

[0033] In the thickness direction, the ratio (thickness ratio) R2 of the second region 5 in the light-transmitting conductive layer 1 is, for example, 0.01 or more, preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.2 or more, particularly preferably 0.3 or more, and, for example, 0.99 or less, preferably 0.95 or less, more preferably 0.9 or less, even more preferably 0.8 or less, particularly preferably 0.7 or less. If the ratio R2 of the second region 5 is equal to or greater than the above-mentioned lower limit, the resistivity of the light-transmitting conductive layer 1 can be reduced, and a large gain in resistivity (described later) can be obtained. If the ratio R2 of the second region 5 is equal to or less than the above-mentioned upper limit, the light-transmitting conductive layer 1 has excellent transparency and electrical conductivity.

[0034] 1, the boundary between the first region 4 and the second region 5 is drawn with a virtual line (two-dot chain line). However, in reality, there are cases where the boundary between the first region 4 and the second region 5 cannot be distinguished. In such cases, the region in the first region 4 and the second region 5 where the content ratio R3 of a rare gas having a larger atomic number than argon is high is the first region 4, and the region in the second region 5 where the content ratio R4 of argon is high is the second region 5.

[0035] [Physical properties of light-transmitting conductive layer] The light-transmitting conductive layer 1 is, for example, amorphous (non-crystalline) or crystalline (crystalline). Amorphous refers to a film that does not contain crystal grains, and crystalline refers to a film that contains crystal grains. From the viewpoint of reducing the resistivity, the light-transmitting conductive layer 1 is preferably crystalline, and more preferably includes a region in which crystal grains exist as a main region. Including a region in which crystal grains exist as a main region means that crystal grains exist in, for example, 60% or more, preferably 80% or more, more preferably 85% or more, even more preferably 90% or more, or, for example, 100% or less of the light-transmitting conductive layer 1 in plan view. If the light-transmitting conductive layer 1 includes a region in which crystal grains exist as a main region, low resistivity can be obtained. In the present application, when the light-transmitting conductive layer 1 has a particularly high crystallinity in plan view, specifically, when the area in which crystal grains exist is 90% or more, preferably 95% or more, and 100% or less, the light-transmitting conductive layer 1 can also be expressed as being crystalline. If the light-transmitting conductive layer 1 is crystalline, the light-transmitting conductive layer 1 has crystal grains over substantially the entire surface, and therefore an even lower resistivity can be obtained. In the vicinity of the grain boundaries, which are the extreme ends of the crystal grains, the crystallinity may inevitably be low, and even if the light-transmitting conductive layer 1 is crystalline, it does not have to be 100% crystalline.

[0036] The crystallinity of the light-transmitting conductive layer 1 can be determined, for example, by observing the surface of the light-transmitting conductive layer 1 from the first principal surface side or the second principal surface side with a TEM to confirm the presence of crystal grains. If crystal grains are observed, the layer is crystalline. A specific observation method will be described in detail in the Examples.

[0037] Whether or not the light-transmitting conductive layer 1 is crystalline can also be determined by immersing the light-transmitting conductive layer 1 in hydrochloric acid (20°C, concentration 5% by mass) for 15 minutes, followed by rinsing with water and drying, and then measuring the inter-terminal resistance at a distance of about 15 mm from the second main surface 3 of the light-transmitting conductive layer 1. If the inter-terminal resistance (resistance between two terminals) at a distance of 15 mm in the light-transmitting conductive layer 1 after the above immersion, rinsing with water and drying is 10 kΩ or less, the light-transmitting conductive layer 1 is crystalline.

[0038] The thickness of the light-transmitting conductive layer 1 is, for example, 5 nm or more, preferably 20 nm or more, more preferably 50 nm or more, even more preferably 100 nm or more, and, for example, 1000 nm or less, preferably less than 300 nm, more preferably 250 nm or less, even more preferably 200 nm or less, particularly preferably 160 nm or less, particularly preferably less than 150 nm, and most preferably 148 nm or less. When the thickness of the light-transmitting conductive layer 1 is within the above range, a light-transmitting conductive layer 1 having excellent transparency and / or resistivity can be obtained.

[0039] The total light transmittance (JIS K 7375-2008) of the light-transmitting conductive layer 1 (amorphous or crystalline light-transmitting conductive layer 1) is, for example, 60% or more, preferably 80% or more, more preferably 85% or more, and is, for example, 100% or less.

[0040] The surface resistance of the light-transmitting conductive layer 1 (crystalline light-transmitting conductive layer 1) is, for example, 200 Ω / □ or less, preferably 100 Ω / □ or less, more preferably 50 Ω / □ or less, even more preferably 15 Ω / □ or less, particularly preferably 13 Ω / □ or less, and is, for example, more than 0 Ω / □ or even 1 Ω / □ or more. The surface resistance can be measured by a four-terminal method in accordance with JIS K7194.

[0041] The resistivity of the light-transmitting conductive layer 1 (crystalline light-transmitting conductive layer 1) is, for example, 5.000×10 -4 Ω cm or less, preferably 2.500×10 -4 Ω cm or less, more preferably 2.000×10 -4 Ω cm or less, more preferably 2.000×10 -4 Less than Ω cm, preferably less than 1.800×10 -4 Ω cm or less, for example, 0.100×10 -4 Ω cm or more, even 0.500×10 -4 Ω cm or more, even 1.000×10 -4 The resistivity is calculated by multiplying the surface resistance by the thickness.

[0042] The total content of argon and rare gas having an atomic number larger than that of argon in the light-transmitting conductive layer 1 (amorphous or crystalline light-transmitting conductive layer 1) is, for example, 1.2 atom% or less, preferably 1.1 atom% or less, more preferably 1.0 atom% or less, even more preferably 0.8 atom% or less, particularly preferably 0.5 atom% or less, even more preferably 0.4 atom% or less, most preferably 0.3 atom% or less, and particularly preferably 0.2 atom% or less, in the entire region in the thickness direction. If the total content of argon and rare gas having an atomic number larger than that of argon is equal to or less than the above-mentioned upper limit, the total content of impurity atoms (i.e., argon and rare gas having an atomic number larger than that of argon) in the light-transmitting conductive layer 1 is small, so that a light-transmitting conductive layer 1 having high electron mobility and low resistivity can be obtained.

[0043] [Light-transmitting conductive film] Next, a light-transmitting conductive film 10 including the light-transmitting conductive layer 1 shown in FIG. 1 will be described with reference to FIG.

[0044] 2, the light-transmitting conductive film 10 has a film shape extending in a planar direction. The light-transmitting conductive film 10 includes a resin layer 11 and a light-transmitting conductive layer 1 in this order toward one side in the thickness direction.

