Transparent Conductive Film, Method for Manufacturing the Same, Dimming Film, and Method for Manufacturing the Same

Abstract

Provided are a transparent conductive film, a method for manufacturing the same, a light control film, and a method for manufacturing the same. The transparent conductive film sequentially includes a transparent substrate, a transparent conductive layer, and an inorganic layer. The thickness of the inorganic layer is 20 nm or less. The water contact angle of the inorganic layer is 50 degrees or less.

Description

[0001] This application is a divisional application of an application with an application date of October 26, 2016, an application number of 2016800631788, and an invention title of "Transparent Conductive Film, Method for Manufacturing the Same, Light-Dimming Film, and Method for Manufacturing the Same". Technical Field

[0002] The present invention relates to a transparent conductive film, a method for manufacturing the same, a light-dimming film, and a method for manufacturing the same. Background Art

[0003] Currently, a liquid crystal optical element including a liquid crystal resin composite in which liquid crystal is dispersed and held in a resin matrix and two substrates sandwiching them is known.

[0004] For example, the following liquid crystal optical element has been proposed: at least one substrate surface of the substrate in contact with the liquid crystal resin composite is covered with a film having almost uniform wettability with respect to the uncured mixed liquid for forming the liquid crystal resin composite (for example, refer to Patent Document 1).

[0005] In the substrate of Patent Document 1, ITO is formed on a glass plate, and then SiO2 is vapor-deposited on the ITO with a thickness of 60 nm to form a film.

[0006] Moreover, in Patent Document 1, since the uncured mixed liquid shows almost uniform wettability on the entire substrate surface, it becomes difficult to leave bubbles on the substrate surface.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent Laid-Open No. 5-34667 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] However, after forming the SiO2 film, ITO is sometimes patterned by etching. In Patent Document 1, a process of forming the SiO2 film after patterning ITO is disclosed, and this process cannot be substantially adopted from the viewpoints of product quality and manufacturing cost. On the other hand, when forming a film having uniform wettability (for example, a 60-nm-thick SiO2 film) after forming ITO and then patterning ITO, there are drawbacks such that the patterning of ITO takes a long time or cannot be patterned substantially.

[0012] An object of the present invention is to provide a transparent conductive film capable of quickly and reliably etching a transparent conductive layer, a method for manufacturing the same, a method for manufacturing a dimming film capable of forming a dimming functional layer with a uniform thickness on the surface of an inorganic layer by a wet method, and a dimming film obtained by using the manufacturing method.

[0013] Solutions for Solving the Problems

[0014] [1] The present invention relates to a transparent conductive film, which is characterized in that it sequentially includes a transparent substrate, a transparent conductive layer, and an inorganic layer, the thickness of the inorganic layer is 20 nm or less, and the water contact angle of the inorganic layer is 50 degrees or less.

[0015] Since the thickness of the inorganic layer of the transparent conductive film is below a specific upper limit, the inorganic layer and the transparent conductive layer can be etched quickly and reliably.

[0016] In addition, the water contact angle of the inorganic layer after 80 hours or more from the formation of the inorganic layer is below a specific value, so that a dimming functional layer with a uniform thickness can be formed on the surface of the inorganic layer by a wet method. Therefore, a dimming film with excellent reliability can be obtained.

[0017] [2] The present invention includes the transparent conductive film described in [1] above, wherein the water contact angle of the inorganic layer after 80 hours or more from the formation of the inorganic layer is 50 degrees or less.

[0018] [3] The present invention includes the transparent conductive film described in [1] or [2] above, wherein the inorganic layer is formed of an inorganic oxide.

[0019] Since the inorganic layer of the transparent conductive film is formed of an inorganic oxide, it has excellent hydrophilicity.

[0020] [4] The present invention includes the transparent conductive film described in any one of [1] to [3] above, wherein the transparent conductive layer has an indium-based conductive oxide layer, and the thickness of the indium-based conductive oxide layer is 50 nm or less.

[0021] Since the thickness of the indium-based conductive oxide layer of the transparent conductive film is below a specific upper limit, the inorganic layer and the transparent conductive layer can be etched quickly and reliably.

[0022] [5] The present invention relates to a method for manufacturing a transparent conductive film, which is characterized by comprising the following steps: a step (1) of preparing a transparent substrate; a step (2) of forming a transparent conductive layer on the surface of the aforementioned transparent substrate; a step (3) of forming an inorganic layer on the surface of the aforementioned transparent conductive layer; a step (4) of etching the aforementioned transparent conductive layer after the aforementioned step (3), wherein the thickness of the aforementioned inorganic layer is 20 nm or less, and the water contact angle of the aforementioned inorganic layer after 80 hours or more from the formation of the aforementioned inorganic layer is 50 degrees or less.

[0023] According to this method, in step (3), an inorganic layer with a thickness below a specific upper limit is formed. Therefore, in step (4) after step (3), the inorganic layer and the transparent conductive layer can be etched quickly and reliably.

[0024] Additionally, the water contact angle of the inorganic layer after 80 hours or more from the formation of the inorganic layer is below a specific value. Therefore, a light control functional layer with a uniform thickness can be formed wet on the surface of the inorganic layer.

[0025] [6] The present invention includes the method for manufacturing a transparent conductive film described in the above [5], in which, in the aforementioned step (2), an amorphous transparent conductive layer is formed, and this manufacturing method further includes: a step (5) of crystallizing the amorphous transparent conductive layer after the aforementioned step (3).

[0026] According to this method, in step (5) after step (3), the amorphous transparent conductive layer is crystallized, so that the surface resistance of the transparent conductive layer can be reduced.

[0027] [7] The present invention relates to a light control film, which is characterized by sequentially including a first transparent conductive film, a light control functional layer, and a second transparent conductive film, wherein the aforementioned first transparent conductive film and / or the aforementioned second transparent conductive film is the transparent conductive film described in any one of the above [1] to [4], and the aforementioned light control functional layer is in contact with the inorganic layer included in the aforementioned transparent conductive film.

[0028] In this light control film, the light control functional layer is in contact with the inorganic layer included in the transparent conductive film, so that it can have a uniform thickness. Therefore, the reliability of this light control film is excellent.

[0029] [8] The present invention relates to a method for manufacturing a light control film, which is characterized by comprising the following steps: a step (6) of manufacturing two transparent conductive films and a step (7) of sandwiching a light control functional layer with the two aforementioned transparent conductive layers. In the aforementioned step (6), at least one of the aforementioned transparent conductive films is manufactured by the manufacturing method described in the above [5] or [6], and in the aforementioned step (7), the aforementioned light control functional layer is brought into contact with the inorganic layer of at least one of the aforementioned transparent conductive films.

[0030] In addition, according to this method, in step (6), the light control functional layer is brought into contact with the inorganic layer of at least one light-transmissive conductive film, so that in step (7), a light control functional layer with a uniform thickness can be obtained. Therefore, the reliability of this light control film is excellent.

[0031] Effects of the Invention

[0032] The light-transmissive conductive film of the present invention can etch the inorganic layer and the light-transmissive conductive layer quickly and reliably, and can form a light control functional layer with a uniform thickness on the surface of the inorganic layer by wet method. Therefore, the reliability of the light-transmissive conductive film is excellent.

[0033] According to the manufacturing method of the light-transmissive conductive film of the present invention, the light-transmissive conductive layer can be etched quickly and reliably, and a light control functional layer with a uniform thickness can be formed on the surface of the inorganic layer by wet method.

[0034] The light control film of the present invention has a light-transmissive conductive film with excellent reliability, so its reliability is excellent.

[0035] According to the manufacturing method of the light control film of the present invention, in step (6), the light control functional layer is brought into contact with the inorganic layer of at least one light-transmissive conductive film, so that in step (7), a light control functional layer with a uniform thickness can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 A cross-sectional view showing a first embodiment of the light-transmissive conductive film of the present invention.

