Light-transmitting conductive layer and light-transmitting conductive film

Abstract

The invention relates to a translucent conductive layer and a translucent conductive film. The translucent conductive layer (1) has a first main surface (2), and a second main surface (3) disposed so as to face one surface side of the first main surface (2) in the thickness direction with a gap therebetween. The translucent conductive layer (1) has a single layer extending in the plane direction. The translucent conductive layer (1) contains a conductive oxide. The conductive oxide contains argon and a rare gas having a larger atomic number than argon.

Description

[0001] This application is a divisional application of the application with application date of March 18, 2021, application number 202180029837.7, and invention name "Transparent Conductive Layer and Transparent Conductive Film". Technical Field

[0002] The present invention relates to a light-transmitting conductive layer and a light-transmitting conductive film. Background Art

[0003] Conventionally, a transparent conductive film formed of ITO is known.

[0004] Transparent conductive films are required to have low resistivity. Therefore, as a method for manufacturing a transparent conductive film formed of ITO having low resistivity, a manufacturing method has been proposed in which a horizontal magnetic field on a target is set to 50 mT and sputtering is performed using a mixed gas containing argon gas (for example, Patent Document 1). In addition, a transparent conductive film formed of ITO in which xenon or krypton is mixed instead of argon gas has been proposed (for example, see Patent Document 2 below).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application No. 2013 / 080995

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 7-262829 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] In recent years, transparent conductive films have been required to have lower resistivity. In Patent Document 1, a transparent conductive film having a sufficiently low resistivity cannot be realized. In addition, even the transparent conductive film described in Patent Document 2 has a limit in achieving a low resistivity. In addition, xenon and krypton are very expensive compared to argon due to their rarity, and are preferably used in small amounts.

[0011] The present invention provides a light-transmitting conductive layer and a light-transmitting conductive film having low resistivity.

[0012] Solutions for solving problems

[0013] The present invention (1) includes a translucent conductive layer having a first main surface and a second main surface arranged relative to the first main surface with a gap therebetween on one side in the thickness direction of the first main surface, and having a single layer extending in a surface direction orthogonal to the thickness direction, wherein the translucent conductive layer comprises a conductive oxide, and the conductive oxide comprises argon and a rare gas having an atomic number greater than that of the argon.

[0014] The present invention (2) comprises the light-transmitting conductive layer described in (1), wherein the light-transmitting conductive layer is crystalline.

[0015] The present invention (3) comprises the light-transmitting conductive layer according to (1) or (2), which has a first region containing the rare gas and a second region containing argon in this order along the thickness direction.

[0016] The present invention (4) comprises the light-transmitting conductive layer according to any one of (1) to (3), wherein the rare gas is krypton.

[0017] The present invention (5) comprises the light-transmitting conductive layer according to any one of (1) to (4), wherein the conductive oxide further contains indium and tin.

[0018] The present invention (6) includes a translucent conductive film comprising: a translucent conductive layer as described in any one of (1) to (5); and a substrate in contact with the first main surface of the translucent conductive layer, wherein the first region includes the first main surface.

[0019] Effects of the Invention

[0020] The light-transmitting conductive layer of the present invention has a low resistivity.

[0021] Since the light-transmitting conductive film of the present invention includes the light-transmitting conductive layer, it has excellent reliability. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is an enlarged cross-sectional view of one embodiment of the light-transmitting conductive layer of the present invention.

[0023] Figure 2 Yes Figure 1 A cross-sectional view of a light-transmitting conductive film showing a light-transmitting conductive layer.

[0024] Figure 3 It is used to manufacture Figure 2 Schematic diagram of a sputtering device for a light-transmitting conductive film is shown.

[0025] Figure 4 yes Figure 2 A cross-sectional view of a modified example of the light-transmitting conductive film shown.

[0026] Figure 5 A~ Figure 5 D is Figure 1 An enlarged cross-sectional view of a modified example of the light-transmitting conductive layer shown in FIG. Figure 5 A is a modified example in which the second region includes the first main surface and the first region includes the second main surface, Figure 5 B and Figure 5 C is a modified example in which the first region and the second region are alternately arranged. Figure 5 D is a modified example in which argon and a rare gas having an atomic number larger than that of argon are mixed.

[0027] Figure 6 This is a graph showing the relationship between the amount of oxygen introduced when an amorphous light-transmitting conductive layer is formed by sputtering and the surface resistance of the amorphous light-transmitting conductive layer.

[0028] Figure 7 A~ Figure 7 B is a cross-sectional view of another example of a laminate including a light-transmitting conductive layer, Figure 7 A is a light-transmitting conductive layer laminate in which a light-transmitting conductive layer is laminated on a functional layer, Figure 7 B is a light-transmitting conductive film in which a light-transmitting conductive layer is laminated on a transparent base film.

[0029] Description of Reference Numerals

[0030] 1 Translucent conductive layer

[0031] 2 First main surface

[0032] 3 Second main surface

[0033] 4. First Area

[0034] 5 Second Area

[0035] 10Light-transmitting conductive film

[0036] 11. Resin layer DETAILED DESCRIPTION

[0037] [One embodiment of the light-transmitting conductive layer]

[0038] Figure 1 The light-transmitting conductive layer 1 shown is a light-transmitting conductive film 10 described later (see Figure 2 ), a touch sensor, a dimming element, a photoelectric conversion element, a heat line control member, an antenna, an electromagnetic wave shielding member, an image display device, a heater member (translucent heater) and a lighting device, etc., and the translucent conductive layer 1 is an intermediate member for manufacturing them. The translucent conductive layer 1 is a layer that can be circulated independently and used in industry.

[0039] The light-transmitting conductive layer 1 has a first principal surface 2 and a second principal surface 3 disposed opposite to the first principal surface 2 with a distance therebetween in the thickness direction. The light-transmitting conductive layer 1 has a single layer extending in a plane direction perpendicular to the thickness direction.

[0040] [Material]

[0041] The light-transmitting conductive layer 1 is formed of a composition including a conductive oxide, preferably a conductive oxide. The conductive oxide is a main component of the light-transmitting conductive layer 1, and contains a trace amount of argon and a rare gas with an atomic number greater than argon. Specifically, a trace amount of argon and a rare gas with an atomic number greater than argon is mixed in the conductive oxide.

[0042] [Argon]

[0043] Argon is derived from argon contained in the sputtering gas in the production method described later, and is mixed into the conductive oxide. Figure 1 Argon is drawn as a white circle in the figure.

[0044] [Noble gases with atomic numbers greater than argon]

[0045] As the rare gas with an atomic number larger than argon, for example, krypton, xenon, radon, etc. can be listed. They can be used alone or in combination. Krypton and xenon can be preferably listed. From the viewpoint of obtaining low price and excellent conductivity, krypton (specifically, krypton alone) can be more preferably listed. The rare gas with an atomic number larger than argon is derived from the rare gas contained in the sputtering gas in the manufacturing method described later, and is mixed into the conductive oxide. Figure 1 In the diagram, the noble gases with atomic numbers greater than argon are drawn with black circles.

[0046] [Conductive oxide]

[0047] The conductive oxide is a matrix in which the above-mentioned argon and a rare gas having an atomic number greater than argon are dispersed. Examples of the conductive oxide include metal oxides containing at least one metal or semimetal selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. The metal oxide may be further doped with metal atoms and / or semimetal atoms shown in the above group as needed.

[0048] As the conductive oxide, specifically, metal oxides such as indium zinc composite oxide (IZO), indium gallium zinc composite oxide (IGZO), indium gallium composite oxide (IGO), indium tin composite oxide (ITO), and antimony tin composite oxide (ATO) can be cited. As the conductive oxide, from the viewpoint of improving transparency and conductivity, indium tin composite oxide (ITO) containing both indium and tin can be preferably cited. If the conductive oxide is ITO, transparency and conductivity are more excellent.