[0045] [Resin layer] The resin layer 11 forms the other surface in the thickness direction of the light-transmitting conductive film 10. The resin layer 11 has a film shape extending toward the surface direction. The resin layer 11 is a base layer. The resin layer 11 is flexible. For example, the resin layer 11 includes a transparent base film 13 and a functional layer 14 in this order toward one side in the thickness direction. The resin layer 11 is preferably not adjacent to a glass substrate.

[0046] The transparent substrate film 13 has a film shape extending in the planar direction. The transparent substrate film 13 forms the other surface in the thickness direction of the resin layer 11. The material of the transparent substrate film 13 is a polymer. Examples of the polymer include olefin resins such as polyethylene, polypropylene, and cycloolefin polymer (COP), polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, (meth)acrylic resins (acrylic resins and / or methacrylic resins) such as polyacrylate and / or polymethacrylate, and resins such as polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, and polystyrene resins, and preferably polyester resins, and more preferably PET. The thickness of the transparent substrate film 13 is, for example, 1 μm or more, preferably 10 μm or more, more preferably 30 μm or more, and for example, 300 μm or less, preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 75 μm or less.

[0047] The transparent substrate film 13 has a total light transmittance (JIS K 7375-2008) of, for example, 60% or more, preferably 80% or more, more preferably 85% or more, and 100% or less.

[0048] The functional layer 14 forms one thickness-wise surface of the resin layer 11. The functional layer 14 is disposed on one thickness-wise surface of the transparent substrate film 13. Specifically, the functional layer 14 contacts the entire one thickness-wise surface of the transparent substrate film 13. The functional layer 14 extends in the planar direction. The functional layer is a layer containing a resin. An example of the functional layer 14 is a hard coat layer. In such a case, the resin layer 11 includes the transparent substrate film 13 and the hard coat layer in that order toward one thickness-wise side. In the following explanation, the case where the functional layer 14 is a hard coat layer will be explained.

[0049] The hard coat layer is an abrasion protection layer for preventing the light-transmitting conductive layer 1 from being scratched. The hard coat layer forms one surface in the thickness direction of the resin layer 11. The hard coat layer is in contact with the entire one surface in the thickness direction of the transparent substrate film 13. Examples of materials for the hard coat layer include a cured product of a hard coat composition (acrylic resin, urethane resin, etc.) described in JP 2016-179686 A. The thickness of the hard coat layer is, for example, 0.1 μm or more, preferably 0.5 μm or more, and, for example, 10 μm or less, preferably 5 μm or less.

[0050] [Physical properties of resin layer] The thickness of the resin layer 11 is, for example, 1 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 30 μm or more, and for example, 310 μm or less, preferably 210 μm or less, more preferably 110 μm or less, and even more preferably 80 μm or less.

[0051] The resin layer 11 has a total light transmittance (JIS K 7375-2008) of, for example, 60% or more, preferably 80% or more, more preferably 85% or more, and for example, 100% or less.

[0052] [Light-transparent conductive layer] The light-transmitting conductive layer 1 forms one surface in the thickness direction of the light-transmitting conductive film 10. The light-transmitting conductive layer 1 is supported by the resin layer 11 from the other side in the thickness direction. The light-transmitting conductive layer 1 is in contact with the entire one surface in the thickness direction of the resin layer 11. That is, the first main surface 2 of the light-transmitting conductive layer 1 is in contact with one surface in the thickness direction of the resin layer 11. Meanwhile, the second main surface 3 of the light-transmitting conductive layer 1 is exposed to one side in the thickness direction. As a result, in this light-transmitting conductive film 10, the resin layer 11, the first region 4, and the second region 5 are arranged in this order toward one side in the thickness direction. The ratio of the thickness of the light-transmitting conductive layer 1 to the thickness of the resin layer 11 is, for example, 0.00001 or more, preferably 0.01 or more, more preferably 0.1 or more, and is, for example, 0.5 or less, preferably 0.25 or less.

[0053] [Method of manufacturing light-transmitting conductive film] Next, a method for producing the light-transmitting conductive film 10 will be described with reference to Fig. 3. In this method, the light-transmitting conductive layer 1 is formed on the resin layer 11 by, for example, a roll-to-roll process.

[0054] In this method, first, a resin layer 11 is prepared. Specifically, a hard coat composition is applied to one surface in the thickness direction of a transparent substrate film 13, dried, and then cured. This prepares a resin layer 11 having the transparent substrate film 13 and the hard coat layer (functional layer 14) in that order on one side in the thickness direction.

[0055] Thereafter, if necessary, the resin layer 11 is degassed. To degas the resin layer 11, the resin layer 11 is degassed by, for example, 1×10 -1 Pa or less, preferably 1×10 -2 Pa or less, for example, 1×10 -6 The resin layer 11 is then left in a reduced pressure atmosphere of at least Pa. Specifically, the atmosphere around the resin layer 11 is reduced pressure using a pump (described later) of the sputtering device 30.

[0056] Next, the light-transmitting conductive layer 1 is formed by sputtering. Specifically, the light-transmitting conductive layer 1 is formed while the resin layer 11 is being transported in a sputtering device 30.

[0057] [Sputtering equipment] The sputtering device 30 includes a payout unit 35, a sputtering unit 36, and a winding unit 37, in that order.

[0058] The payout section 35 includes a payout roll 38 and a discharge port of the payout side pump 33 .

[0059] The sputtering section 36 includes a film-forming roll 40, a first film-forming chamber 41, and a second film-forming chamber 42.

[0060] The film-forming roll 40 includes a cooling device (not shown) configured to cool the film-forming roll 40 .

[0061] The first film formation chamber 41 accommodates a first target 51, a first gas supplier 61, and an outlet of a first pump 71. The first target 51, the first gas supplier 61, and the outlet of the first pump 71 are disposed opposite the film formation roll 40 with a gap therebetween.

[0062] The material of the first target 51 may be the same as the conductive oxide described above. The material of the first target 51 includes a sintered body of a conductive oxide. However, these conductive oxides are not yet mixed with argon and a rare gas having an atomic number larger than that of argon. The first target 51 is configured to apply electric power.

[0063] A magnet (not shown) is disposed on the opposite side of the deposition roll 40 to the first target 51. The horizontal magnetic field strength on the surface of the first target 51 is, for example, 10 mT or more, preferably 60 mT or more, and is, for example, 300 mT or less. By disposing the magnet and setting the horizontal magnetic field strength on the surface of the first target 51 within the above range, it is possible to adjust the content of the rare gas having an atomic number larger than that of argon contained in the first amorphous conductive film 81 (first region 4) described later.

[0064] The first gas supply unit 61 is configured to supply a first sputtering gas to the first film formation chamber 41. The first sputtering gas includes a rare gas having an atomic number greater than that of argon. Specifically, the first sputtering gas includes, for example, a rare gas having an atomic number greater than that of argon, and a first mixed gas including, for example, a rare gas having an atomic number greater than that of argon and a reactive gas such as oxygen. Preferably, the first mixed gas is used.