[0037] Figure 2 Showing Figure 1 A cross-sectional view of a light control film having the light-transmissive conductive film shown.

[0038] Figure 3 Showing Figure 1 A modified example of the light-transmissive conductive film shown.

[0039] Figure 4 A cross-sectional view showing a second embodiment of the light-transmissive conductive film of the present invention.

[0040] Figure 5 Showing Figure 4 A cross-sectional view of a light control film having the light-transmissive conductive film shown.

[0041] Figure 6 Showing Figure 4 A modified example of the light-transmissive conductive film shown. DETAILED DESCRIPTION OF THE INVENTION

[0042] In Figure 1In this case, the up-and-down direction on the paper surface is the up-and-down direction (thickness direction, first direction), the upper side of the paper surface is the upper side (one side in the thickness direction, one side in the first direction), and the lower side of the paper surface is the lower side (the other side in the thickness direction, the other side in the first direction). In Figure 1 In this case, the left-and-right direction on the paper surface is the left-and-right direction (width direction, second direction perpendicular to the first direction), the left side of the paper surface is the left side (one side in the second direction), and the right side of the paper surface is the right side (the other side in the second direction). In Figure 1 In this case, the paper thickness direction is the front-and-back direction (third direction perpendicular to the first direction and the second direction), the side of the paper surface close to the reader is the front side (one side in the third direction), and the side of the paper surface away from the reader is the back side (the other side in the third direction). Specifically, it is based on the direction arrows in each figure.

[0043] <First Embodiment>

[0044] 1. Transparent Conductive Film

[0045] This transparent conductive film 1 is in the form of a film (including a sheet) having a predetermined thickness, and has a flat upper surface and a flat lower surface (two main surfaces) along a predetermined direction (front-and-back direction and left-and-right direction, i.e., the surface direction) perpendicular to the thickness direction. The transparent conductive film 1 is, for example, a component of a dimming film 20 (described later, refer to Figure 1 ), etc., that is, it is not a dimming device (described later). That is, the transparent conductive film 1 is a component for manufacturing the dimming film 20, etc., and does not include a dimming functional layer 5 (described later, refer to the dashed line in Figure 2 , refer to the solid line in Figure 1 ), etc., and circulates separately in the form of a component, and is an industrially utilizable device. Figure 2 Specifically, the transparent conductive film 1 sequentially includes a transparent substrate 2, a transparent conductive layer 3, and an inorganic layer 4. That is, the transparent conductive film 1 includes a transparent substrate 2, a transparent conductive layer 3 disposed on the upper surface of the transparent substrate 2, and an inorganic layer 4 disposed on the upper surface of the transparent conductive layer 3. In addition, it is preferable that the transparent conductive layer 3 and the inorganic layer 4 are in contact with each other. More preferably, the transparent conductive film 1 is formed only by the transparent substrate 2, the transparent conductive layer 3, and the inorganic layer 4. Each layer is described in detail below.

[0046] Specifically, the transparent conductive film 1 sequentially includes a transparent substrate 2, a transparent conductive layer 3, and an inorganic layer 4. That is, the transparent conductive film 1 includes a transparent substrate 2, a transparent conductive layer 3 disposed on the upper surface of the transparent substrate 2, and an inorganic layer 4 disposed on the upper surface of the transparent conductive layer 3. In addition, it is preferable that the transparent conductive layer 3 and the inorganic layer 4 are in contact with each other. More preferably, the transparent conductive film 1 is formed only by the transparent substrate 2, the transparent conductive layer 3, and the inorganic layer 4. Each layer is described in detail below.

[0047] 2. Transparent Substrate

[0048] The transparent substrate 2 is the lowermost layer of the transparent conductive film 1 and is a support material for ensuring the mechanical strength of the transparent conductive film 1. The transparent substrate 2 includes a base substrate 6. In addition, the transparent substrate 2 further includes a functional layer 7 disposed on one main surface (upper surface) of the base substrate 6. That is, this transparent substrate 2 sequentially includes a base substrate 6 and a functional layer 7.

[0049] 2-1. Base substrate

[0050] The base substrate 6 is a layer forming the lower surface of the light-transmissive substrate 2 and has a film shape (including a sheet shape).

[0051] The base substrate 6 is formed of, for example, an organic film or an inorganic plate such as a glass plate. From the viewpoint of effectively manufacturing the light-transmissive conductive film 1 by a continuous manufacturing method such as roll-to-roll, the base substrate 6 is preferably formed of an organic film, and more preferably formed of a polymer film.

[0052] The polymer film has light-transmittance. As materials for the polymer film, for example, polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, etc., (meth)acrylic resins such as polymethacrylate, etc. (acrylic resin and / or methacrylic resin), olefin resins such as polyethylene, polypropylene, cycloolefin polymer, etc., polycarbonate resin, polyethersulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, polystyrene resin, norbornene resin, etc. can be cited. These polymer films can be used alone or in combination of two or more. From the viewpoints of light-transmittance, heat resistance, mechanical properties, etc., polyester resins are preferably cited, and PET is more preferably cited.

[0053] The thickness of the base substrate 6 is, for example, 2 μm or more, preferably 20 μm or more, more preferably 40 μm or more, and, for example, 300 μm or less, preferably 200 μm or less.

[0054] 2-2. Functional layer

[0055] The functional layer 7 is provided on one main surface (upper surface) of the base substrate 6 and is a layer imparting functionality corresponding to the purpose. As the functional layer 7, for example, an easy-adhesion layer, a primer layer, or a hard coat layer, etc. can be cited. The easy-adhesion layer has a function of improving the adhesion to the layer formed on the base substrate 6 (for example: the light-transmissive conductive layer 3). The primer layer has a function of adjusting the reflectance and optical hue of the light-transmissive conductive film 1. The hard coat layer improves the scratch resistance of the light-transmissive conductive film 1.

[0056] The functional layer 7 preferably contains a resin composition and is more preferably formed only of a resin composition.

[0057] The resin composition contains, for example, a resin and particles. The resin composition preferably contains only a resin and is more preferably formed only of a resin.

[0058] As the resin, curable resins, thermoplastic resins (such as polyolefin resins), etc. can be cited, and curable resins are preferably cited.

[0059] As the curable resin, examples thereof include active energy ray curable resins that are cured by irradiation with active energy rays (specifically, ultraviolet rays, electron rays, etc.), and thermosetting resins that are cured by heating, etc. Active energy ray curable resins are preferably cited.

[0060] Examples of the active energy ray curable resin include polymers having a functional group containing a polymerizable carbon-carbon double bond in the molecule. Examples of such functional groups include vinyl group, (meth)acryloyl group (methacryloyl group and / or acryloyl group), etc.

[0061] Examples of the active energy ray curable resin include (meth)acrylic resins (acrylic resins and / or methacrylic resins) having a functional group in the side chain, etc.

[0062] The curable resin can be used alone or in combination of two or more.

[0063] The thickness of the functional layer 7 is, for example, 0.01 μm or more, preferably 0.1 μm or more, more preferably 1 μm or more, and, for example, 10 μm or less, preferably 5 μm or less.

[0064] The total thickness of the light-transmissive substrate 2, that is, the thickness of the base substrate 6 and the thickness of the functional layer 7, is, for example, 5 μm or more, preferably 20 μm or more, more preferably 45 μm or more, and, for example, 300 μm or less, preferably 200 μm or less.

[0065] 3. Light-transmissive conductive layer

[0066] The light-transmissive conductive layer 3 is a conductive layer that can be optionally patterned by etching in a subsequent process.

[0067] The light-transmissive conductive layer 3 has a thin film shape (including sheet shape) and is disposed over the entire upper surface of the light-transmissive substrate 2 in contact with the upper surface of the light-transmissive substrate 2.