[0049] When the conductive oxide is ITO, the ratio of the content of tin oxide in the ITO to the total content of indium oxide (In2O3) and tin oxide (SnO2) is, for example, 0.1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, and further preferably 10% by mass or more. The ratio of the number of tin atoms in the ITO used to the number of indium atoms (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, further preferably 0.07 or more, and further preferably 0.10 or more. If the ratio of the content of tin oxide to the number of indium atoms is above the above lower limit, and / or the ratio of the number of tin atoms is above the above lower limit, the durability of the light-transmitting conductive layer 1 can be ensured.

[0050] The ratio of the content of tin oxide in the ITO used to the total content of indium oxide (In2O3) and tin oxide (SnO2) is, for example, 20% by mass or less, preferably 15% by mass or less, more preferably 13% by mass or less, and further preferably 12% by mass or less. The ratio of the number of tin atoms in the ITO used to the number of indium atoms (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 further preferably 0.13 or less. If the content ratio of tin oxide is below the above upper limit, and / or the ratio of the number of tin atoms to the number of indium atoms is below the above upper limit, a light-transmitting conductive layer 1 that is easily crystallized by heating can be obtained.

[0051] The ratio of the number of tin atoms in ITO to the number of indium atoms is obtained as follows: for example, the ratio of the presence of indium atoms to tin atoms is determined by X-ray photoelectron spectroscopy for the object to be measured. The above-mentioned content ratio of tin oxide in ITO is obtained, for example, from the ratio of the presence of indium atoms to tin atoms determined by such operation. The ratio of the presence of indium atoms to tin atoms in ITO and the above-mentioned content ratio of tin oxide can be determined based on the content ratio of indium oxide (In2O3) to tin oxide (SnO2) of the ITO target used for sputtering film formation.

[0052] [First area, second area]

[0053] In this embodiment, if Figure 1 As shown, the light-transmitting conductive layer 1 includes, in this order along the thickness direction, a first region 4 containing a rare gas having an atomic number greater than argon and a second region 5 containing argon.

[0054] [First Area]

[0055] 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 argon with respect to the conductive oxide is dispersed in the thickness direction and the surface direction.

[0056] In the first region 4, the content ratio of the rare gas having an atomic number greater than 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, further preferably 0.5 atom% or less, further preferably 0.3 atom% or less, particularly preferably 0.2 atom% or less, and most preferably 0.15 atom% or less. If the content ratio of the rare gas having an atomic number greater than argon is within the above range, the resistivity and transparency of the light-transmitting conductive layer 1 are excellent.

[0057] It should be noted that in Figure 1 Although not shown in the figure, argon is allowed to be mixed in the first region 4. However, in this case, the content ratio R of the rare gas having an atomic number greater than that of argon in the first region 4 is rg1 is greater than the content ratio R of the rare gas having an atomic number greater than argon in the second region 5 rg2 Specifically, R rg1 / R rg2 For example, it is greater than 1, preferably greater than 1.2, more preferably greater than 1.5, and, for example, less than 10000. The rare gas with an atomic number greater than argon in the first region 4 is identified (determined whether it exists) by, for example, Rutherford Backscattering Spectrometry, secondary ion mass spectrometry, laser resonance ionization mass spectrometry and / or fluorescent X-ray analysis. From the perspective of simplicity of analysis, it is preferably identified by fluorescent X-ray analysis. The details of the fluorescent X-ray analysis are described in the embodiments. In the first region 4 and the translucent conductive layer 1 including the first region 4, when Rutherford backscattering analysis is performed, it is impossible to quantify because the content of the rare gas atoms is not above the detection limit (lower limit). On the other hand, when fluorescent X-ray analysis is performed, when the presence of the rare gas atoms is identified, it is judged that the translucent conductive layer 1 contains a region with a Kr content of more than 0.0001 atom%.

[0058] 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, further preferably 0.8 or less, and particularly preferably 0.7 or less, and is, for example, 0.01 or more, preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.2 or more, and particularly preferably 0.3 or more. If the ratio R1 of the first region 4 is below the upper limit, the resistivity of the light-transmitting conductive layer 1 can be reduced, and a significant gain in resistivity can be obtained (described later).

[0059] [Second Area]

[0060] The second region 5 includes a second main surface 3. In the second region 5, argon is dispersed in the thickness direction and the surface direction relative to the conductive oxide. In addition, in the light-transmitting conductive layer 1, the content ratio of the rare gas having an atomic number greater than that of argon is, for example, greater than 0.001 atom%, and further, for example, less than 0.5 atom%. In addition, in the light-transmitting conductive layer 1, the content ratio of argon is, for example, greater than 0.001 atom%, preferably greater than 0.01 atom%, and further, for example, less than 0.5 atom%, preferably less than 0.4 atom%, more preferably less than 0.3 atom%, and further preferably less than 0.2 atom%. Even in the case where the light-transmitting conductive layer 1 cannot be formed using high temperature conditions (for example, 200°C), if the content ratio 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.

[0061] It should be noted that in Figure 1 Although not shown in the figure, a rare gas having an atomic number greater than argon is allowed to be mixed into the second region 5. However, in this case, the content ratio R of argon in the second region 5 is Ar2 Greater than the argon content R in the first region 4 Ar1 Specifically, R Ar2 / R Ar1 For example, it is greater than 1, preferably greater than 1.2, more preferably greater than 1.5, and for example less than 10000. Argon in the light-transmitting conductive layer 1 is identified (determined whether it exists) by, for example, Rutherford backscattering spectrometry (RBS) and quantified. The details of Rutherford backscattering spectrometry are described in the examples.

[0062] In the thickness direction, the ratio (thickness ratio) R2 of the second region 5 in the light-transmitting conductive layer 1 is, for example, greater than 0.01, preferably greater than 0.05, more preferably greater than 0.1, further preferably greater than 0.2, and particularly preferably greater than 0.3, and, for example, less than 0.99, preferably less than 0.95, more preferably less than 0.9, further preferably less than 0.8, and particularly preferably less than 0.7. If the ratio R2 of the second region 5 is greater than the above lower limit, the resistivity of the light-transmitting conductive layer 1 can be reduced, and a significant gain in resistivity can be obtained (described later). If the ratio R2 of the second region 5 is less than the above upper limit, the transparency and conductivity of the light-transmitting conductive layer 1 are excellent.

[0063] It should be noted that in Figure 1 In FIG. 1 , the boundary between the first region 4 and the second region 5 is depicted by an imaginary line (two-dot chain line). However, in reality, the boundary between the first region 4 and the second region 5 may not be discerned. In this case, in the first region 4 and the second region 5, the region with a high content ratio R3 of a rare gas having an atomic number greater than argon is the first region 4, and the region with a high content ratio R4 of argon is the second region 5.

[0064] [Physical properties of light-transmitting conductive layer]

[0065] The light-transmitting conductive layer 1 is, for example, amorphous (non-crystalline) or crystalline (crystalline). Amorphous refers to a film property that does not contain crystal grains, and crystalline refers to a film property that contains crystal grains. From the viewpoint of reducing resistivity, the light-transmitting conductive layer 1 is preferably crystalline, and more preferably includes a region where crystal grains exist as a main region. Including a region where crystal grains exist as a main region means that, when viewed from above, for example, crystal grains exist in a region of, for example, more than 60%, preferably more than 80%, more preferably more than 85%, further preferably more than 90%, and for example less than 100% of the light-transmitting conductive layer 1. If the light-transmitting conductive layer 1 includes a region where crystal grains exist as a main region, a low resistivity can be obtained. In addition, in the present application, when viewed from above, especially in the case of a light-transmitting conductive layer 1 with high crystallinity, specifically, when the region where crystal grains exist is more than 90%, preferably more than 95%, and less than 100%, it can also be expressed as the light-transmitting conductive layer 1 being crystalline. If it is crystalline, it has crystal grains on substantially the entire surface, so a lower resistivity can be obtained. In the vicinity of the grain boundary at the end of the crystal grain, the crystallinity may inevitably decrease, and even if it is crystalline, it does not need to be 100%.

[0066] The crystallinity of the light-transmitting conductive layer 1 can be determined by observing the surface of the light-transmitting conductive layer 1 from the first main surface side or the second main surface side using TEM, for example, and confirming the presence of crystal grains. If crystal grains are observed, it is crystallinity. The specific observation method is described in detail in the examples.