[0065] When the sputtering gas is the first mixed gas, the first gas supply unit 61 includes a rare gas supply unit 63 and a first oxygen gas supply unit 64, which supply a rare gas having an atomic number higher than that of argon and oxygen to the first film formation chamber 41, respectively. Note that the "rare gas" in the rare gas supply unit 63 means a rare gas that does not include argon and has an atomic number higher than that of argon.

[0066] The second film forming chamber 42 is disposed adjacent to the first film forming chamber 41 in the circumferential direction of the film forming roll 40. As a result, the first film forming chamber 41 and the second film forming chamber 42 are disposed in order in the circumferential direction. The second film forming chamber 42 accommodates the second target 52, the second gas supplier 62, and the exhaust port of the second pump 72. The second target 52, the second gas supplier 62, and the exhaust port of the second pump 72 are disposed opposite the film forming roll 40 with a gap therebetween.

[0067] The material of the second target 52 may be the same as the conductive oxide described above. The material of the second target 52 includes a sintered body of a conductive oxide. However, these conductive oxides are not yet mixed with argon and a rare gas having an atomic number larger than that of argon. The second target 52 is configured to apply electric power.

[0068] A magnet (not shown) is disposed on the opposite side of the film-forming roll 40 to the second target 52. The horizontal magnetic field strength on the surface of the second target 52 is, for example, 10 mT or more, preferably 60 mT or more, and is, for example, 300 mT or less. By disposing the magnet and setting the horizontal magnetic field strength on the surface of the second target 52 within the above range, the content of argon contained in the second amorphous conductive film 82 (second region 5) described later can be adjusted.

[0069] The second gas supply 62 is configured to supply a second sputtering gas to the second film formation chamber 42. Examples of the second sputtering gas include argon and a second mixed gas containing argon and a reactive gas such as oxygen. The second mixed gas is preferable. If the second sputtering gas is the second mixed gas, the second gas supply 62 includes an argon supply 65 and a second oxygen gas supply 66, from which argon and oxygen are supplied to the second film formation chamber 42, respectively.

[0070] The winding section 37 includes a winding roll 39 and a discharge port of the winding-side pump 34 .

[0071] [Manufacturing of light-transmitting conductive film] To form the light-transmitting conductive layer 1 on the resin layer 11 using this sputtering device 30, first, the resin layer 11 is laid over a payout roll 38, a film-forming roll 40, and a take-up roll 39.

[0072] While driving the first pump 71, the sputtering gas is supplied from the first gas supply unit 61 to the first film formation chamber 41. The pressure of the rare gas having an atomic number higher than that of argon (if the sputtering gas is the first mixed gas, the partial pressure of the rare gas having an atomic number higher than that of argon) is, for example, 0.01 Pa or more, preferably 0.05 Pa or more, and for example, 0.8 Pa or less, preferably 0.5 Pa or less, and more preferably 0.2 Pa or less.

[0073] While driving the second pump 72, the sputtering gas is supplied from the second gas supply unit 63 to the first film formation chamber 41. The pressure of argon (if the sputtering gas is the second mixed gas, the partial pressure of argon) is, for example, 0.02 Pa or more, preferably 0.1 Pa or more, and for example, 1 Pa or less, preferably 0.5 Pa or less.

[0074] Moreover, the cooling device is driven to cool (the surface of) the film-forming roll 40. The temperature (surface temperature) of the film-forming roll 40 is, for example, 20.0°C or less, preferably 10.0°C or less, more preferably 0.0°C or less, and is, for example, -50°C or more, preferably -25°C or more. By sufficiently cooling the resin layer 11, it is possible to suppress the excessive generation of gas (water and / or organic solvent) from the resin layer 11 during sputtering. As a result, the amount of impurities contained in the light-transmitting conductive layer 1 can be reduced, and a light-transmitting conductive layer 1 having excellent resistivity can be obtained.

[0075] Next, the payout roll 38, the film-forming roll 40, and the take-up roll 39 are driven to pay out the resin layer 11 from the payout roll 38. The resin layer 11 moves in sequence through the first film-forming chamber 41 and the second film-forming chamber 42 while in contact with the surface of the film-forming roll 40. At this time, the resin layer 11 is cooled by contact with the surface of the film-forming roll 40.

[0076] The sputtering gas is ionized near the first target 51 to generate an ionized gas. The ionized gas then collides with the first target 51, and the target material of the first target 51 is knocked out as particles, and the particles adhere (deposit) to the resin layer 11 to form a first amorphous conductive film 81. At this time, a rare gas (a rare gas having an atomic number larger than that of argon, preferably krypton) contained in the sputtering gas is taken into the first amorphous conductive film 81 together with the particles. The amount of the rare gas taken into the first amorphous conductive film 81 is adjusted by the magnetic field strength, the power density of the power applied to the first target 51, and / or the pressure in the first film formation chamber 41. The thickness of the first amorphous conductive film 81 is adjusted by the power density of the power applied to the first target 51.

[0077] Next, the sputtering gas is ionized near the second target 52 to generate an ionized gas. Next, the ionized gas collides with the second target 52, and the target material of the second target 52 is knocked out as particles, and the particles adhere (deposit) to the first amorphous conductive film 81 to form the second amorphous conductive film 82. At this time, argon contained in the sputtering gas is taken into the second amorphous conductive film 82 together with the particles. The amount of the rare gas taken into the second amorphous conductive film 82 is adjusted by the magnetic field strength, the power density of the power applied to the second target 52, and / or the pressure in the second film formation chamber 42. The thickness of the second amorphous conductive film 82 is adjusted by the power density of the power applied to the second target 52.

[0078] As a result, an amorphous light-transmitting conductive film 10 including the resin layer 11, the first amorphous conductive film 81, and the second amorphous conductive film 82 is obtained.

[0079] The first amorphous conductive film 81 and the second amorphous conductive film 82 respectively constitute the first region 4 and the second region 5. Since the first amorphous conductive film 81 and the second amorphous conductive film 82 each contain the same conductive oxide as a main component, the boundary therebetween may not be observed.

[0080] 2, a light-transmitting conductive layer 1 (amorphous light-transmitting conductive layer 1) is formed on one surface in the thickness direction of the resin layer 11. In this way, a light-transmitting conductive film 10 including the resin layer 11 and the light-transmitting conductive layer 1 is manufactured.

[0081] The total light transmittance (JIS K 7375-2008) of this light-transmitting conductive film 10 is, for example, 60% or more, preferably 80% or more, more preferably 83% or more, and for example, 100% or less, preferably 95% or less.

[0082] Thereafter, the amorphous light-transmitting conductive layer 1 is crystallized. Specifically, for example, the amorphous light-transmitting conductive film 10 is heated. As heating conditions, the heating temperature is, for example, 80° C. or more, preferably 110° C. or more, more preferably 150° C. or more, and for example, less than 200° C., preferably 180° C. or less, and the heating time is, for example, 0.2 minutes or more, preferably 5 minutes or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, particularly preferably 1 hour or more, and for example, 5 hours or less, preferably 3 hours or less.