[0068] The light-transmissive conductive layer 3 successively includes a first inorganic oxide layer 8, a metal layer 9, and a second inorganic oxide layer 10. That is, the light-transmissive conductive layer 3 includes: a first inorganic oxide layer 8 disposed on the light-transmissive substrate 2, a metal layer 9 disposed on the first inorganic oxide layer 8, and a second inorganic oxide layer 10 disposed on the metal layer 9. In addition, the light-transmissive conductive layer 3 is preferably formed only of the first inorganic oxide layer 8, the metal layer 9, and the second inorganic oxide layer 10. The first inorganic oxide layer 8 and the second inorganic oxide layer 10 are preferably amorphous.

[0069] 3-1. First inorganic oxide layer

[0070] The first inorganic oxide layer 8 is a conductive layer that, together with the metal layer 9 and the second inorganic oxide layer 10, imparts conductivity to the transparent conductive layer 3. The first inorganic oxide layer may not maintain conductivity and preferably has conductivity. In addition, the first inorganic oxide layer 8 is also a barrier layer that prevents active gases from the organic substances contained in the transparent substrate 2 from invading the metal layer 9. The first inorganic oxide layer 8 is the lowermost layer of the transparent conductive layer 3, has a thin film shape (including a sheet shape), and is disposed over the entire upper surface of the transparent substrate 2 in contact with the upper surface of the transparent substrate 2.

[0071] The first inorganic oxide layer 8 contains an inorganic oxide that can be dissolved in an etching solution described later as a main component.

[0072] Examples of the inorganic oxide include metal oxides formed of at least one metal selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. For the metal oxide, metal atoms shown in the above group may be doped as needed.

[0073] As the inorganic oxide, from the viewpoints of reducing the resistivity and ensuring excellent translucency, indium oxide (including indium-based conductive oxides) is preferably cited, and indium tin composite oxide (ITO) is more preferably cited. That is, the first inorganic oxide layer 8 is preferably an indium-based conductive oxide layer, and more preferably an ITO layer.

[0074] In indium tin composite oxide (ITO), the content ratio of tin oxide (SnO2) (SnO2 / (SnO2 + In2O3)) is, for example, 6% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more, further preferably 12% by mass or more, and, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 17% by mass or less, relative to the total mass of indium oxide (In2O3) and tin oxide (SnO2). When the mass ratio of tin oxide (SnO2) does not satisfy the above lower limit, the change over time in the crystallinity of the first inorganic oxide layer 8 becomes large, and there is a concern that the etchability is difficult to control. When the mass ratio of tin oxide (SnO2) exceeds the above upper limit, the humidity resistance reliability sometimes decreases.

[0075] The first inorganic oxide layer 8 can be either crystalline or amorphous, for example. From the viewpoint of facilitating patterning in subsequent processes, the first inorganic oxide layer 8 is preferably amorphous.

[0076] The thickness T8 of the first inorganic oxide layer 8 is, for example, 5 nm or more, preferably 20 nm or more, more preferably 30 nm or more, and, for example, 100 nm or less, preferably 60 nm or less, more preferably 50 nm or less. As long as the thickness T8 of the first inorganic oxide layer 8 is below the above upper limit, the transparent conductive layer 3 can be etched quickly and reliably in subsequent processes. As long as the thickness T8 of the first inorganic oxide layer 8 is above the above lower limit, it can function as a barrier layer.

[0077] 3-2. Metal layer

[0078] The metal layer 9 is a conductive layer that imparts conductivity to the transparent conductive layer 3 together with the first inorganic oxide layer 8 and the second inorganic oxide layer 10. In addition, the metal layer 9 is also a low-resistivity layer that reduces the resistivity of the transparent conductive layer 3.

[0079] The metal layer 9 has a thin film shape (including a sheet shape) and is disposed on the upper surface of the first inorganic oxide layer 8 in contact with the upper surface of the first inorganic oxide layer 8.

[0080] The metal forming the metal layer 9 is, for example, a metal with a small resistivity and is a metal that can be dissolved in the same etching solution as the etching solution for etching the first inorganic oxide layer 8. There is no particular limitation on the metal. For example, it can be mentioned that it is formed of one metal selected from the group consisting of Ti, Si, Nb, In, Zn, Sn, Au, Ag, Cu, Al, Co, Cr, Ni, Pb, Pd, Pt, Cu, Ge, Ru, Nd, Mg, Ca, Na, W, Zr, Ta, and Hf, or an alloy containing two or more metals.

[0081] As the metal, silver (Ag) and silver alloys are preferably mentioned, and silver alloys are more preferably mentioned.

[0082] The silver alloy contains silver as the main component and other metals as the secondary components, and its composition is not limited. As the composition of the silver alloy, for example, Ag-Pd alloy, Ag-Pd-Cu alloy, Ag-Pd-Cu-Ge alloy, Ag-Cu-Au alloy, Ag-Cu alloy, Ag-Cu-Sn alloy, Ag-Ru-Cu alloy, Ag-Ru-Au alloy, Ag-Pd alloy, Ag-Nd alloy, Ag-Mg alloy, Ag-Ca alloy, Ag-Na alloy, etc. can be mentioned. As the silver alloy, Ag-Pd alloy is preferably mentioned.

[0083] The content ratio of silver in the silver alloy (preferably an Ag-Pd alloy) is, for example, 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, still more preferably 95.0% by mass or more, and, for example, 99.9% by mass or less. The content ratio of other metals in the silver alloy is the remainder of the above silver content ratio. When the metal is an Ag-Pd alloy, the content ratio of Pd in the Ag-Pd alloy is, specifically, for example, 0.1% by mass or more and, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 1.0% by mass or less.

[0084] From the viewpoint of improving the transmittance of the transparent conductive layer 3, the thickness of the metal layer 9 is, for example, 1 nm or more, preferably 5 nm or more, and, for example, 30 nm or less, preferably 20 nm or less, more preferably 10 nm or less.

[0085] 3-3. The second inorganic oxide layer

[0086] The second inorganic oxide layer 10 is a conductive layer that, together with the first inorganic oxide layer 8 and the metal layer 9, imparts conductivity to the transparent conductive layer 3. The second inorganic oxide layer 10 may not maintain conductivity and preferably has conductivity. In addition, the second inorganic oxide layer 10 is also a barrier layer that prevents oxygen, water vapor, or trace amounts of sulfur oxides (SO x ) etc. that are always present in the atmosphere from corroding the metal layer 9. The second inorganic oxide layer 10 is the uppermost layer of the transparent conductive layer 3, has a thin film shape (including a sheet shape), and is disposed over the entire upper surface of the metal layer 9 in contact with the upper surface of the metal layer 9.

[0087] The second inorganic oxide layer 10 contains the inorganic oxides exemplified in the first inorganic oxide layer 8. Specifically, it is an inorganic oxide that can be dissolved in the same etching solution as the etching solution for etching the first inorganic oxide layer 8. Preferably, it contains indium oxide, and more preferably, it is formed of ITO. That is, the second inorganic oxide layer 10 is preferably an indium-based conductive oxide layer, and more preferably an ITO layer.

[0088] In indium tin composite oxide (ITO), with respect to the total mass of indium oxide (In2O3) and tin oxide (SnO2), the content ratio of tin oxide (SnO2) (SnO2 / (SnO2 + In2O3)) is, for example, 6% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more, and further preferably 12% by mass or more. Additionally, for example, it is 30% by mass or less, preferably 20% by mass or less, and more preferably 17% by mass or less. When the content ratio of tin oxide (SnO2) does not meet the above lower limit, the change over time in the crystallinity of the second inorganic oxide layer 10 becomes large, and there is a concern that it is difficult to control the etchability. When the content ratio of tin oxide (SnO2) exceeds the above upper limit, the humidity resistance reliability sometimes decreases.