[0067] In addition, whether the light-transmitting conductive layer 1 is crystalline can also be judged as follows: the light-transmitting conductive layer 1 is immersed in hydrochloric acid (20° C., concentration of 5 mass %) for 15 minutes, followed by water washing and drying, and then the terminal resistance between about 15 mm is measured for the second main surface 3 of the light-transmitting conductive layer 1. In the light-transmitting conductive layer 1 after the above immersion / water washing / drying, when the terminal resistance between 15 mm (the resistance between two terminals) is 10 kΩ or less, the light-transmitting conductive layer 1 is crystalline.

[0068] 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, and further preferably 100 nm or more, and is, for example, 1000 nm or less, preferably less than 300 nm, more preferably less than 250 nm, further preferably less than 200 nm, further preferably less than 160 nm, particularly preferably less than 150 nm, and most preferably less than 148 nm. If 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.

[0069] The total light transmittance (JIS K7375-2008) 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 for example, 100% or less.

[0070] The surface resistance of the light-transmitting conductive layer 1 (crystalline light-transmitting conductive layer 1) is, for example, 200Ω / □ or less, preferably 100Ω / □ or less, more preferably 50Ω / □ or less, further preferably 15Ω / □ or less, and particularly preferably 13Ω / □ or less, and, for example, exceeds 0Ω / □, and further is 1Ω / □ or more. The surface resistance can be measured by a four-terminal method according to JIS K7194.

[0071] 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 less than 2.000×10 -4 Ω·cm, more preferably 1.800×10 -4 Ω·cm or less, and for example, 0.100×10 -4 Ω·cm or more, and further 0.500×10 -4 Ω·cm or more, and further 1.000×10 -4 Ω·cm or more. The resistivity is obtained by multiplying the surface resistance by the thickness.

[0072] The total content ratio of argon and the rare gas with an atomic number larger than 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, further preferably 0.8 atom% or less, particularly preferably 0.5 atom% or less, further 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 ratio of argon and the rare gas with an atomic number larger than argon is below the above upper limit, the total content ratio of impurity atoms (in other words, argon and the rare gas with an atomic number larger than argon) in the light-transmitting conductive layer 1 is small, and therefore, a light-transmitting conductive layer 1 with high electron mobility and low resistivity can be obtained.

[0073] [Light-transmitting conductive film]

[0074] Next, refer to Figure 2 To illustrate the Figure 1 The light-transmitting conductive film 10 of the light-transmitting conductive layer 1 is shown.

[0075] like Figure 2 As shown, the light-transmitting conductive film 10 has a film shape extending in the surface 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.

[0076] [Resin layer]

[0077] The resin layer 11 forms the other side of the light-transmitting conductive film 10 in the thickness direction. The resin layer 11 has a film shape extending in the surface direction. The resin layer 11 is a substrate layer. The resin layer 11 has flexibility. For example, the resin layer 11 has a transparent substrate film 13 and a functional layer 14 in sequence on one side in the thickness direction. The resin layer 11 is preferably not adjacent to the glass substrate.

[0078] The transparent substrate film 13 has a film shape extending in the surface direction. The transparent substrate film 13 forms the other side of the resin layer 11 in the thickness direction. 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 such as polyacrylate and / or polymethacrylate (acrylic resins and / or methacrylic resins); resins such as polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, and polystyrene resins. Preferably, polyester resins are listed, and more preferably, PET is listed. The thickness of the transparent base 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, further preferably 75 μm or less.

[0079] The total light transmittance (JIS K 7375-2008) of the transparent base film 13 is, for example, 60% or more, preferably 80% or more, more preferably 85% or more, and is 100% or less.

[0080] The functional layer 14 forms one surface in the thickness direction of the resin layer 11. The functional layer 14 is arranged on one surface in the thickness direction of the transparent substrate film 13. Specifically, the functional layer 14 contacts all of one surface in the thickness direction of the transparent substrate film 13. The functional layer 14 extends in the surface direction. The functional layer is a layer containing resin. As the functional layer 14, for example, a hard coating layer can be cited. In this case, the resin layer 11 has a transparent substrate film 13 and a hard coating layer in sequence on one side in the thickness direction. In the following description, the description is made for the case where the functional layer 14 is a hard coating layer.

[0081] The hard coating layer is a scratch protection layer for preventing the light-transmitting conductive layer 1 from being easily scratched. The hard coating layer forms one surface of the resin layer 11 in the thickness direction. The hard coating layer is in contact with the entire surface of one surface of the transparent substrate film 13 in the thickness direction. As a material for the hard coating layer, a cured product of a hard coating composition (acrylic resin, urethane resin, etc.) described in Japanese Patent Publication No. 2016-179686 can be cited. The thickness of the hard coating 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.

[0082] [Physical properties of resin layer]

[0083] 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, further preferably 30 μm or more, and is, for example, 310 μm or less, preferably 210 μm or less, more preferably 110 μm or less, further preferably 80 μm or less.

[0084] The total light transmittance (JIS K 7375-2008) of the resin layer 11 is, for example, 60% or more, preferably 80% or more, more preferably 85% or more, and for example, 100% or less.

[0085] [Light-transmitting conductive layer]

[0086] 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 surface of one surface in the thickness direction of the resin layer 11. In other words, the first principal surface 2 of the light-transmitting conductive layer 1 is in contact with one surface in the thickness direction of the resin layer 11. On the other hand, the second principal surface 3 of the light-transmitting conductive layer 1 is exposed on one side in the thickness direction. Thus, in the light-transmitting conductive film 10, the resin layer 11, the first region 4, and the second region 5 are sequentially arranged 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, for example, 0.5 or less, preferably 0.25 or less.

[0087] [Method for producing light-transmitting conductive film]

[0088] Next, refer to Figure 3 The following describes a method for producing the light-transmitting conductive film 10. In this method, the light-transmitting conductive layer 1 is formed on the resin layer 11 by, for example, a roll-to-roll method.

[0089] In this method, first, a resin layer 11 is prepared. Specifically, a hard coating composition is applied to one surface in the thickness direction of a transparent substrate film 13 and dried, and then the hard coating composition is cured. Thus, a resin layer 11 having a transparent substrate film 13 and a hard coating layer (functional layer 14) in this order on one side in the thickness direction is prepared.

[0090] Thereafter, the resin layer 11 is subjected to a degassing treatment as required. In order to perform a degassing treatment on the resin layer 11, the resin layer 11 is placed in a 1×10 -1 Pa or less, preferably 1×10 -2 Pa or less, and for example, 1×10 -6 The resin layer 11 is placed in a reduced pressure atmosphere of not less than 100 Pa. Specifically, the atmosphere around the resin layer 11 is reduced in pressure using a pump (described later) of the sputtering device 30 .

[0091] 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 conveyed in the sputtering device 30 .

[0092] [Sputtering device]

[0093] The sputtering device 30 includes a drawing unit 35 , a sputtering unit 36 ​​, and a winding unit 37 in this order.

[0094] The delivery section 35 includes a delivery roller 38 and a discharge port of the delivery-side pump 33 .

[0095] The sputtering unit 36 ​​includes a film forming roller 40 , a first film forming chamber 41 , and a second film forming chamber 42 .

[0096] The film-forming roller 40 includes a cooling device (not shown) configured to cool the film-forming roller 40 .

[0097] The first film forming chamber 41 accommodates the first target 51, the first gas supplier 61, and the discharge port of the first pump 71. The first target 51, the first gas supplier 61, and the discharge port of the first pump 71 are arranged to face the film forming roll 40 with a gap therebetween.

[0098] The material of the first target 51 may be the same material as the above-mentioned conductive oxide. It should be noted that the material of the first target 51 includes a sintered body of a conductive oxide. In these conductive oxides, a rare gas and argon having an atomic number greater than argon are not mixed. The first target 51 is configured in a manner to apply electricity.