[0083] In this way, a light-transmitting conductive film 10 is manufactured, which includes the resin layer 11 and the light-transmitting conductive layer 1 including a crystalline region.

[0084] The total light transmittance (JIS K 7375-2008) of the crystalline light-transmitting conductive film 10 after heating the amorphous light-transmitting conductive layer 1 is, for example, 65% or more, preferably 80% or more, more preferably 83% or more, and for example, 100% or less, preferably 95% or less.

[0085] This light-transmitting conductive film 10 is used in various articles, such as touch sensors, electromagnetic wave shields, light control elements (e.g., voltage-driven light control elements such as PDLC, PNLC, and SPD, and current-driven light control elements such as electrochromic (EC)), photoelectric conversion elements (electrodes of solar cell elements such as organic thin-film solar cells and dye-sensitized solar cells), heat ray control members (e.g., near-infrared reflective and / or absorbing members, e.g., far-infrared reflective and / or absorbing members), antenna members (light-transmitting antennas), heater members (light-transmitting heaters), image display devices, and lighting.

[0086] The articles include a light-transmitting conductive film 10 and a member corresponding to each article.

[0087] Such articles can be obtained by fixing the light-transmitting conductive film 10 to a member corresponding to each article.

[0088] Specifically, for example, the light-transmitting conductive layer 1 (including the light-transmitting conductive layer 1 having a pattern shape) in the light-transmitting conductive film 10 and a member corresponding to each article are fixed via an adhesive functional layer.

[0089] The adhesive functional layer includes, for example, an adhesive layer and a bonding layer.

[0090] The adhesive layer can be made of any material that has transparency. The adhesive layer is preferably made 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, acrylic resin is preferably selected as the resin from the viewpoint of excellent optical transparency, adhesive properties such as moderate wettability, cohesiveness, and adhesiveness, and excellent weather resistance and heat resistance.

[0091] A known corrosion inhibitor and migration inhibitor (e.g., materials disclosed in JP 2015-022397 A) may be added to the resin forming the adhesion functional layer in order to suppress corrosion and migration of the light-transmitting conductive layer 1. A known ultraviolet absorbing agent may also be added to the adhesion functional layer (resin forming the adhesion functional layer) in order to suppress deterioration during outdoor use of the article. Examples of ultraviolet absorbing agents include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxalic acid anilide compounds, cyanoacrylate compounds, and triazine compounds.

[0092] Also, the resin layer 11 in the light-transmitting conductive film 10 and a member corresponding to each article can be fixed via an adhesive functional layer. In such a case, the light-transmitting conductive layer 1 (including the light-transmitting conductive layer 1 having a pattern shape) is exposed in the light-transmitting conductive film 10. Therefore, a cover layer can be disposed on one surface of the light-transmitting conductive layer 1 in the thickness direction.

[0093] The cover layer is a layer that covers the light-transmitting conductive layer 1, and can improve the reliability of the light-transmitting conductive layer 1 and suppress deterioration of its function due to scratches.

[0094] The material of the cover layer is preferably a dielectric material. The cover layer is formed from a mixture of a resin and an inorganic material. The resin may be any of the resins exemplified in the adhesive layer. The inorganic material may be any of the materials exemplified in the intermediate layer described below.

[0095] Further, from the same viewpoint as in the adhesive layer, a corrosion inhibitor, a migration inhibitor, and an ultraviolet absorbing agent may be added to the mixture of the resin and the inorganic material.

[0096] The above-mentioned articles have excellent reliability because they include the above-mentioned light-transmitting conductive film 10. Specifically, touch sensors, light control elements, photoelectric conversion elements, heat ray control members, antennas, electromagnetic wave shielding members, image display devices, heater members, and lighting have excellent reliability because they include the above-mentioned light-transmitting conductive film 10.

[0097] [Effects] In general, one light-transmitting conductive layer A made of a conductive oxide containing a rare gas having an atomic number greater than that of argon has a lower resistivity than another light-transmitting conductive layer B made of a conductive oxide containing argon. Specifically, one light-transmitting conductive layer A made of only the first region 4 (corresponding to Comparative Example 2) has a lower resistivity than another light-transmitting conductive layer B made of only the second region 5 (corresponding to Comparative Example 1).

[0098] As shown in FIG. 1, the light-transmitting conductive layer 1 of this embodiment has a first region 4 and a second region 5, and is therefore expected (predicted) to have a resistivity (surface resistance) that is a combination of the resistivity (surface resistance) of one light-transmitting conductive layer A and the resistivity (surface resistance) of the other light-transmitting conductive layer B described above.

[0099] However, the resistivity of the light-transmitting conductive layer 1 of this embodiment is lower than the expected resistivity (expected value, described later) as described above, which is demonstrated by the gain in resistivity described in the examples below.

[0100] The resistivity gain of this light-transmitting conductive layer 1 is, for example, 1.0% or more, preferably 5.0% or more, more preferably 10.0% or more, further 12.0% or more, further 14.0% or more, further 15.0% or more, further 17.0% or more, further 18.0% or more, or further 20.0% or more is preferable, and for example, 50.0% or less. The method of determining the resistivity gain will be described later in the Examples.

[0101] Furthermore, in one embodiment of the light-transmitting conductive layer 1, the conductive oxide contains argon and a rare gas having an atomic number higher than that of argon, yet the resistivity of the light-transmitting conductive layer 1 in one embodiment is surprisingly lower than the resistivity of the light-transmitting conductive layer A.

[0102] The light-transmitting conductive film 10 (see FIG. 2), touch sensor, light control element, photoelectric conversion element, heat ray control member, antenna, electromagnetic wave shielding member, and image display device have excellent resistance characteristics and reliability because they include the above-mentioned light-transmitting conductive layer 1. In other words, the above-mentioned articles have excellent resistance characteristics and reliability because they include the above-mentioned light-transmitting conductive layer 1.

[0103] [Variations] In the modified example, the same components and steps as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. In addition, the modified example can achieve the same effects as those in the first embodiment, unless otherwise specified. Furthermore, the first embodiment and its modified example can be appropriately combined.

[0104] In one embodiment, the first region 4 containing a rare gas having an atomic number greater than that of argon includes the first main surface 2 in contact with the resin layer 11.

[0105] 4, the second region 5 containing argon may include the first main surface 2. The second region 5 is in contact with the resin layer 11.

[0106] Preferably, as in one embodiment, the first region 4 is located on the side of the first main surface 2. With this configuration, a large gain in resistivity (described in detail in the examples below) can be ensured.