[0089] The second inorganic oxide layer 10 can be either crystalline or amorphous, for example. From the viewpoint of facilitating patterning in subsequent processes, the second inorganic oxide layer 10 is preferably amorphous.

[0090] From the viewpoint of obtaining a good pattern cross-section during etching, the first inorganic oxide layer 8 and the second inorganic oxide layer 10 are preferably of the same film quality, and more preferably both are amorphous.

[0091] The thickness T10 of the second inorganic oxide layer 10 is, for example, 5 nm or more, preferably 20 nm or more, and further preferably 30 nm or more. Additionally, for example, it is 100 nm or less, preferably 60 nm or less, and more preferably 50 nm or less.

[0092] As long as the thickness T10 of the second inorganic oxide layer 10 is below the above upper limit, the transparent conductive layer 3 can be etched quickly and reliably in subsequent processes. As long as the thickness T10 of the second inorganic oxide layer 10 is above the above lower limit, it can function as a barrier layer.

[0093] In addition, among the thickness T8 of the first inorganic oxide layer 8 and the thickness T10 of the second inorganic oxide layer 10, the thickness of at least one layer is, for example, 80 nm or less, preferably 50 nm or less. Preferably, both the thickness T8 of the first inorganic oxide layer 8 and the thickness T10 of the second inorganic oxide layer 10 are, for example, 50 nm or less. As long as the thickness T8 of the first inorganic oxide layer 8 and / or the thickness T10 of the second inorganic oxide layer 10 is below the above upper limit, the transparent conductive layer 3 can be etched quickly and reliably in subsequent processes.

[0094] Moreover, the thickness of the transparent conductive layer 3, that is, the total thickness of the first inorganic oxide layer 8, the metal layer 9, and the second inorganic oxide layer 10 is preferably 20 nm or more, more preferably 40 nm or more. Additionally, for example, it is 230 nm or less, preferably 120 nm or less, and more preferably 100 nm or less.

[0095] 4. Inorganic layer

[0096] The inorganic layer 4 is the uppermost layer of the transparent conductive film 1 and has a film shape (including a sheet shape). The inorganic layer 4 is disposed over the entire upper surface of the second inorganic oxide layer 10 in contact with the upper surface of the second inorganic oxide layer 10.

[0097] The inorganic layer 4 is a hydrophilic layer that imparts hydrophilicity to the upper surface (surface) of the transparent conductive layer 3 (specifically, the second inorganic oxide layer 10).

[0098] In addition, the inorganic layer 4 is preferably formed by a sputtering method as described later, and thus is a sputtered layer.

[0099] The inorganic layer 4 is formed of a hydrophilic material, for example. There is no limitation on the hydrophilic material, and it is formed of a hydrophilic material, for example. Examples of the hydrophilic material include inorganic oxides such as silicon oxide, titanium oxide (specifically TiO2), and aluminum oxide (specifically Al2O3), and metal salts such as zeolite. As the hydrophilic material, inorganic oxides are preferably cited, and silicon oxide is more preferably cited.

[0100] Silicon oxide is specifically represented by SiO x where x is, for example, 1.0 or more, preferably 1.5 or more, and, for example, 2.0 or less. Specifically, examples of silicon oxide include SiO and SiO2 (silicon dioxide), and SiO2 is preferably cited.

[0101] The thickness T4 of the inorganic layer 4 is 20 nm or less, preferably 10 nm or less, more preferably less than 10 nm, further preferably 5.0 nm or less, particularly preferably less than 5.0 nm, most preferably 4.5 nm or less, further 3.0 nm or less, and, for example, 0.01 nm or more, preferably 0.1 nm or more, more preferably 0.5 nm or more, and further preferably 1.0 nm or more.

[0102] When the thickness T4 of the inorganic layer 4 is higher than the above upper limit, the transparent conductive layer 3 cannot be etched quickly and reliably. Further, when the thickness T4 of the inorganic layer 4 is higher than the above upper limit, although the water contact angle θ0 of the inorganic layer 4 immediately after the formation of the inorganic layer 4 can be set low, the ratio of the water contact angles (θ1 / θ0) described later becomes high (specifically, 4.0 or more), and thus the water contact angle θ1 of the inorganic layer 4 after 80 hours or more from the formation of the inorganic layer 4 becomes high. Therefore, sometimes the water contact angle θ1 of the inorganic layer 4 after 80 hours or more from the formation of the inorganic layer 4 deviates.

[0103] On the other hand, as long as the thickness T4 of the inorganic layer 4 is equal to or more than the above lower limit, excellent wettability can be obtained.

[0104] In addition, the ratio of the thickness T4 of the inorganic layer 4 to the thickness T10 of the second inorganic oxide layer 10 (thickness T4 of the inorganic layer 4 / thickness T10 of the second inorganic oxide layer 10) is, for example, 0.01 or more, preferably 0.02 or more, and, for example, 0.50 or less, preferably 0.25 or less, more preferably 0.15 or less, and further preferably 0.10 or less.

[0105] As long as the above thickness ratio is at least the above lower limit, excellent wettability can be obtained.

[0106] If the above thickness ratio exceeds the above upper limit, the transparent conductive layer 3 cannot be etched quickly and reliably. As long as the above thickness ratio exceeds the above lower limit, the water contact angle θ1 of the inorganic layer 4 after 80 hours or more from the formation of the inorganic layer 4 may deviate.

[0107] Moreover, the water contact angle θ1 of the inorganic layer 4 (described later, the water contact angle θ1 after 80 hours or more from the formation of the inorganic layer 4) is 50 degrees or less, preferably 40 degrees or less, more preferably 30 degrees or less, further preferably 20 degrees or less, particularly preferably less than 20 degrees, and most preferably 10 degrees or less. In addition, for example, it is 0 degrees or more, preferably 1 degree or more, and more preferably 5 degrees or more.

[0108] The water contact angle θ1 of the inorganic layer 4 is measured based on JIS R1753:2013 for the inorganic layer 4 placed in an atmosphere of normal temperature (specifically, 20 to 40 °C) and normal humidity (specifically, relative humidity of 30% or more and 70% or less) for 80 hours or more after the formation of the inorganic layer 4. A more specific method for measuring the water contact angle θ1 will be described in the examples below.

[0109] When the water contact angle θ1 of the inorganic layer 4 after 80 hours or more from the formation of the inorganic layer 4 is higher than the above upper limit, a light control functional layer 5 (described later) with a uniform thickness cannot be formed wet on the surface of the inorganic layer 4.

[0110] 5. Method for manufacturing a transparent conductive thin film

[0111] Next, a method for manufacturing the transparent conductive thin film 1 will be described.

[0112] This method includes: a step (1) of preparing a transparent substrate 2; a step (2) of forming a transparent conductive layer 3 on the surface of the transparent substrate 2; and a step (3) of forming an inorganic layer 4 on the surface of the transparent conductive layer 3. Each step will be described in detail below.

[0113] 5-1. Step (1)

[0114] In step (1), first, a base substrate 6 is prepared.

[0115] Next, a functional layer 7 is disposed on the upper surface of the base substrate 6. For example, the functional layer 7 is disposed by a wet method. Specifically, first, a resin composition is coated on the upper surface of the base substrate 6. Thereafter, when the resin composition contains a radiation curable resin, radiation is irradiated.

[0116] Thereby, a functional layer 7 in the form of a film is formed over the entire upper surface of the light-transmissive substrate 2. That is, the light-transmissive substrate 2 having the base substrate 6 and the functional layer 7 is produced.

[0117] 5-2. Step (2)

[0118] In step (2), after step (1), a light-transmissive conductive layer 3 is disposed (laminated) on the upper surface of the functional layer 7, for example, by a dry method.