[0099] A magnet (not shown) is arranged on the opposite side of the film forming roller 40 with respect to the first target 51. The horizontal magnetic field intensity on the surface of the first target 51 is, for example, 10 mT or more, preferably 60 mT or more, and, for example, 300 mT or less. By arranging the magnet, the horizontal magnetic field intensity on the surface of the first target 51 is set to the above range, so that the content of the rare gas with an atomic number larger than argon contained in the first amorphous conductive film 81 (first region 4) described later can be adjusted.

[0100] The first gas supply device 61 is configured to supply the first sputtering gas to the first film forming chamber 41. The first sputtering gas includes a rare gas having an atomic number greater than argon. Specifically, the first sputtering gas includes, for example, a rare gas having an atomic number greater than argon, or, for example, a first mixed gas including a rare gas having an atomic number greater than argon and a reactive gas such as oxygen. Preferably, the first mixed gas is used.

[0101] When the sputtering gas is the first mixed gas, the first gas supply machine 61 includes a rare gas supply machine 63 and a first oxygen supply machine 64, thereby supplying a rare gas with an atomic number greater than argon and oxygen respectively into the first film forming chamber 41. It should be noted that the "rare gas" in the rare gas supply machine 63 does not contain argon, but refers to a rare gas with an atomic number greater than argon.

[0102] The second film forming chamber 42 is arranged adjacent to the first film forming chamber 41 in the circumferential direction of the film forming roller 40. Thus, the first film forming chamber 41 and the second film forming chamber 42 are arranged in sequence in the circumferential direction. The second film forming chamber 42 accommodates the second target 52, the second gas supply machine 62, and the discharge port of the second pump 72. The second target 52, the second gas supply machine 62, and the discharge port of the second pump 72 are arranged relative to the film forming roller 40 with a gap therebetween.

[0103] The material of the second target 52 may be the same material as the above-mentioned conductive oxide. It should be noted that the material of the second target 52 includes a sintered body of a conductive oxide. In these conductive oxides, a rare gas and argon having an atomic number greater than argon are not mixed. The second target 52 is configured in a manner that electricity is applied.

[0104] A magnet (not shown) is disposed on the opposite side of the film forming roller 40 relative to the second target 52. The horizontal magnetic field intensity on the surface of the second target 52 is, for example, 10 mT or more, preferably 60 mT or more, and, for example, 300 mT or less. By disposing the magnet, the horizontal magnetic field intensity on the surface of the second target 52 is set to the above range, so that the content of argon contained in the second amorphous conductive film 82 (second region 5) described later can be adjusted.

[0105] The second gas supply machine 62 is configured to supply the second sputtering gas to the second film forming chamber 42. As the second sputtering gas, for example, argon or a second mixed gas containing reactive gases such as argon and oxygen can be listed. Preferably, the second mixed gas can be listed. If the second sputtering gas is the second mixed gas, the second gas supply machine 62 includes an argon supply machine 65 and a second oxygen supply machine 66, thereby supplying argon and oxygen to the second film forming chamber 42 respectively.

[0106] The winding section 37 includes a winding roller 39 and a discharge port of the winding-side pump 34 .

[0107] [Manufacturing of light-transmitting conductive film]

[0108] In order to form the light-transmitting conductive layer 1 on the resin layer 11 using the sputtering device 30 , first, the resin layer 11 is laid on the delivery roll 38 , the film-forming roll 40 , and the winding roll 39 .

[0109] While driving the first pump 71, the sputtering gas is supplied from the first gas supply machine 61 into the first film forming chamber 41. The pressure of the noble gas having an atomic number larger than argon (if the sputtering gas is the first mixed gas, the partial pressure of the noble gas having an atomic number larger than 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.

[0110] While driving the second pump 72, the sputtering gas is supplied from the second gas supply machine 63 into the first film forming 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.

[0111] In addition, the cooling device is driven to cool the film-forming roller 40 (the surface). The temperature (surface temperature) of the film-forming roller 40 is, for example, 20.0°C or less, preferably 10.0°C or less, more preferably 0.0°C or less, and, for example, -50°C or more, preferably -25°C or more. By sufficiently cooling the resin layer 11, it is possible to suppress 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 translucent conductive layer 1 can be reduced, and a translucent conductive layer 1 having excellent resistivity can be obtained.

[0112] Next, the resin layer 11 is drawn out from the drawing roll 38 by driving the drawing roll 38, the film forming roll 40, and the winding roll 39. The resin layer 11 moves sequentially in the first film forming chamber 41 and the second film forming chamber 42 while contacting the surface of the film forming roll 40. At this time, the resin layer 11 is cooled by contacting the surface of the film forming roll 40.

[0113] In the vicinity of the first target 51, the sputtering gas is ionized to generate an ionized gas. Then, the ionized gas hits the first target 51, and the target material of the first target 51 forms particles and is knocked out, and the particles are attached (deposited) on the resin layer 11 to form the first amorphous conductive film 81. At this time, the rare gas contained in the sputtering gas (a rare gas with an atomic number greater than argon, preferably krypton) enters the first amorphous conductive film 81 together with the particles. The amount of the rare gas entering the first amorphous conductive film 81 is adjusted by the magnetic field strength, the power density of the electric power applied to the first target 51, and / or the pressure in the first film forming chamber 41. In addition, the thickness of the first amorphous conductive film 81 is adjusted by the power density of the electric power applied to the first target 51.

[0114] Next, the sputtering gas is ionized near the second target 52 to generate an ionized gas. Next, the ionized gas hits the second target 52, and the target material of the second target 52 forms particles and is knocked out, and the particles are attached (deposited) on the first amorphous conductive film 81 to form the second amorphous conductive film 82. At this time, the argon contained in the sputtering gas enters the second amorphous conductive film 82 together with the particles. The amount of the rare gas entering the second amorphous conductive film 82 is adjusted by the magnetic field strength, the power density of the electric power applied to the second target 52, and / or the pressure in the second film forming chamber 42. In addition, the thickness of the second amorphous conductive film 82 is adjusted by the power density of the electric power applied to the second target 52.

[0115] Thus, the 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.

[0116] The first amorphous conductive film 81 and the second amorphous conductive film 82 respectively form the first region 4 and the second region 5. Since the first amorphous conductive film 81 and the second amorphous conductive film 82 contain the same conductive oxide as a main component, the boundary between them may not be observed.

[0117] Therefore, if Figure 2 As shown, the 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. Thus, the light-transmitting conductive film 10 including the resin layer 11 and the light-transmitting conductive layer 1 is manufactured.

[0118] The total light transmittance (JIS K 7375-2008) of the 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.

[0119] 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, further preferably 30 minutes or more, and further preferably 1 hour or more, and, for example, 5 hours or less, preferably 3 hours or less.

[0120] In this way, the light-transmitting conductive film 10 including the resin layer 11 and the light-transmitting conductive layer 1 including the crystalline region is manufactured.

[0121] The total light transmittance (JISK 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.

[0122] The light-transmitting conductive film 10 can be used for various articles. As articles, it can be used for example, a touch sensor, an electromagnetic wave shielding member, a dimming element (voltage-driven dimming element such as PDLC, PNLC, SPD, etc.; current-driven dimming element such as electrochromic (EC), etc.), a photoelectric conversion element (electrodes of solar cell elements represented by organic thin-film solar cells and dye-sensitized solar cells, etc.), a heat control member (e.g., a near-infrared reflection and / or absorption member, such as a far-infrared reflection and / or absorption member), an antenna member (light-transmitting antenna), a heater member (light-transmitting heater), an image display device, lighting, etc.

[0123] The article includes the light-transmitting conductive film 10 and components corresponding to the articles.

[0124] Such an article is obtained by fixing the light-transmitting conductive film 10 and members corresponding to each article.

[0125] Specifically, 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 members corresponding to the respective articles are fixed via, for example, an anchoring functional layer.

[0126] Examples of the anchoring function layer include an adhesive layer and a bonding layer.

[0127] As the fixing function layer, as long as it has transparency, it can be used without special material limitation. The fixing function layer is preferably formed by resin. As the resin, for example, 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 can be listed. In particular, from the viewpoint of excellent optical transparency, showing appropriate adhesive properties such as wettability, cohesion and adhesion, and excellent weather resistance and heat resistance, as the resin, acrylic resin is preferably selected.