[0107] For example, as shown in FIG. 5B and FIG. 5C, the first region 4 and the second region 5 may be arranged alternately and repeatedly. Specifically, in the modified example of FIG. 5B, the first region 4, the second region 5, the first region 4, and the second region 5 are arranged in order toward one side in the thickness direction. In the modified example of FIG. 5C, the second region 5, the first region 4, the second region 5, and the first region 4 are arranged in order toward one side in the thickness direction. In addition, although not shown, the first region 4 may be arranged in a configuration in which the first region 4 and the second region 5 are arranged alternately and repeatedly toward one side in the thickness direction. In addition, the second region 5 may be arranged in a configuration in which the second region 5 and the first region 4 are arranged alternately and repeatedly toward one side in the thickness direction. In addition, the first region 4, the second region 5, and the first region 4 may be arranged in order in the thickness direction. In addition, the second region 5, the first region 4, and the second region 5 may be arranged in order in the thickness direction.

[0108] Although outside the scope of the present invention (corresponding to Comparative Example 3 described later), as shown in Fig. 5D, the light-transmitting conductive layer 1 may not have the first region 4 and the second region 5, and argon and a rare gas having an atomic number higher than that of argon may be mixed (uniformly dispersed) in the light-transmitting conductive layer 1. To form the light-transmitting conductive layer 1 shown in Fig. 5D, a sputtering gas containing both argon and a rare gas having an atomic number higher than that of argon is supplied from a gas supply device to a film formation chamber. More specifically, both argon and a rare gas having an atomic number higher than that of argon are supplied from a rare gas supply device 63. The volume ratio of the rare gas having an atomic number higher than that of argon to the total volume of the rare gas having an atomic number higher than that of argon and argon gas is, for example, 1 volume% or more, preferably 10 volume% or more, more preferably 30 volume% or more, even more preferably 60 volume% or more, particularly preferably 70 volume% or more, and most preferably 80 volume% or more, and is, for example, 99 volume% or less, preferably 90 volume% or less, more preferably 88 volume% or less.

[0109] Immediately after sputtering, the amorphous light-transmitting conductive layer 1 is made of a third amorphous conductive film 83. Argon and a rare gas having an atomic number larger than that of argon are mixed (uniformly dispersed) in the third amorphous conductive film 83. After deposition, the third amorphous conductive film 83 is heated and crystallized.

[0110] In one embodiment, in the light-transmitting conductive film 10, the light-transmitting conductive layer 1 is in contact with the entire surface of one side in the thickness direction of the resin layer 11, but the light-transmitting conductive layer 1 may be patterned so that an arbitrary region remains, although not shown. That is, there may be a region on the resin layer 11 where the light-transmitting conductive layer 1 does not exist. By patterning, the film can be suitably used for a touch sensor, a light control element, a photoelectric conversion element, and the like.

[0111] The resin layer 11 may further include other functional layers. For example, as shown by the imaginary lines in Figures 2 and 4, an anti-blocking layer 12 may be provided on the other surface in the thickness direction of the transparent substrate film 13. The anti-blocking layer 12 imparts anti-blocking properties to the respective surfaces of the multiple light-transmitting conductive films 10 that are in contact with each other, for example, when the light-transmitting conductive films 10 are stacked in the thickness direction.

[0112] Moreover, the resin layer 11 may further include an easy-adhesion layer between the antiblocking layer 12 and the transparent substrate film 13 .

[0113] The resin layer 11 may also include an intermediate layer (not shown) made of an inorganic layer on one side of the transparent substrate film 13. The intermediate layer has the functions of improving the surface hardness of the resin layer 11, adjusting the optical properties (specifically, the refractive index) of the light-transmitting conductive film 10, and alleviating the stress that the light-transmitting conductive layer 1 receives from the resin layer 11 at an intermediate point. The intermediate layer may be provided at any position with respect to the transparent substrate film 13, the functional layer 14, and the anti-blocking layer 12, and may include a plurality of layers. For example, the resin layer 11 includes the transparent substrate film 13, the functional layer 14, and the intermediate layer, in this order, toward one side in the thickness direction. The resin layer 11 also includes, for example, the intermediate layer, the anti-blocking layer 12, the transparent substrate film 13, and the functional layer 14, in this order, toward one side in the thickness direction. The intermediate layer is preferably an inorganic dielectric material, and has a surface resistance of, for example, 1×10 6 Ω / □ or more, preferably 1×10 8 The material of the intermediate layer is, for example, a composition containing an inorganic oxide such as silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide, or calcium oxide, or a fluoride such as magnesium fluoride. The composition of the inorganic functional layer may or may not be a stoichiometric composition.

[0114] The functional layer 14 may be an optical adjustment layer (not shown). In this modification, the resin layer 11 includes a transparent substrate film 13 and an optical adjustment layer in this order toward one side in the thickness direction. The optical adjustment layer is a layer that suppresses the visibility of the pattern formed from the light-transmitting conductive layer 1 and adjusts the optical properties (specifically, the refractive index) of the light-transmitting conductive film 10.

[0115] The functional layer 14 may be a peelable functional layer (not shown). In this modification, the resin layer 11 includes a transparent substrate film 13 and a peelable functional layer in this order toward one side in the thickness direction. The peelable functional layer is a layer (easy peelable layer) that is easily peeled from the transparent substrate film 13. If the resin layer 11 includes a peelable functional layer, the light-transmitting conductive layer 1 can be peeled off from the transparent substrate film 13. The peeled light-transmitting conductive layer 1 can be used, for example, by transferring and bonding it to another member constituting a touch sensor.

[0116] The functional layer 14 may be an easy-adhesion layer (not shown). In this modification, the resin layer 11 includes a transparent substrate film 13 and an easy-adhesion layer in this order toward one side in the thickness direction. The easy-adhesion layer improves the adhesion between the transparent substrate film 13 and the light-transmitting conductive layer 1.

[0117] The functional layer 14 may be a multilayer. That is, the functional layer 14 may include two or more layers selected from the group consisting of a hard coat layer, an optical adjustment layer, a release functional layer, and an easy-adhesion layer. In detail, the resin layer 11 may include a transparent substrate film 13, an easy-adhesion layer, a hard coat layer, and an optical adjustment layer in order toward one side in the thickness direction, or the resin layer 11 may include a transparent substrate film 13, a release functional layer, and a hard coat layer and / or an optical adjustment layer in order toward one side in the thickness direction.

[0118] When the resin layer 11 has a transparent substrate film 13, a peelable functional layer, and a hard coat layer and / or an optical adjustment layer, in that order toward one side in the thickness direction, a laminate having the hard coat layer and / or the optical adjustment layer and the light-transmitting conductive layer 1 can be peeled off from the light-transmitting conductive film 10.

[0119] As shown in Figures 7A and 7B, the resin layer 11 can include only one of the functional layer 14 and the transparent substrate film 13. Figures 7A and 7B depict another example of a laminate including a light-transmitting conductive layer.