[0119] Specifically, a first inorganic oxide layer 8, a metal layer 9, and a second inorganic oxide layer 10 are sequentially disposed by a dry method.

[0120] Examples of the dry method include a vacuum evaporation method, a sputtering method, an ion plating method, etc. The sputtering method is preferably cited.

[0121] Examples of the gas used in the sputtering method include inert gases such as Ar. In addition, a reactive gas such as oxygen can be used in combination as needed. When a reactive gas is used in combination, the ratio of the flow rate of the reactive gas to the flow rate of the inert gas (flow rate of reactive gas / flow rate of inert gas) is, for example, 0.1 / 100 or more, preferably 0.5 / 100 or more, and, for example, 10 / 100 or less, preferably 5 / 100 or less.

[0122] Specifically, in the formation of each of the first inorganic oxide layer 8 and the second inorganic oxide layer 10, an inert gas and a reactive gas are preferably used in combination as the gas.

[0123] On the other hand, in the formation of the metal layer 9, an inert gas is preferably used alone as the gas. In the formation of the second inorganic oxide layer 10, an inert gas and a reactive gas are preferably used in combination as the gas.

[0124] Preferably, the light-transmissive conductive layer 3 is formed in an amorphous form. Specifically, an amorphous first inorganic oxide layer 8 and an amorphous second inorganic oxide layer 10 are formed.

[0125] Thereby, a light-transmissive conductive layer 3 in which the first inorganic oxide layer 8, the metal layer 9, and the second inorganic oxide layer 10 are sequentially formed is formed on the light-transmissive substrate 2.

[0126] The surface resistance of the transparent conductive layer 3 (specifically, the surface resistance of the amorphous transparent conductive layer 3) is, for example, 1 Ω / square or more, preferably 3 Ω / square or more, more preferably 8 Ω / square or more. Further, for example, it is 100 Ω / square or less, preferably 50 Ω / square or less, and still more preferably 30 Ω / square or less.

[0127] 5 - 3. Process (3)

[0128] In process (3), after process (2), an inorganic layer 4 is disposed (laminated) on the upper surface of the second inorganic oxide layer 10, for example, by a dry process.

[0129] Examples of the dry process include a vacuum evaporation method, a sputtering method, an ion plating method, etc. From the viewpoint of uniformly forming the inorganic layer 4 with the above thickness T4, the sputtering method is preferably cited. On the other hand, as long as it is a vacuum evaporation method, the deviation of the thickness T4 of the inorganic layer 4 sometimes becomes large, and in addition, the wettability of the inorganic layer 4 decreases, and further, the inorganic layer 4 sometimes peels off from the transparent conductive layer 3.

[0130] Examples of the gas used in the sputtering method include an inert gas such as Ar. Further, a reactive gas such as oxygen can be used in combination as needed. When a reactive gas is used in combination, the ratio of the flow rate of the reactive gas to the flow rate of the inert gas (flow rate of the reactive gas / flow rate of the inert gas) is, for example, 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more. Further, for example, it is 90 / 100 or less, preferably 50 / 100 or less.

[0131] The water contact angle θ0 of the inorganic layer 4 immediately after the formation of the inorganic layer 4 (specifically, within 500 minutes after the formation of the inorganic layer 4) is 50 degrees or less, preferably 40 degrees or less, more preferably 20 degrees or less, still more preferably 10 degrees or less. Further, for example, it is 0 degrees or more, preferably 5 degrees or more, more preferably more than 6 degrees, still more preferably 7 degrees or more.

[0132] On the other hand, the water contact angle θ1 of the inorganic layer 4 changes with respect to the water contact angle θ0 immediately after the formation of the inorganic layer 4 after 80 hours or more from the formation of the inorganic layer 4. Specifically, the ratio (θ1 / θ0) of the water contact angle θ1 after 80 hours or more from the formation of the inorganic layer 4 to the water contact angle θ0 immediately after the formation of the inorganic layer 4 is, for example, 0.3 or more, preferably 0.5 or more, more preferably 1.0 or more, still more preferably 2.0 or more. Further, for example, it is less than 4.5, preferably 4.0 or less, more preferably 3.5 or less, still more preferably 3.0 or less, and particularly preferably less than 3.0. As long as the above ratio is below the above upper limit, the deviation of the water contact angle θ1 of the inorganic layer 4 after 80 hours or more from the formation of the inorganic layer 4 can be suppressed.

[0133] Thus, a transparent conductive film 1 having a transparent substrate 2, a transparent conductive layer 3, and an inorganic layer 4 in sequence is obtained.

[0134] The total thickness of the transparent conductive film 1 is, for example, 2 μm or more, preferably 20 μm or more, and, for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less.

[0135] This transparent conductive film 1 is a device that can be industrially utilized.

[0136] 5-4. Step (4)

[0137] The manufacturing method of the transparent conductive film 1 further includes a step (4) of etching the transparent conductive layer 3 after step (3).

[0138] In step (4), after step (3), the transparent conductive layer 3 is etched. Specifically, the transparent conductive layer 3 and the inorganic layer 4 are etched to pattern the transparent conductive layer 3 and the inorganic layer 4 into a specified shape.

[0139] As the etching solution, there is no particular limitation as long as it can dissolve the transparent conductive layer 3. For example, nitric acid, phosphoric acid, acetic acid, hydrochloric acid, sulfuric acid, oxalic acid, and their mixed solutions can be cited.

[0140] The etching time is, for example, 5 minutes or less, preferably 4 minutes or less, more preferably 3 minutes or less, and, for example, 0.05 minutes or more, preferably 0.1 minutes or more, more preferably 0.5 minutes or more. If the etching time is below the above upper limit, the manufacturing method of the transparent conductive film 1 can be implemented by a roll-to-roll method with excellent production efficiency.

[0141] Thus, a transparent conductive film 1 having a transparent substrate 2, a patterned transparent conductive layer 3, and a patterned inorganic layer 4 in sequence is obtained.

[0142] It should be noted that the above manufacturing method is implemented by a roll-to-roll method. In addition, part or all of it can be implemented by an intermittent method.

[0143] 6. Manufacturing method of the light control film

[0144] Next, with reference to Figure 2 A method for manufacturing the light control film 20 using the above transparent conductive film 1 will be described.

[0145] This method, as Figure 2 shown, includes a step (6) of manufacturing two pieces of the above transparent conductive film 1 and a step (7) of sandwiching a light control functional layer 5 with two pieces of the transparent conductive film 1.

[0146] 6-1. Step (6)

[0147] In step (6), two pieces of the above-described transparent conductive thin film 1 are manufactured. It should be noted that one piece of the transparent conductive thin film 1 may also be cut to prepare two pieces of the transparent conductive thin film 1.

[0148] The two pieces of the transparent conductive thin film 1 are a first transparent conductive thin film 1A and a second transparent conductive thin film 1B.

[0149] 6-2. Step (7)

[0150] Step (7) is carried out after step (6). In step (7), for example, a light control functional layer 5 is formed on the upper surface (surface) of the inorganic layer 4 in the first transparent conductive thin film 1A by a wet method.

[0151] The light control functional layer 5 is, for example, an electrochromic layer, a liquid crystal layer, etc., and preferably a liquid crystal layer.

[0152] In this step (7), for example, a solution containing a liquid crystal composition is coated on the upper surface of the inorganic layer 4 in the first transparent conductive thin film 1A. The liquid crystal composition may include known substances contained in the solution, and for example, a liquid crystal dispersion resin described in Japanese Patent Laid-Open No. 8-194209 can be cited.