[0128] In order to suppress the corrosion and migration of the light-transmitting conductive layer 1, a known anticorrosive agent and an anti-migration agent (such as the material disclosed in Japanese Patent Application Laid-Open No. 2015-022397) may be added to the resin forming the fixing function layer. In addition, in order to suppress the degradation of the article when it is used outdoors, a known ultraviolet absorber may be added to the fixing function layer (the resin forming the fixing function layer). Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxalic anilide compounds, cyanoacrylate compounds, and triazine compounds.

[0129] In addition, the resin layer 11 in the light-transmitting conductive film 10 and the components corresponding to the articles may be fixed by means of the fixing functional layer. In this case, the light-transmitting conductive layer 1 (the light-transmitting conductive layer 1 having a pattern shape) is exposed in the light-transmitting conductive film 10. Therefore, a covering layer may be arranged on one surface of the light-transmitting conductive layer 1 in the thickness direction.

[0130] The cover layer is a layer covering the light-transmitting conductive layer 1 , and can improve the reliability of the light-transmitting conductive layer 1 and suppress functional degradation due to damage.

[0131] The material of the covering layer is preferably a dielectric. The covering layer is formed of a mixture of a resin and an inorganic material. As the resin, the resins exemplified in the fixing function layer can be cited. As the inorganic material, the materials exemplified in the materials of the intermediate layer described later can be cited.

[0132] In addition, from the same viewpoint as the above-mentioned anchor function layer, a corrosion inhibitor, an anti-migration agent, and an ultraviolet absorber may be added to the mixture of the above-mentioned resin and the inorganic material.

[0133] The above-mentioned articles have excellent reliability because they include the above-mentioned light-transmitting conductive film 10. Specifically, since the touch sensor, dimming element, photoelectric conversion element, hot line control component, antenna, electromagnetic wave shielding component, image display device, heater component and lighting have the above-mentioned light-transmitting conductive film 10, they have excellent reliability.

[0134] [Effects]

[0135] Generally, one light-transmitting conductive layer A formed of a conductive oxide containing a rare gas having an atomic number greater than argon has a lower resistivity than another light-transmitting conductive layer B formed of a conductive oxide containing argon. Specifically, one light-transmitting conductive layer A consisting only of the first region 4 (equivalent to Comparative Example 2) has a lower resistivity than another light-transmitting conductive layer B consisting only of the second region 5 (equivalent to Comparative Example 1).

[0136] like Figure 1As shown, the translucent conductive layer 1 of this embodiment has a first region 4 and a second region 5, and therefore it can be expected (predicted) that it has a resistivity (surface resistance) obtained by combining the resistivity (surface resistance) of one translucent conductive layer A and the resistivity (surface resistance) of the other translucent conductive layer B mentioned above.

[0137] 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. This conclusion is verified by the gain in resistivity described in the examples described later.

[0138] The gain in resistivity of the light-transmitting conductive layer 1 is, for example, 1.0% or more, preferably 5.0% or more, more preferably 10.0% or more, more preferably 12.0% or more, more preferably 14.0% or more, more preferably 15.0% or more, more preferably 17.0% or more, more preferably 18.0% or more, more preferably 20.0% or more, and, for example, 50.0% or less. The method for obtaining the gain in resistivity will be described in the examples described later.

[0139] Furthermore, in the light-transmitting conductive layer 1 of one embodiment, although the conductive oxide contains argon and a rare gas having an atomic number larger than argon, surprisingly, the resistivity of the light-transmitting conductive layer 1 of one embodiment is lower than that of the light-transmitting conductive layer A.

[0140] The light-transmitting conductive film 10 (see Figure 2 ), a touch sensor, a dimming element, a photoelectric conversion element, a heat line control member, an antenna, an electromagnetic wave shielding member, and an image display device have the above-mentioned light-transmitting conductive layer 1, and therefore have excellent resistance characteristics and reliability. In other words, the above-mentioned articles have the above-mentioned light-transmitting conductive layer 1, and therefore have excellent resistance characteristics and reliability.

[0141] [Modifications]

[0142] In the variant, the same reference numerals are used for the same components and processes as those in one embodiment, and detailed description thereof is omitted. In addition, unless otherwise specified, the variant can have the same effects as those in one embodiment. Furthermore, one embodiment and its variant can be appropriately combined.

[0143] In one embodiment, the first region 4 into which the rare gas having an atomic number greater than argon is mixed includes the first main surface 2 in contact with the resin layer 11 .

[0144] However, if Figure 4 As shown, the second region 5 into which argon is mixed may include the first main surface 2 . The second region 5 is in contact with the resin layer 11 .

[0145] As in one embodiment, it is preferable that the first region 4 is located on the side of the first main surface 2. According to this configuration, a gain in resistivity can be significantly ensured (described in detail in the later-described Examples).

[0146] For example, Figure 5 B and Figure 5 As shown in C, the first region 4 and the second region 5 can be repeatedly arranged alternately. Figure 5 In the modified example of B, the first region 4, the second region 5, the first region 4 and the second region 5 are sequentially arranged toward one side in the thickness direction. Figure 5 In the modified example of C, the second region 5, the first region 4, the second region 5, and the first region 4 are sequentially arranged on one side in the thickness direction. In addition, although not shown in the figure, the first region 4 may be further arranged in a structure in which the first region 4 and the second region 5 are alternately and repeatedly arranged on one side in the thickness direction. The second region 5 may also be further arranged in a structure in which the second region 5 and the first region 4 are alternately and repeatedly arranged on one side in the thickness direction. In addition, the first region 4, the second region 5, and the first region 4 may be sequentially arranged in the thickness direction. In addition, the second region 5, the first region 4, and the second region 5 may be sequentially arranged in the thickness direction.

[0147] Furthermore, if Figure 5 As shown in D, the light-transmitting conductive layer 1 may not have the first region 4 and the second region 5, but may contain a mixture of argon and a rare gas having an atomic number greater than argon (uniformly dispersed) in the light-transmitting conductive layer 1. Figure 5 In the translucent conductive layer 1 shown in D, a sputtering gas containing both argon and a rare gas with an atomic number larger than argon is supplied from a gas supply machine into a film forming chamber. More specifically, both argon and a rare gas with an atomic number larger than argon are supplied from a rare gas supply machine 63. The ratio of the volume of the rare gas with an atomic number larger than argon to the total volume of the rare gas with an atomic number larger than argon and the argon gas is, for example, 1% by volume or more, preferably 10% by volume or more, more preferably 30% by volume or more, further preferably 60% by volume or more, particularly preferably 70% by volume or more, and most preferably 80% by volume or more, and, for example, 99% by volume or less, preferably 90% by volume or less, and more preferably 88% by volume or less.

[0148] The amorphous light-transmitting conductive layer 1 immediately after sputtering is formed of the third amorphous conductive film 83. Argon and a rare gas having an atomic number greater than argon are mixed (uniformly dispersed) in the third amorphous conductive film 83. After film formation, the third amorphous conductive film 83 is heated to be crystallized.

[0149] In one embodiment, in the light-transmitting conductive film 10, the light-transmitting conductive layer 1 is in contact with the entire surface of the resin layer 11 in the thickness direction, and although not shown, the light-transmitting conductive layer 1 may be patterned so that an arbitrary region remains. That is, the light-transmitting conductive layer 1 may have a region that does not exist on the resin layer 11. By patterning, it can be suitably used in a touch sensor, a dimming element, a photoelectric conversion element, etc.

[0150] The resin layer 11 may further include other functional layers. Figure 2 and Figure 4 As shown by the imaginary line of , an anti-blocking layer 12 may be provided on the other side in the thickness direction of the transparent base film 13. When the light-transmitting conductive films 10 are stacked in the thickness direction, the anti-blocking layer 12 imparts anti-blocking properties to the surfaces of the plurality of light-transmitting conductive films 10 in contact with each other.