[0120] 7A, in this light-transmitting conductive layer laminate 20, the resin layer 11 may be composed of only a functional layer 14 without including a transparent substrate film 13. The light-transmitting conductive layer laminate 20 does not have a film shape, and has a resin layer 11 (a hard coat layer and / or an optical adjustment layer) and a light-transmitting conductive layer 1 in this order in the thickness direction.

[0121] 7B, the light-transmitting conductive film 10 has a film shape. The resin layer 11 may not include the functional layer 14 and may be composed of only the transparent base film 13. In other words, the light-transmitting conductive film 10 has the transparent base film 13 and the light-transmitting conductive layer 1 in this order in the thickness direction.

[0122] Furthermore, in the resin layer 11, a transparent base material (not shown) containing glass may be provided in the functional layer 14.

[0123] In one embodiment, one is illustrated as a suitable number of light-transmitting conductive layers 1 in the light-transmitting conductive film 10, but it may be, for example, two, although not shown. In this modification, two light-transmitting conductive layers 1 are disposed on both sides of the resin layer 11 in the thickness direction. That is, in this modification, the number of light-transmitting conductive layers 1 for one resin layer 11 is preferably two.

[0124] As one embodiment of a method for producing a light-transmitting conductive layer 1 including a crystalline region, a manufacturing method in which an amorphous light-transmitting conductive layer 1 is heated has been described. However, a manufacturing method in which the layer is stored in a temperature environment of less than 80°C (e.g., 25°C) for a long period of time (e.g., 1000 hours) may also be used. EXAMPLES

[0125] The present invention will be described in more detail below with reference to examples and comparative examples. The specific values ​​of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the upper limit (a value defined as "not more than" or "less than") or lower limit (a value defined as "not less than" or "exceeding") of the corresponding blending ratio (content ratio), physical property values, parameters, etc. described in the above "Form for carrying out the invention". In addition, unless otherwise specified in the following description, "parts" and "%" are based on mass.

[0126] Example 1 A UV-curable hard coat composition containing an acrylic resin was applied to one surface in the thickness direction of a transparent substrate film 13 made of a long PET film (manufactured by Toray Industries, Inc., thickness 50 μm), and then cured by UV irradiation to form a hard coat layer (functional layer 14) having a thickness of 2 μm. In this way, a resin layer 11 including the transparent substrate film 13 and the hard coat layer was prepared.

[0127] Next, the resin layer 11 was set in the sputtering device 30. Next, in the sputtering device 30, the payout side pump 33, the take-up side pump 34, the first pump 71, and the second pump 72 were driven to achieve a vacuum of 0.9×10 -4 The pressure in the sintered body was adjusted to 10 Pa, and the resin layer 11 was degassed. The temperature of the film-forming roll 40 was adjusted to -8°C. In the sputtering device 30, the materials of the first target 51 and the second target were both sintered bodies of indium oxide and tin oxide. In the sintered body, the ratio of the content of tin oxide to the total content of indium oxide and tin oxide was 10 mass%. In the sintered body, the ratio of the number of tin atoms to the number of indium atoms (number of tin atoms / number of indium atoms) was 0.102.

[0128] Thereafter, the resin layer 11 was transported from the unwinding section 35 to the winding section 37 along the film-forming roll 40 .

[0129] In the first film formation chamber 41, krypton was supplied from the rare gas supplier 63 and oxygen was supplied from the first oxygen gas supplier 64 while driving the first pump 71. The pressure in the first film formation chamber 41 was set to 0.2 Pa, and the first target 51 was sputtered (power supply: DC, horizontal magnetic field strength on the first target: 90 mT) to form a first amorphous conductive film 81 (first region 4) having a thickness of 50 nm.

[0130] In the second film formation chamber 42, while driving the second pump 72, argon was supplied from the argon supplier 65, and oxygen was supplied from the second oxygen gas supplier 66. The pressure in the second film formation chamber 42 was set to 0.4 Pa, and the second target 52 was sputtered (power supply: DC, horizontal magnetic field strength on the second target: 90 mT) to form a second amorphous conductive film 82 (second region 5) having a thickness of 80 nm.

[0131] The amounts of oxygen introduced from the first oxygen gas supplier 64 and the second oxygen gas supplier 66 were adjusted so that the surface resistance of the amorphous light-transmitting conductive layer 1 was in the first region X of the surface resistance-oxygen introduction amount curve and was 50 Ω / □, as shown in Fig. 6. In this case, the ratio of oxygen gas to the total amount of krypton gas and oxygen gas introduced was about 2.5 flow %. The ratio of oxygen gas to the total amount of argon gas and oxygen gas introduced was about 1.5 flow %.

[0132] As a result, as shown in FIG. 2, a first amorphous conductive film 81 and a second amorphous conductive film 82 were formed in this order on one side of the resin layer 11 in the thickness direction.

[0133] In this way, a light-transmitting conductive film 10 consisting of the resin layer 11 and the amorphous light-transmitting conductive layer 1 was obtained.

[0134] Examples 2 to 4 and 6 to 7 A light-transmitting conductive film 10 was obtained in the same manner as in Example 1, except that the power densities of the first target 51 and the second target 52 were adjusted so that the thickness of the first amorphous conductive film 81 (first region 4), the thickness of the second amorphous conductive film 82 (second region 5), and the surface resistance of the amorphous light-transmitting conductive layer 1 were as shown in Table 1.

[0135] Example 5 A second mixed gas (containing Ar and O2) was supplied to the first film formation chamber 41 to set the pressure in the first film formation chamber 41 to 0.4 Pa, and a second amorphous conductive film 82 (second region 5) having a thickness of 42 nm was formed by sputtering. Then, a first mixed gas (containing Kr and O2) was supplied to the second film formation chamber 42 to set the pressure in the second film formation chamber 42 to 0.2 Pa, and a first amorphous conductive film 81 (first region 4) having a thickness of 76 nm was formed by sputtering. The surface resistance of the amorphous light-transmitting conductive layer 1 was adjusted to 55 Ω / □. The light-transmitting conductive film 10 of Example 5 corresponds to the light-transmitting conductive film 10 shown in FIG. 4.

[0136] Comparative Example 3 A mixed gas of krypton and argon (krypton 85 volume %, argon 15 volume %) was supplied from a rare gas supplier 63, oxygen was supplied from a first oxygen gas supplier 64, the amount of oxygen introduced from the first oxygen gas supplier 64 was adjusted so that the surface resistance of the amorphous light-transmitting conductive layer 1 was in the first region X of the surface resistance-oxygen introduction amount curve shown in FIG. 6 and the surface resistance of the amorphous light-transmitting conductive layer 1 was 39Ω / □ (the ratio of oxygen gas to the total amount of krypton gas and oxygen gas introduced was about 2.6 flow rate %), and the power density of the first target 51 was adjusted so that a third amorphous conductive film 83 having a thickness of 147 nm was formed in the first film formation chamber 41, and a second amorphous conductive film 82 (second region 5) was not formed in the second film formation chamber 42. The light-transmitting conductive film 10 was obtained in the same manner as in Example 1. The light-transmitting conductive film 10 of Comparative Example 3 corresponds to the light-transmitting conductive film 10 shown in FIG. 5D.