[0153] Next, the second transparent conductive thin film 1B is laminated on the surface of the coating film in such a manner that the inorganic layer 4 of the second transparent conductive thin film 1B is in contact with the surface of the coating film. Thus, the coating film is sandwiched between two pieces of the transparent conductive thin film 1, that is, the first transparent conductive thin film 1A and the second transparent conductive thin film 1B.

[0154] Thereafter, an appropriate treatment is performed on the coating film (ultraviolet irradiation when the liquid crystal composition contains an ultraviolet curable composition) to form the light control functional layer 5. The light control functional layer 5 is formed between the inorganic layer 4 of the first transparent conductive thin film 1A and the inorganic layer 4 of the second transparent conductive thin film 1B.

[0155] Thus, a light control thin film 20 having the first transparent conductive thin film 1A, the light control functional layer 5, and the second transparent conductive thin film 1B in this order is obtained.

[0156] In addition, the light control thin film 20 is incorporated in a light control device (not shown, such as a light control window, etc.) having a power source (not shown), a control device (not shown), etc. In the light control device not shown, a voltage is applied to the transparent conductive layer 3 in the first transparent conductive thin film 1A and the transparent conductive layer 3 in the second transparent conductive thin film 1B by the power source, and thus an electric field is generated between them.

[0157] Further, based on the control device, the above-mentioned electric field is controlled so that the light control function layer 5 located between the first light-transmissive conductive film 1A and the second light-transmissive conductive film 1B blocks light or allows it to pass through.

[0158] 7. Effects of the First Embodiment

[0159] Since the light-transmissive conductive film 1 has the inorganic layer 4, it can stably maintain the hydrophilic property. Therefore, the reliability of the light-transmissive conductive film 1 is excellent.

[0160] Moreover, in the light-transmissive conductive film 1, the thickness T4 of the inorganic layer 4 is below the above-mentioned upper limit, so the inorganic layer 4 and the light-transmissive conductive layer 3 can be etched quickly and reliably. Therefore, the pattern processability of the light-transmissive conductive film 1 is excellent.

[0161] In addition, the water contact angle θ1 of the inorganic layer 4 after 80 hours or more from the formation of the inorganic layer 4 is below the above-mentioned upper limit, so a light control function layer 5 with a uniform thickness can be formed on the surface of the inorganic layer 4 by wet process. Therefore, a light control film 20 with excellent reliability can be obtained.

[0162] In addition, in the light-transmissive conductive film 1, as long as the inorganic layer 4 is formed by sputtering method, that is, as long as the inorganic layer 4 is a sputtered layer, the inorganic layer 4 is uniform and can have the above-mentioned thickness T4. In addition, the abrasion resistance is excellent and the adhesion to the light-transmissive substrate 2 (specifically, the functional layer 7) becomes good.

[0163] In addition, in the light-transmissive conductive film 1, if the inorganic layer 4 is formed of an inorganic oxide, the hydrophilicity is particularly excellent.

[0164] In addition, in the light-transmissive conductive film 1, as long as the thickness T8 of the first inorganic oxide layer 8 and the thickness T10 of the second inorganic oxide layer 10 are at least one of them below the above-mentioned upper limit, the inorganic layer 4 and the light-transmissive conductive layer 3 can be etched quickly and reliably.

[0165] In addition, according to this method, in step (3), as long as an inorganic layer 4 with a thickness T4 below the above-mentioned upper limit is formed, in step (4) after step (3), the inorganic layer 4 and the light-transmissive conductive layer 3 can be etched quickly and reliably.

[0166] In addition, the water contact angle θ1 of the inorganic layer 4 after 80 hours or more from the formation of the inorganic layer 4 is below the above-mentioned upper limit, so a light control function layer 5 with a uniform thickness can be formed on the surface of the inorganic layer 4 by wet process.

[0167] In the dimming film 20, the dimming functional layer 5 is in contact with the inorganic layer 4 of the first light-transmissive conductive film 1A and the inorganic layer 4 of the second light-transmissive conductive film 1B, so it can have a uniform thickness. Moreover, since the dimming film 20 has the above-described light-transmissive conductive film 1 with excellent reliability, its reliability is excellent.

[0168] In addition, according to the manufacturing method of the dimming film 20, in step (6), the inorganic layer 4 is brought into contact with the inorganic layer 4 of the first light-transmissive conductive film 1A and the inorganic layer 4 of the second light-transmissive conductive film 1B, so that a dimming functional layer 5 with a uniform thickness T5 can be obtained. Therefore, the reliability of the dimming film 20 is excellent.

[0169] 8. Modification Example of the First Embodiment

[0170] Furthermore, according to the use and purpose of the dimming film 20, in the manufacturing method of the dimming film 20, when forming the amorphous light-transmissive conductive layer 3 in step (2), before and after step (4), a step (5) for crystallizing the amorphous light-transmissive conductive layer 3 may also be provided. Preferably, after step (4), a step (5) for crystallizing the amorphous light-transmissive conductive layer 3 is provided.

[0171] The amorphous light-transmissive conductive layer 3 is formed in step (2). Specifically, an amorphous first inorganic oxide layer 8 and an amorphous second inorganic oxide layer 10 are respectively formed.

[0172] Preferably, step (5) is carried out after step (4). In step (5), the amorphous first inorganic oxide layer 8 and the second inorganic oxide layer 10 are crystallized.

[0173] In order to crystallize the light-transmissive conductive layer 3, for example, the patterned light-transmissive conductive layer 3 is heated (annealing treatment) in an air atmosphere at a temperature of, for example, 80°C or higher and 150°C or lower for, for example, 30 minutes or longer and 90 minutes or shorter.

[0174] The surface resistance of the crystallized light-transmissive conductive layer 3 is, for example, 0.5 Ω / square or higher, preferably 1 Ω / square or higher, more preferably 5 Ω / square or higher. Additionally, for example, it is 50 Ω / square or lower, preferably 20 Ω / square or lower, more preferably 15 Ω / square or lower.

[0175] In addition, in the first embodiment, the light-transmissive substrate 2 has the functional layer 7. For example, it may also be as Figure 3 shown, without the functional layer 7, and the light-transmissive substrate 2 is composed only of the base substrate 6. That is, as Figure 3 shown, at this time, the light-transmissive substrate 2 does not have the functional layer 7 and is composed only of the base substrate 6.

[0176] The transparent conductive layer 3 (specifically, the first inorganic oxide layer 8) is disposed in contact with the upper surface of the base substrate 6 (the light-transmissive substrate 2).

[0177] The transparent conductive layer 3 is disposed on the upper surface of the base substrate 6. Specifically, the first inorganic oxide layer 8 is disposed over the entire upper surface of the base substrate 6.

[0178] In addition, as Figure 2 shown, each of the two transparent conductive films 1, namely the first transparent conductive film 1A and the second transparent conductive film 1B, has a specific inorganic layer 4. For example, although not shown, specifically, the second transparent conductive film 1B may be configured such that only the first transparent conductive film 1A has the inorganic layer 4 and the second transparent conductive film 1B does not have the inorganic layer 4.

[0179] In this modification, although not shown, the second transparent conductive film 1B sequentially includes a light-transmissive substrate 2 and a transparent conductive layer 3.

[0180] In addition, as Figure 1 shown, in the transparent conductive film 1 of the first embodiment, the transparent conductive layer 3 sequentially includes a first inorganic oxide layer 8, a metal layer 9, and a second inorganic oxide layer 10. However, for example, although not shown, a second metal layer and a third inorganic oxide layer may be sequentially disposed on the second inorganic oxide layer 10. In this case, the transmissive conductive layer 3 sequentially includes a first inorganic oxide layer 8, a metal layer 9, a second inorganic oxide layer 10, a second metal layer, and a third inorganic oxide layer. Further, a third metal layer and a fourth inorganic oxide layer may be sequentially disposed on the third inorganic oxide layer. In this case, the transmissive conductive layer 3 includes: a first inorganic oxide layer 8, a metal layer 9, a second inorganic oxide layer 10, a second metal layer, a third inorganic oxide layer, a third metal layer, and a fourth inorganic oxide layer.