[0151] In addition, the resin layer 11 may further include an easy-adhesion layer between the anti-blocking layer 12 and the transparent base film 13 .

[0152] In addition, the resin layer 11 may also have an intermediate layer (not shown) formed of an inorganic layer on one side of the transparent substrate film 13. The intermediate layer has the function of increasing the surface hardness of the resin layer 11, adjusting the optical properties (specifically, the refractive index) of the light-transmitting conductive film 10, or alleviating the stress on the light-transmitting conductive layer 1 from the resin layer 11 at an intermediate location. The intermediate layer may exist in any position relative to the transparent substrate film 13, the functional layer 14, and the anti-adhesion layer 12, and may have multiple layers. For example, the resin layer 11 has a transparent substrate film 13, a functional layer 14, and an intermediate layer in sequence on one side facing the thickness direction. In addition, the resin layer 11, for example, has an intermediate layer, an anti-adhesion layer 12, a transparent substrate film 13, and a functional layer 14 in sequence on one side facing the thickness direction. The intermediate layer is preferably an inorganic dielectric, and its surface resistance is, for example, 1×10 6 Ω / □ or more, preferably 1×10 8 Ω / □ or more. The material of the intermediate layer is formed of, for example, inorganic oxides such as silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide, calcium oxide, and fluorides such as magnesium fluoride. It should be noted that the composition of the inorganic functional layer may or may not be a stoichiometric composition.

[0153] The functional layer 14 may be an optical adjustment layer (not shown). In this modification, the resin layer 11 includes a transparent base film 13 and an optical adjustment layer in sequence on one side in the thickness direction. The optical adjustment layer is a layer that suppresses the pattern formed by the light-transmitting conductive layer 1 from being visually recognized and adjusts the optical properties (specifically, the refractive index) of the light-transmitting conductive film 10.

[0154] The functional layer 14 may be a peeling functional layer (not shown). In this modification, the resin layer 11 has a transparent substrate film 13 and a peeling functional layer in sequence on one side in the thickness direction. The peeling functional layer is a layer (easy peeling layer) that is easily peeled from the transparent substrate film 13. If the resin layer 11 has a peeling 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 by, for example, transferring and pasting to other components constituting the touch sensor.

[0155] The functional layer 14 may be an adhesive layer (not shown). In this modification, the resin layer 11 includes a transparent substrate film 13 and an adhesive layer in this order on one side in the thickness direction. The adhesive layer improves the adhesion between the transparent substrate film 13 and the light-transmitting conductive layer 1 .

[0156] The functional layer 14 may be a multilayer. In other words, the functional layer 14 may optionally include two or more layers selected from the group consisting of a hard coating layer, an optical adjustment layer, a peeling functional layer, and an easy-adhesion layer. Specifically, the resin layer 11 may include a transparent substrate film 13, an easy-adhesion layer, a hard coating layer, and an optical adjustment layer in sequence on one side in the thickness direction, or the resin layer 11 may include a transparent substrate film 13, a peeling functional layer, a hard coating layer, and / or an optical adjustment layer in sequence on one side in the thickness direction.

[0157] When the resin layer 11 has a transparent base film 13, a release functional layer, a hard coat layer and / or an optical adjustment layer in sequence on one side in the thickness direction, the laminate having the hard coat layer and / or the optical adjustment layer and the translucent conductive layer 1 can be peeled off from the translucent conductive film 10.

[0158] like Figure 7 A and Figure 7 As shown in B in FIG. 1 , the resin layer 11 may include only one of the functional layer 14 and the transparent base film 13 . Figure 7 A and Figure 7 B depicts another example of a laminate including a light-transmitting conductive layer.

[0159] For example, Figure 7 As shown in A, in the light-transmitting conductive layer laminate 20, the resin layer 11 may not have the transparent base film 13 but may be composed only of the functional layer 14. The light-transmitting conductive layer laminate 20 does not have a film shape, and has the resin layer 11 (hard coating layer and / or optical adjustment layer) and the light-transmitting conductive layer 1 in this order in the thickness direction.

[0160] On the other hand, Figure 7As shown in FIG. 1B , the light-transmitting conductive film 10 has a film shape. The resin layer 11 may not have the functional layer 14 but may be composed only of 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.

[0161] In addition, in the resin layer 11 , a transparent base material (not shown) made of glass may be provided on the functional layer 14 .

[0162] In one embodiment, one is shown as an example of the appropriate number of the light-transmitting conductive layer 1 in the light-transmitting conductive film 10, but for example, although not shown, it may be two. In this modification, the two light-transmitting conductive layers 1 are respectively arranged on both sides in the thickness direction of the resin layer 11. In other words, in this modification, the number of the light-transmitting conductive layers 1 relative to one resin layer 11 is preferably two.

[0163] As one embodiment of a method for manufacturing a light-transmitting conductive layer 1 including a crystalline region, a manufacturing method of heating the amorphous light-transmitting conductive layer 1 is described, but for example, a manufacturing method of storing the layer for a long time (e.g., 1000 hours) in a temperature environment of less than 80°C (e.g., 25°C) may also be adopted.

[0164] Example

[0165] Hereinafter, examples and comparative examples are shown to more specifically describe the present invention. It should be noted that the specific numerical values ​​of the blending ratio (containing ratio), physical property values, parameters, etc. used in the following description can be replaced by the upper limit value (numerical value defined in the form of "below", "less than") or lower limit value (numerical value defined in the form of "above", "exceeding") of the corresponding blending ratio (containing ratio), physical property values, parameters, etc. recorded in the above-mentioned "Specific Implementation Methods". In addition, in the following description, as long as there is no special mention, "parts" and "%" are mass references.

[0166] Example 1

[0167] On one side of the thickness direction of a long transparent substrate film 13 formed of a PET film (manufactured by Toray Industries, Ltd., with a thickness of 50 μm), a UV-curable hard coating composition containing an acrylic resin was applied, and the composition was cured by UV irradiation to form a hard coating layer (functional layer 14) with a thickness of 2 μm. Thus, a resin layer 11 having a transparent substrate film 13 and a hard coating layer was prepared.

[0168] Next, the resin layer 11 is placed in the sputtering device 30. Next, in the sputtering device 30, the extraction side pump 33, the take-up side pump 34, the first pump 71 and the second pump 72 are driven to set the ultimate vacuum degree to 0.9×10 -4Pa, the resin layer 11 is degassed. In addition, the temperature of the film forming roller 40 is set to -8°C. In the sputtering device 30, the materials of the first target 51 and the second target are 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 is 10% by mass. In the sintered body, the ratio of the number of tin atoms to the number of indium atoms (the number of tin atoms / the number of indium atoms) is 0.102.

[0169] Thereafter, the resin layer 11 is conveyed from the delivery unit 35 toward the winding unit 37 along the film-forming roll 40 .

[0170] In the first film forming chamber 41, krypton is supplied from the rare gas supply machine 63 while the first pump 71 is driven, and oxygen is supplied from the first oxygen gas supply machine 64. The pressure of the first film forming chamber 41 is set to 0.2 Pa, and the first target 51 is sputtered (power supply: DC, horizontal magnetic field intensity on the first target: 90 mT), thereby forming a first amorphous conductive film 81 (first region 4) with a thickness of 50 nm.

[0171] In the second film forming chamber 42, while the second pump 72 is driven, argon is supplied from the argon supply machine 65, and oxygen is supplied from the second oxygen supply machine 66. The pressure of the second film forming chamber 42 is set to 0.4 Pa, and the second target 52 is sputtered (power supply: DC, horizontal magnetic field intensity on the second target: 90 mT), thereby forming a second amorphous conductive film 82 (second region 5) with a thickness of 80 nm.

[0172] It should be noted that if Figure 6 As shown in FIG. 1 , the amount of oxygen introduced from the first oxygen supply machine 64 and the second oxygen supply machine 66 is adjusted so that the surface resistance of the amorphous light-transmitting conductive layer 1 is 50Ω / □ and the surface resistance is located in the first region X of the surface resistance-oxygen introduction amount curve. At this time, the ratio of oxygen to the total amount of krypton gas and oxygen introduced is set to about 2.5% by flow rate. The ratio of oxygen to the total amount of argon gas and oxygen introduced is set to about 1.5% by flow rate.