[0137] Comparative Example 1 A light-transmitting conductive film 10 was obtained in the same manner as in Example 1, except that a second mixed gas (containing Ar and O2) was supplied to both the first film-forming chamber 41 and the second film-forming chamber 42, and the pressure in the first film-forming chamber 41 and the second film-forming chamber 42 was changed to 0.4 Pa.

[0138] Comparative Example 2 A light-transmitting conductive film 10 was obtained in the same manner as in Example 1, except that a first mixed gas (containing Kr and O2) was supplied to both the first film-forming chamber 41 and the second film-forming chamber 42, and the pressure in the first film-forming chamber 41 and the second film-forming chamber 42 was changed to 0.2 Pa.

[0139] [evaluation] The light-transmitting conductive films 10 of the respective Examples and Comparative Examples were evaluated for the following items. The results are shown in Table 1.

[0140] Thickness [Thickness of light-transmitting conductive layer] A cross-sectional observation sample of the light-transmitting conductive layer 1 of each of the examples and comparative examples was prepared by FIB microsampling, and then the thickness of the light-transmitting conductive layer 1 in the cross-sectional observation sample was measured by FE-TEM observation (cross-sectional observation). The details of the apparatus and measurement conditions are as follows.

[0141] FIB microsampling method FIB equipment: Hitachi FB2200 Acceleration voltage: 10 kV

[0142] FE-TEM observation FE-TEM equipment: JEOL JEM-2800 Accelerating voltage: 200 kV

[0143] [Thickness of the first amorphous conductive film and the second amorphous conductive film in Examples 1 to 4 and 6 to 7] In Examples 1 to 4 and 6 to 7, samples were taken immediately after the formation of the first amorphous conductive film 81 and before the formation of the second amorphous conductive film 82, and the thickness of the first amorphous conductive film 81 (first region 4) of the sample was determined by FE-TEM observation (cross-sectional observation).

[0144] Next, the thickness of the second amorphous conductive film 82 (second region 5) in Examples 1 to 4 and 6 to 7 was determined by the following formula.

[0145] Thickness of the second amorphous conductive film 82=thickness of the light-transmitting conductive layer 1−thickness of the first amorphous conductive film 81

[0146] [Thickness of the first amorphous conductive film and the second amorphous conductive film in Example 5] In Example 5, a sample was taken immediately after the formation of the second amorphous conductive film 82 but before the formation of the first amorphous conductive film 81, and the thickness of the second amorphous conductive film 82 (second region 5) of the sample was determined by FE-TEM observation (cross-sectional observation).

[0147] Next, the thickness of the first amorphous conductive film 81 (first region 4) of Example 5 was calculated by the following formula.

[0148] Thickness of the first amorphous conductive film 81=thickness of the light-transmitting conductive layer 1−thickness of the second amorphous conductive film 82

[0149] [Thickness of the third amorphous conductive film in Comparative Example 3] In Comparative Example 3, the thickness of the third amorphous conductive film 83 immediately after sputtering was determined by FE-TEM observation (cross-sectional observation).

[0150] [Identification of Kr (confirmation of presence or absence)] Using a scanning X-ray fluorescence analyzer (ZSX PrimusIV, manufactured by Rigaku Corporation), it was confirmed whether Kr was mixed into the light-transmitting conductive layer 1. Specifically, measurements were repeated five times under the following conditions, and the average value of each scanning angle was calculated to create an X-ray spectrum. Kr was identified by confirming that a peak appeared in the vicinity of 28.2° in the created X-ray spectrum. As a result, the inclusion of Kr was confirmed in Examples 1 to 8 and Comparative Example 2. On the other hand, the inclusion of Kr was not confirmed in Comparative Example 1.

[0151] <Measurement conditions> Spectrum: Kr-KA Measuring diameter: 30mm 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 Spectroscopic crystal: LiF(200) Detector: SC PHA: 100-300

[0152] [Identification of Kr and Ar (quantitative)] The contents of Kr and Ar atoms contained in the light-transmitting conductive layer 1 of Examples 1 to 7 and Comparative Examples 1 to 3 were analyzed by Rutherford Backscattering Spectrometry (RBS). The contents (atom%) of Kr atoms and Ar atoms in the light-transmitting conductive layer 1 were obtained by calculating the element ratios of the five elements, In+Sn (since it is difficult to measure In and Sn separately in Rutherford Backscattering Spectrometry, the two elements were evaluated as a sum), O, Ar, and Kr, which were the detection elements. The specific apparatus used and measurement conditions are as follows. Table 1 shows the analysis results, Kr content (atom%), Ar content (atom%), and rare gas (Kr+Ar) content (atom%).

[0153] Regarding the analysis of the Kr content, in Examples 1 to 7 and Comparative Examples 2 and 3, no reliable measured value was obtained that was equal to or greater than the detection limit (lower limit) (the detection limit may vary depending on the thickness of the light-transmitting conductive layer 1 subjected to the measurement). Therefore, in Table 1, the Kr content in the light-transmitting conductive layer 1 is expressed as "<the specific detection limit in the thickness of the light-transmitting conductive layer 1 subjected to the measurement" to indicate that the Kr content is below the detection limit in the thickness of the light-transmitting conductive layer 1 (the same applies to the expression of the rare gas (Kr+Ar) content).

[0154] In addition, in Comparative Example 1, the quantitative analysis of Kr using the above-mentioned scanning X-ray fluorescence analyzer did not confirm the presence of Kr contamination, so Table 1 does not indicate "<the specific detection limit value at the thickness of the light-transmitting conductive layer 1 subjected to measurement" described in Examples 1 to 8 and Comparative Example 2.

[0155] <Equipment used> Pelletron 3SDH (manufactured by National Electrostatics Corporation)

[0156] <Measurement conditions> Incident ions: 4He++ Incident energy: 2300keV Incident angle: 0 deg Scattering angle: 160deg Specimen current: 6nA Beam diameter: 2mmφ In-plane rotation: None Irradiation dose: 75μC

[0157] [Surface resistance] The surface resistance (initial) of the light-transmitting conductive layer 1 was measured by a four-terminal method in accordance with JIS K7194 (1994).

[0158] After heating in a hot air oven at 155° C. for 2 hours, the surface resistance (after heating) of the light transmissible conductive layer 1 was measured in the same manner as above.

[0159] [Resistivity] [Actual resistivity values] The actual resistivity value of the light-transmitting conductive layer 1 after heating in each of the Examples and Comparative Examples was calculated by multiplying the surface resistance and the thickness of the light-transmitting conductive layer 1. The actual resistivity value of the light-transmitting conductive layer 1 is calculated based on the actually measured surface resistance of the light-transmitting conductive layer 1, and is therefore expressed as "actual value."