[0181] In the second transparent conductive film 1B, the surface of the transparent conductive layer 3, specifically, the surface of the second inorganic oxide layer 10, is exposed. The second inorganic oxide layer 10 of the second transparent conductive film 1B is in direct contact with the light control functional layer 5.

[0182] In addition, in the first embodiment, as Figure 1 shown, the functional layer 7 is disposed on the upper surface of the base substrate 6. However, although not shown, the functional layer 7 may be disposed on both the upper surface and the lower surface of the base substrate 6.

[0183] According to the above-described respective modifications, the same effects as those of the first embodiment can be achieved.

[0184] <Second Embodiment>

[0185] In the second embodiment, the same reference numerals are given to the same components and processes as in the first embodiment, and the detailed description thereof is omitted.

[0186] 1. Transparent conductive film

[0187] The transparent conductive layer 3, as Figure 1 shown, includes three layers: a first inorganic oxide layer 8, a metal layer 9, and a second inorganic oxide layer 10. As Figure 4 shown, in the second embodiment, only the first inorganic oxide layer 8 is provided. The transparent conductive layer 3, as Figure 4 shown, does not include the metal layer 9. Therefore, from the viewpoint of obtaining a low resistivity, it is preferably crystalline.

[0188] 1-1. Transparent conductive layer

[0189] The transparent conductive layer 3 is composed only of the first inorganic oxide layer 8.

[0190] The thickness T3 of the transparent conductive layer 3 is the same as the thickness T8 of the first inorganic oxide layer 8. Specifically, for example, it is 15 nm or more, preferably 20 nm or more. Additionally, for example, it is 300 nm or less, preferably 150 nm or less, more preferably 50 nm or less, further preferably 40 nm or less, and particularly preferably 35 nm or less.

[0191] As long as the thickness T3 of the transparent conductive layer 3 is below the above upper limit, in subsequent processes, the inorganic layer 4 and the transparent conductive layer 3 can be etched quickly and reliably. As long as the thickness T3 of the transparent conductive layer 3 is above the above lower limit, crystallization can be reliably performed even in the case where crystallinity is required.

[0192] The transparent conductive layer 3 is preferably crystalline. Compared with an amorphous film, a crystalline film sometimes has significantly poor hydrophilicity. Since the hydrophilic inorganic layer 4 is disposed on the transparent conductive layer 3 in the transparent conductive film 1 of the present application, the transparent conductive layer 3 can be suitably used even if it is a crystalline film.

[0193] The transparent conductive layer 3 may be a laminate of multiple inorganic oxide layers (refer to Figure 4The first inorganic oxide layer 8 formed by the symbols 13 and 14). Preferably, the first inorganic oxide layer 8 is formed by a laminate of indium tin composite oxides (ITO) composed of different layers (for example: two layers). Specifically, the first inorganic oxide layer 8 includes a third indium tin composite oxide layer 13 disposed on the upper surface of the light-transmissive substrate 2 and a fourth indium tin composite oxide layer 14 disposed on the upper surface of the third indium tin composite oxide layer 13. Among the first inorganic oxide layer 8, the tin oxide content rate in the indium tin composite oxide layer disposed on the inorganic layer 4 side (facing the inorganic layer 4) (specifically, the fourth indium tin composite oxide layer 14) is not the largest compared to the tin oxide content rates in the respective indium tin composite oxide layers constituting the first inorganic oxide layer 8, and is preferably the smallest. That is, in the first inorganic oxide layer 8, it is preferred that the tin oxide content rate decreases from the lower layer to the upper layer. Specifically, when the first inorganic oxide layer 8 is formed by a laminate of the third indium tin composite oxide layer 13 and the fourth indium tin composite oxide layer 14, the tin oxide content rate of the fourth indium tin composite oxide layer 14 is smaller than the tin oxide content rate of the third indium tin composite oxide layer 13. More specifically, the fourth indium tin composite oxide layer 14 has the smallest tin oxide content rate in the first inorganic oxide layer 8.

[0194] Thus, even when the inorganic layer 4 is disposed thereon, the transparent conductive layer 3 can become a crystalline ITO film in a short time.

[0195] The tin oxide content rate of the fourth indium tin composite oxide layer 14 is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more. In addition, for example, it is 8% by mass or less, preferably 6% by mass or less, more preferably 5% by mass or less.

[0196] On the other hand, the tin oxide content rate of the layer other than the fourth indium tin composite oxide layer 14 (specifically, the third indium tin composite oxide layer 13) is, for example, 5% by mass or more, preferably 6% by mass or more, more preferably 9% by mass or more, further preferably 10% by mass or more. In addition, for example, it is 20% by mass or less, preferably 15% by mass or less, more preferably 13% by mass or less.

[0197] 1-2. Inorganic layer

[0198] The inorganic layer 4 is disposed on the upper surface of the first inorganic oxide layer 8.

[0199] 2. Manufacturing method of the transparent conductive thin film

[0200] The manufacturing method of the transparent conductive thin film includes step (5) on the basis of the above steps (1) to (4).

[0201] 2-1. Step (2)

[0202] In step (2), the transparent conductive layer 3 is formed only of the amorphous first inorganic oxide layer 8.

[0203] 2-2. Step (5)

[0204] Step (5) is carried out after step (4).

[0205] In step (5), the patterned transparent conductive layer 3 formed of the amorphous first inorganic oxide layer 8 is crystallized.

[0206] In order to crystallize the transparent conductive layer 3, for example, the patterned transparent conductive layer 3 is heated (annealed) in an atmospheric atmosphere at a temperature of, for example, 80°C or higher and 150°C or lower for, for example, 30 minutes or longer and 90 minutes or shorter.

[0207] The surface resistance of the crystallized transparent conductive layer 3 is, for example, 30 Ω / sq or higher, preferably 60 Ω / sq or higher, and, for example, 200 Ω / sq or lower, preferably 150 Ω / sq or lower, more preferably 100 Ω / sq or lower, and further preferably 90 Ω / sq or lower.

[0208] 3. Effects of the Second Embodiment

[0209] The second embodiment can exhibit the same effects as the first embodiment.

[0210] Furthermore, in step (5) after step (3), more specifically, in step (5) after step (4), the transparent conductive layer 3 formed of the amorphous first inorganic oxide layer 8 is crystallized, so that the surface resistance of the transparent conductive layer 3 can be reduced.

[0211] 4. Modifications of the Second Embodiment

[0212] In the second embodiment, step (5) is carried out after step (4), but step (5) may also be carried out after step (3) and before step (4).

[0213] That is, in step (3), the inorganic layer 4 is formed, and then, in step (5), the transparent conductive layer 3 is crystallized, and thereafter, in step (4), the transparent conductive layer 3 is etched.

[0214] In the second embodiment, step (5) may also be carried out following step (2).

[0215] For example: In step (2), the amorphous transparent conductive layer 3 is formed, and then, in step (5), the amorphous transparent conductive layer 3 is crystallized, and thereafter, in step (3), the inorganic layer 4 is formed on the crystalline transparent conductive layer 3.

[0216] For example: in step (2), an amorphous light-transmissive conductive layer 3 is formed. Then, in step (5), the amorphous light-transmissive conductive layer 3 is crystallized. After that, in step (3), an inorganic layer 4 is formed on the crystalline light-transmissive conductive layer 3. Furthermore, the crystalline light-transmissive conductive layer 3 can also be etched in step (4).

[0217] In addition, although the practicality is poor, for example, in step (2), an amorphous light-transmissive conductive layer is formed. Then, in step (5), the amorphous light-transmissive conductive layer is crystallized. After that, in step (4), the crystalline light-transmissive conductive layer is etched. Furthermore, an inorganic layer can also be formed on the crystalline light-transmissive conductive layer in step (3).