[0173] Therefore, if Figure 2 As shown, a first amorphous conductive film 81 and a second amorphous conductive film 82 are sequentially formed on one surface side in the thickness direction of the resin layer 11 .

[0174] Thus, the light-transmitting conductive film 10 including the resin layer 11 and the amorphous light-transmitting conductive layer 1 is obtained.

[0175] Examples 2 to 4 and 6 to 7

[0176] The power densities of the first target 51 and the second target 52 are 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 translucent conductive layer 1 are as recorded in Table 1. Otherwise, the same operations are performed as in Example 1 to obtain a translucent conductive film 10.

[0177] Example 5

[0178] A second mixed gas (containing Ar and O2) was supplied to the first film forming chamber 41, and the pressure of the first film forming chamber 41 was set to 0.4 Pa. After that, 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 forming chamber 42, and the pressure of the second film forming chamber 42 was set to 0.2 Pa. After that, 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 / □. Except for this, the same operation as in Example 1 was performed to obtain a light-transmitting conductive film 10. The light-transmitting conductive film 10 of Example 5 corresponds to Figure 4 The light-transmitting conductive film 10 is shown.

[0179] Example 8

[0180] A mixed gas of krypton and argon (85 volume % krypton and 15 volume % argon) is supplied from the rare gas supply machine 63, and oxygen is supplied from the first oxygen supply machine 64. Figure 6 The oxygen introduction amount of the first oxygen supply machine 64 was adjusted so that the surface resistance of the amorphous light-transmitting conductive layer 1 became 39Ω / □ (the ratio of oxygen to the total introduction amount of krypton gas and oxygen was about 2.6 flow %), and the power density of the first target 51 was adjusted, thereby forming a third amorphous conductive film 83 with a thickness of 147nm in the first film-forming chamber 41, and no second amorphous conductive film 82 (second region 5) was formed in the second film-forming chamber 42. Except for this, the same operation as in Example 1 was performed to obtain a light-transmitting conductive film 10. The light-transmitting conductive film 10 of Example 8 corresponds to Figure 5 The light-transmitting conductive film 10 is shown in D.

[0181] Comparative Example 1

[0182] The light-transmitting conductive film 10 was obtained in the same manner as in Example 1 except that the second mixed gas (containing Ar and O 2 ) was supplied to both the first film forming chamber 41 and the second film forming chamber 42 and the pressures of the first film forming chamber 41 and the second film forming chamber 42 were changed to 0.4 Pa.

[0183] Comparative Example 2

[0184] The light-transmitting conductive film 10 was obtained in the same manner as in Example 1 except that the first mixed gas (containing Kr and O 2 ) was supplied to both the first film forming chamber 41 and the second film forming chamber 42 and the pressure of the first film forming chamber 41 and the second film forming chamber 42 was changed to 0.2 Pa.

[0185] [evaluate]

[0186] The following items were evaluated about the light-transmitting conductive film 10 of each example and comparative example.

[0187] The results are shown in Table 1.

[0188] [thickness]

[0189] [Thickness of light-transmitting conductive layer]

[0190] The cross-sectional observation samples of the light-transmitting conductive layer 1 of each example and comparative example were 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). Details of the apparatus and measurement conditions are as follows.

[0191] FIB microsampling method

[0192] FIB device: FB2200 manufactured by Hitachi

[0193] Accelerating voltage: 10 kV

[0194] FE-TEM observation

[0195] FE-TEM device: JEM-2800 manufactured by JEOL

[0196] Accelerating voltage: 200 kV

[0197] [Thickness of the First Amorphous Conductive Film and the Thickness of the Second Amorphous Conductive Film in Examples 1 to 4 and 6 to 7]

[0198] In Examples 1 to 4 and 6 to 7, samples were taken immediately after the first amorphous conductive film 81 was formed and before the second amorphous conductive film 82 was formed, 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).

[0199] Next, the thickness of the second amorphous conductive film 82 (second region 5 ) in Examples 1 to 4 and 6 to 7 is calculated using the following formula.

[0200] The thickness of the second amorphous conductive film 82 = the thickness of the light-transmitting conductive layer 1 - the thickness of the first amorphous conductive film 81

[0201] [Thickness of the First Amorphous Conductive Film and the Thickness of the Second Amorphous Conductive Film in Example 5]

[0202] In Example 5, a sample was taken immediately after the second amorphous conductive film 82 was formed and before the first amorphous conductive film 81 was formed, 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).

[0203] Next, the thickness of the first amorphous conductive film 81 (first region 4 ) in Example 5 is calculated using the following formula.

[0204] The thickness of the first amorphous conductive film 81 = the thickness of the light-transmitting conductive layer 1 - the thickness of the second amorphous conductive film 82

[0205] [Thickness of the Third Amorphous Conductive Film of Example 8]

[0206] In Example 8, the thickness of the third amorphous conductive film 83 immediately after sputtering was determined by FE-TEM observation (cross-sectional observation).

[0207] [Identification of Kr (confirmation of its existence)]

[0208] A scanning fluorescent X-ray analyzer (ZSX Primus IV, manufactured by Rigaku Corporation) was used to confirm whether Kr was mixed in the translucent conductive layer 1. Specifically, the following conditions were used to perform repeated measurements 5 times, and the average value of each scanning angle was calculated to produce an X-ray spectrum. Kr was determined by confirming the presence of a peak near 28.2° in the produced X-ray spectrum. As a result, the mixing of Kr was confirmed in Examples 1 to 8 and Comparative Example 2. On the other hand, the mixing of Kr was not confirmed in Comparative Example 1.

[0209] <Measurement Conditions>

[0210] Spectrum: Kr-KA

[0211] Measuring diameter: 30mm

[0212] Atmosphere: Vacuum

[0213] Target: Rh

[0214] Tube voltage: 50kV

[0215] Tube current: 60mA

[0216] Primary filter: Ni40

[0217] Scanning angle (deg): 27.0-29.5

[0218] Step size (deg): 0.020

[0219] Speed ​​(Deg / min): 0.75

[0220] Attenuator: 1 / 1

[0221] Slit: S2

[0222] Spectroscopic crystal: LiF(200)

[0223] Detector: SC

[0224] PHA: 100-300

[0225] [Identification (quantification) of Kr and Ar]

[0226] The content of Kr and Ar atoms contained in the light-transmitting conductive layer 1 of Examples 1 to 8 and Comparative Examples 1 to 2 was analyzed using Rutherford Backscattering Spectrometry (RBS). The element ratios of the five elements In+Sn (in Rutherford Backscattering Spectrometry, it is difficult to measure In and Sn separately, so the evaluation is performed as a total of the two elements), O, Ar, and Kr as detection elements were determined, and the content (atom%) of Kr atoms and Ar atoms in the light-transmitting conductive layer 1 was thus determined. The specific apparatus used and the measurement conditions are as follows. As analysis results, the Kr content (atom%), the Ar content (atom%), and the rare gas (Kr+Ar) content (atom%) are shown in Table 1.

[0227] Regarding the analysis of the Kr content, in Examples 1 to 8 and Comparative Example 2, no exact measured value above the detection limit (lower limit) could be obtained (the detection limit may vary depending on the thickness of the translucent conductive layer 1 to be measured). Therefore, in Table 1, the Kr content of the translucent conductive layer 1 is expressed as "< the specific detection limit in the thickness of the translucent conductive layer 1 to be measured" in order to indicate the detection limit below the thickness of the translucent conductive layer 1 (the same expression is also used for the content of the rare gas (Kr+Ar)).

[0228] It should be noted that in Comparative Example 1, the mixing of Kr was not confirmed by the quantitative analysis of Kr using the above-mentioned scanning fluorescent X-ray analyzer. Therefore, it is not expressed in Table 1 as the "specific detection limit value of the thickness of the transparent conductive layer 1 provided for measurement" recorded in Examples 1 to 8 and Comparative Example 2.