[0160] [Expected resistivity value] The expected values ​​of the resistivity of the light-transmitting conductive layer 1 in Examples 1 to 7 and Comparative Example 3 were determined. Specifically, the resistivity of the light-transmitting conductive layer 1 after heating in Comparative Example 1 (Ar mixed) was 2.301×10 -4 By dividing Ωcm by the thickness of the second amorphous conductive film 82 in each example, the expected value (AV Ar) was calculated (Equation (1)). Next, the resistivity after heating of Comparative Example 2 (Kr mixed) was 1.599 × 10 -4 By dividing Ωcm by the thickness of the first amorphous conductive film 81 in each example, the expected value (AV kr ) was calculated (Equation (2)). Ar and A.V. kr By substituting the thickness of the light-transmitting conductive layer 1 of each example into the following formula (3), the expected resistivity of the light-transmitting conductive layer 1 of each example after heating (heating at 155°C for 2 hours) was calculated.

[0161] Formula (1) Expected value (AV Ar )={specific resistance of the light-transmitting conductive layer 1 of Comparative Example 1 / thickness of the second amorphous conductive film 82

[0162] Equation (2) Expected value (AV kr )={specific resistance of light-transmitting conductive layer 1 in Comparative Example 2 / thickness of first amorphous conductive film 81

[0163] Equation (3) Expected value of resistivity of light-transmitting conductive layer 1={(AV Ar ×AV kr ) / (AV Ar +AV kr )} × thickness of light-transmitting conductive layer 1

[0164] In addition, when the light-transmitting conductive layer 1 is a layer in which argon and a rare gas having an atomic number larger than that of argon are mixed as shown in FIG. 5D of the present application, the ratio of the amount of the introduced argon gas and the amount of the rare gas having an atomic number larger than that of argon was replaced with the ratio between the first region 4 and the second region 5 of the light-transmitting conductive layer 1 to calculate the expected value. For example, when the light-transmitting conductive layer 1 was formed with a mixed gas of krypton:argon=2:1, the thickness of the first region 4:the second region 5 was converted to be 2:1, and the expected value of the resistivity of the light-transmitting conductive layer 1 was calculated using the formulas (1) to (3). Specifically, in Comparative Example 3, the light-transmitting conductive layer 1 was formed with a mixed gas of krypton:argon=85:15 (volume ratio), so the thickness of the first region 4:the second region 5 was converted to be 85:15, and the expected value of the resistivity was calculated using the formulas (1) to (3).

[0165] The expected value of resistivity is a resistivity that can be expected by calculation, and more specifically, it is a resistivity that is expected (obtained) as a guideline for calculation, based on the resistivity of the light-transmitting conductive layer 1 of each Example having a first region 4 and a second region 5, the resistivity of the light-transmitting conductive layer 1 (another light-transmitting conductive layer B) of Comparative Example 1 consisting only of the second region 5, and the resistivity of the light-transmitting conductive layer 1 (one light-transmitting conductive layer A) of Comparative Example 2 consisting only of the first region 4.

[0166] [Gain in resistivity] The gain in resistivity of the light-transmitting conductive layer 1 in Examples 1 to 8 was calculated from the following formula.

[0167] Gain of resistivity of light-transmitting conductive layer 1 (%)=[(expected resistivity value−actual measured resistivity value)] / (expected resistivity value)×100

[0168] The resistivity gain of the light-transmitting conductive layer 1 is the percentage by which the actual measured resistivity value of the light-transmitting conductive layer 1 after heating at 155° C. for 2 hours falls below the expected resistivity value of the light-transmitting conductive layer 1. If the resistivity gain of the light-transmitting conductive layer 1 is positive, it means that the actual measured resistivity value of the light-transmitting conductive layer 1 falls below the expected value, that is, the incorporation of Ar and Kr has a significant effect of reducing the resistivity of the light-transmitting conductive layer 1.

[0169] [Transmittance] After heating at 155° C. for 2 hours, the total light transmittance of the light-transmitting conductive film 10 was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd., model: HGM-2DP).

[0170] [Evaluation of crystallinity] Although not shown in Table 1, the results of Examples 1 to 3 after heating for 2 hours in a hot air oven at 155°C were 7 The light-transmitting conductive layer 1 of each of the examples and comparative examples 1 to 3 was observed from the surface with a transmission electron microscope (TEM) to confirm the presence of crystal grains, and it was confirmed that all of them were crystalline. Specifically, the light-transmitting conductive film 10 of each of the examples and comparative examples after heating at 155°C for 2 hours was cut out and fixed to a sample holder of an ultramicrotome. Next, a microtome knife was placed at an extremely acute angle to the ITO film surface, and the cut surface was cut so as to be approximately parallel to the ITO film surface to obtain an observation sample. This observation sample was observed in plan view using a TEM (magnification: 50,000 times). A 1.5 μm x 1.5 μm area was arbitrarily selected from the TEM observation photograph, and the presence or absence of crystal grains in that area was confirmed. Note that in each of the examples and comparative examples, the presence of crystal grains was confirmed over the entire surface direction in plan view, and it was found that the area in which the crystal grains existed was included as the main area (crystalline, and crystalline).

[0171] [Table 1]

[0172] The above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be interpreted as being limited. 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]

[0173] The light-transmitting conductive layer and light-transmitting conductive film of the present invention are used in, for example, touch sensors, light control elements, photoelectric conversion elements, heat ray control members, antennas, electromagnetic wave shielding members, image display devices, heater members, and lighting. [Explanation of symbols]

[0174] 1 Light-transparent conductive layer 2 First main surface 3 Second main surface 4 First area 5 Second area 10. Light-transmitting conductive film 11 Resin layer

Claims

1. A light-transmitting conductive layer having a first main surface and a second main surface disposed on one side of the first main surface in a thickness direction and opposed to the first main surface with a gap therebetween, the light-transmitting conductive layer having a layer extending in a plane direction perpendicular to the thickness direction, the light-transmitting conductive layer comprises a conductive oxide, the conductive oxide contains an indium tin composite oxide, argon, and krypton; The light-transmitting conductive layer is characterized in that it has a peak at about 28.2° in an X-ray spectrum measured by a scanning X-ray fluorescence analyzer, and has a region in which the krypton atom content is less than the detection limit value by Rutherford backscattering spectrometry.

2. The light-transmitting conductive layer according to claim 1 , wherein the light-transmitting conductive layer is crystalline.

3. 3. The light-transmitting conductive layer according to claim 1, further comprising a first region containing krypton and a second region containing argon, the first region being arranged in that order in a thickness direction.

4. The light-transmitting conductive layer according to any one of claims 1 to 3, a substrate in contact with the first main surface of the light-transmitting conductive layer; A light-transmitting conductive film comprising: A light-transmitting conductive film, wherein the first region includes the first main surface.

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