[0229] <Device used>

[0230] Pelletron 3SDH (manufactured by National Electrostatics Corporation)

[0231] <Measurement Conditions>

[0232] Incident ion: 4He++

[0233] Incident energy: 2300keV

[0234] Angle of incidence: 0deg

[0235] Scattering angle: 160deg

[0236] Sample current: 6nA

[0237] Electron beam diameter: 2mmφ

[0238] In-plane rotation: No

[0239] Irradiation: 75μC

[0240] [Surface resistance]

[0241] The surface resistance (initial) of the light-transmitting conductive layer 1 was measured by a four-probe method in accordance with JIS K7194 (1994).

[0242] In the same manner as above, the surface resistance (after heating) of the light-transmitting conductive layer 1 after heating in a hot air oven at 155° C. for 2 hours was measured.

[0243] [Resistivity]

[0244] [Measured value of resistivity]

[0245] Regarding the resistivity of the light-transmitting conductive layer 1 after heating in each example and comparative example, the measured value of the resistivity was obtained by multiplying the surface resistance by the thickness of the light-transmitting conductive layer 1. It should be noted that the measured value of the resistivity of the light-transmitting conductive layer 1 is calculated based on the surface resistance of the light-transmitting conductive layer 1 actually measured, and therefore, is expressed as a "measured value".

[0246] [Expected value of resistivity]

[0247] The expected values ​​of the resistivity of the light-transmitting conductive layer 1 of Examples 1 to 8 were obtained. Specifically, the resistivity of the light-transmitting conductive layer 1 after heating in Comparative Example 1 (with Ar mixed therein) was 2.301×10 -4 Ωcm was divided by the thickness of the second amorphous conductive film 82 of each example to calculate the expected value (AV) of the surface resistance of the second amorphous conductive film 82 after heating (155° C., 2 hours). Ar ) (Formula (1)). Next, the resistivity after heating of Comparative Example 2 (mixed with Kr) is 1.599×10 -4Ωcm was divided by the thickness of the first amorphous conductive film 81 of each example to calculate the expected value (AV) of the surface resistance of the first amorphous conductive film 81 after heating (155° C., heating for 2 hours). kr ) (Formula (2)). By performing the above operation, the AV Ar and AV kr , and the thickness of the light-transmitting conductive layer 1 of each example were substituted into the following formula (3) to determine the expected value of the resistivity of the light-transmitting conductive layer 1 after heating (155° C., after heating for 2 hours) of each example.

[0248] The expected value (AV) of the surface resistance of the second amorphous conductive film 82 after heating is given by equation (1). Ar )={resistivity of the light-transmitting conductive layer 1 of Comparative Example 1 / thickness of the second amorphous conductive film 82}

[0249] The expected value (AV) of the surface resistance of the first amorphous conductive film 81 after heating is given by equation (2). kr )={resistivity of the light-transmitting conductive layer 1 of Comparative Example 2 / thickness of the first amorphous conductive film 81}

[0250] Formula (3) Expected value of resistivity of the light-transmitting conductive layer 1 = {(AV Ar ×AV kr ) / (AV Ar +AV kr )}×thickness of the light-transmitting conductive layer 1

[0251] In addition, in the light-transmitting conductive layer 1 as in the present application Figure 5 When the light-transmitting conductive layer 1 is a layer mixed with argon and a rare gas with an atomic number greater than argon, as in D, the ratio of the amount of the introduced argon gas to the amount of the rare gas with an atomic number greater than argon is changed to the ratio of the first region 4 to 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 is formed using a mixed gas of krypton:argon = 2:1, the thickness is converted to the first region 4:second region 5 = 2:1, and the expected value of the resistivity of the light-transmitting conductive layer 1 is calculated using formulas (1) to (3). Specifically, in Example 8, since the light-transmitting conductive layer 1 is formed using a mixed gas of krypton:argon = 85:15 (volume ratio), the thickness is converted to the first region 4:second region 5 = 85:15, and the expected value of the resistivity is calculated using formulas (1) to (3).

[0252] The expected value of resistivity refers to the resistivity that can be expected in calculation. More specifically, the resistivity of the translucent conductive layer 1 of each embodiment having the first region 4 and the second region 5 is the resistivity that is expected (calculated) as a calculation basis based on the resistivity of the translucent conductive layer 1 (another translucent conductive layer B) of the comparative example 1 composed only of the second region 5 and the resistivity of the translucent conductive layer 1 (a translucent conductive layer A) of the comparative example 2 composed only of the first region 4.

[0253] [Gain in resistivity]

[0254] The gain in resistivity of the light-transmitting conductive layer 1 of Examples 1 to 8 was determined according to the following formula.

[0255] The gain in resistivity of the light-transmitting conductive layer 1 (%) = [(expected value of resistivity - measured value of resistivity)] / (expected value of resistivity) × 100

[0256] The gain in resistivity of the light-transmitting conductive layer 1 is the percentage of the expected value of the resistivity of the light-transmitting conductive layer 1 relative to the amount of decrease in the measured value of the resistivity of the light-transmitting conductive layer 1 after heating at 155°C for 2 hours. If the gain in resistivity of the light-transmitting conductive layer 1 is positive, it means that the measured value of the resistivity of the light-transmitting conductive layer 1 is smaller than the expected value, which means that the effect of reducing the resistivity of the light-transmitting conductive layer 1 by mixing Ar and Kr has a significant effect.

[0257] [Transmittance]

[0258] The total light transmittance of the light-transmitting conductive film 10 after heating at 155° C. for 2 hours was measured using a haze meter (manufactured by Suga Test Instruments, model: HGM-2DP).

[0259] [Evaluation of Crystallinity]

[0260] Although not described in Table 1, the presence of crystal grains was confirmed by observing the surface of each of the light-transmitting conductive layers 1 of Examples 1 to 8 and Comparative Examples 1 to 2 after being heated in a hot air oven at 155°C for 2 hours using a transmission electron microscope (TEM), thereby confirming that they are all crystalline. Specifically, the light-transmitting conductive film 10 of each of the Examples and Comparative Examples after being heated at 155°C for 2 hours was cut out and fixed to the sample holder of the slicer. Next, the slicer was set at an extremely acute angle relative to the ITO film surface, and the cutting surface was roughly parallel to the ITO film surface to obtain an observation sample. The observation sample was observed using TEM in a top view (magnification: 50,000 times). In the TEM observation photograph, an area of ​​1.5μm×1.5μm was arbitrarily selected, and the presence or absence of crystal grains was confirmed in the area. It should be noted that in each of the Examples and Comparative Examples, the presence of crystal grains was confirmed on the entire surface in the plane direction in a top view, and it can be seen that the area containing the crystal grains is the main area (showing crystallinity and being crystalline).

[0261] [Table 1]

[0262]

[0263] It should be noted that the above invention is provided in the form of an exemplary embodiment of the present invention, but it is only a simple example and is not to be interpreted as limiting. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of protection of the above claims.

[0264] Industrial Applicability

[0265] The light-transmitting conductive layer and light-transmitting conductive film of the present invention are used, for example, for touch sensors, light-adjusting elements, photoelectric conversion elements, heat-ray control members, antennas, electromagnetic wave shielding members, image display devices, heater members, and lighting.

Claims

1. A light-transmitting conductive layer, characterized in that: It has a first main surface and a second main surface disposed opposite to the first main surface at a distance from one side in the thickness direction of the first main surface, and has a layer extending in a plane direction orthogonal to the thickness direction. The light-transmitting conductive layer comprises a conductive oxide. The conductive oxide contains indium tin composite oxide, argon and krypton, The light-transmitting conductive layer has a peak near 28.2° in an X-ray spectrum measured using a scanning fluorescent X-ray analyzer and has a region where the krypton atom content based on Rutherford backscattering analysis is below the detection limit. In the light-transmitting conductive layer, a content ratio of argon is greater than or equal to 0.01 atom % and less than or equal to 0.5 atom %.

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

3. The light-transmitting conductive layer according to claim 1 or 2, characterized in that: The semiconductor device has a first region including krypton and a second region including argon in sequence along a thickness direction.

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

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