[0218] In the second embodiment, the light-transmissive substrate 2 has a functional layer 7. However, for example, as Figure 6 shown, it may not have the functional layer 7 and the light-transmissive substrate 2 is composed only of the base substrate 6. That is, as Figure 6 shown, at this time, the light-transmissive substrate 2 does not have the functional layer 7 and is formed only by the base substrate 6.

[0219] The light-transmissive conductive layer 3 (specifically, the first inorganic oxide layer 8) is arranged in contact with the upper surface of the base substrate 6 (light-transmissive substrate 2).

[0220] According to these modified examples, the same effects as those of the second embodiment can be achieved.

[0221] In addition, the above first embodiment, second embodiment and their modified examples can be appropriately combined.

[0222] Examples

[0223] The present invention will be described in detail below using examples. The present invention is not limited to the examples as long as it does not exceed its gist, and various modifications and changes can be made based on the technical concept of the present invention.

[0224] Examples and comparative examples are shown below to more specifically describe the present invention. It should be noted that the present invention is not limited by the examples and comparative examples. In addition, the specific values such as the compounding ratio (content ratio), physical property values, parameters, etc. used in the following descriptions can be replaced by the upper limits (values defined by "below" and "less than") or lower limits (values defined by "above" and "more than") of the corresponding compounding ratios (content ratios), physical property values, parameters, etc. described in the above "Detailed Description".

[0225] Example 1

[0226] Step (1): Production of the light-transmissive substrate

[0227] Prepare a base substrate 6 made of a polyethylene terephthalate (PET) film (manufactured by Mitsubishi Resin) with a thickness of 50 μm. Next, coat the surface of the base substrate 6 (the main surface on the side where the light-transmissive conductive layer 3 is to be formed) with an ultraviolet-curable resin made of an acrylic resin, and cure it by ultraviolet irradiation to form a hard coat 7' with a thickness of 2 μm. Thus, a light-transmissive substrate 2 having the base substrate 6 and the hard coat 7' in sequence is produced.

[0228] Step (2): Fabrication of the light-transmissive conductive layer

[0229] Next, a light-transmissive conductive layer 3 formed of a laminate having a first inorganic oxide layer 8, a metal layer 9, and a second inorganic oxide layer 10 in sequence is formed on the hard coat 7' of the light-transmissive substrate 2.

[0230] Both the first inorganic oxide layer 8 and the second inorganic oxide layer 10 are indium tin oxide layers formed of indium tin oxide. Specifically, both the first inorganic oxide layer 8 and the second inorganic oxide layer 10 are indium tin conductive oxides with a thickness of 40 nm formed by sputtering an ITO target (manufactured by Mitsui Mining & Smelting Co., Ltd.) formed of a sintered body of 12 mass% tin oxide and 88 mass% indium oxide in a vacuum atmosphere into which a film-forming gas (a mixed gas formed of Ar and O2 (flow ratio Ar:O2 = 100:3)) is introduced.

[0231] In addition, the metal layer 9 is formed of an Ag-Pd alloy. Specifically, the metal layer 9 is a silver alloy layer with a thickness of 8 nm formed by sputtering a silver alloy target formed of an alloy in which 99 mass% of Ag and 1 mass% of Pd are mixed in a vacuum atmosphere into which a film-forming gas (Ar) is introduced.

[0232] Step (3): Fabrication of the inorganic layer

[0233] Next, an inorganic layer 4 with a thickness of 0.5 nm formed of silicon oxide (SiO2) is formed on the second inorganic oxide layer 10 of the light-transmissive conductive layer 3. The inorganic layer 4 is formed by sputtering a Si target (manufactured by Daido Steel Co., Ltd.) formed of a Si plate with a purity of 99.99% or more in a vacuum atmosphere into which a film-forming gas (a mixed gas formed of Ar and O2 (flow ratio Ar:O2 = 100:41)) is introduced.

[0234] Thus, a light-transmissive conductive film 1 having the light-transmissive conductive layer 3, the inorganic layer 4, and the light control function layer 5 in sequence is manufactured.

[0235] Examples 2 to 8

[0236] As shown in Table 1, the thickness and manufacturing method of the inorganic layer 4 were changed, and other than that, the same treatment as in Example 1 was performed to manufacture the transparent conductive film 1.

[0237] Comparative Example 1

[0238] As shown in Table 1, the inorganic layer 4 was not formed, and other than that, the same treatment as in Example 1 was performed to manufacture the transparent conductive film 1.

[0239] Example 9

[0240] In step (2), the flow rate ratio of Ar and O2 as the film-forming gas was set to Ar:O2 = 100:1, and the transparent conductive layer 3 was formed only from the first inorganic oxide layer 8. Other than that, according to Table 1, the same treatment as in Example 1 was performed to manufacture the transparent conductive film 1.

[0241] It should be noted that the first inorganic oxide layer 8 was formed by a laminate of a third indium tin composite oxide layer 13 with a tin oxide content of 10% by mass and a fourth indium tin composite oxide layer 14 with a tin oxide content of 3% by mass.

[0242] Example 10

[0243] In step (3), the inorganic layer 4 was formed from a SiO2 layer with a thickness of 0.5 nm by vacuum evaporation (electron beam heating method). Other than that, the same treatment as in Example 1 was performed to manufacture the transparent conductive film 1.

[0244] Evaluation

[0245] The following items were evaluated, and the results are shown in Table 1.

[0246] (1) Water contact angle

[0247] The water contact angles (θ0, θ1) of the inorganic layer 4 in Examples 1 to 10 were measured as follows: A water droplet with a diameter of 1.5 mm was formed at the tip of the needle, brought into contact with the surface of the inorganic layer 4, and the water droplet was moved onto the inorganic layer 4. The static contact angle between the water droplet and the inorganic layer 4 was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., CA-X type). Five measurements were made. When the difference between the maximum angle and the minimum angle was 5.0 degrees or less, it was judged that the measurement was accurate, and the wettability was judged using the simple average value of the water contact angle. When the water contact angle exceeded 5.0 degrees, since the measurement could not be accurately performed and it was considered that the dimming functional layer 5 was partially repelled, regardless of the value, the wettability was set to "low".

[0248] It should be noted that regarding the water contact angle θ1, the water contact angle of the inorganic layer 4 after being placed in an atmosphere of 25°C and a relative humidity of 40% for 80 hours after the formation of the inorganic layer 4 was measured.

[0249] In addition, for Comparative Example 1, since the inorganic layer 4 is not provided, the water contact angle of the transparent conductive layer 3 was measured in the same manner as described above.

[0250] It should be noted that although the water contact angle of the transparent conductive thin film 1 of Example 10 is 50 degrees or less, there are deviations in the water contact angle values depending on the measurement position, and it is difficult to measure the true value.

[0251] (2) Thickness

[0252] The thickness of the base substrate 6 was measured using a film thickness gauge (manufactured by Ozaki Seisakusho Co., Ltd. (Peacock (registered trademark)), device name "digital dial gauge DG-205").

[0253] The thicknesses of the hard coat layer 7, the first inorganic oxide layer 8, the metal layer 9, and the second inorganic oxide layer 10 were measured by cross-sectional observation using a transmission electron microscope (manufactured by Hitachi, Ltd., device name "HF-2000").

[0254] The thickness of the inorganic layer 4 was measured using an X-ray fluorescence analyzer (manufactured by Rigaku Corporation, device name "ZSX Primus II") (the thickness of the inorganic layer was obtained by subtracting the SiKa intensity from the transparent substrate).

[0255] It should be noted that the following preliminary preparations are carried out each time X-ray fluorescence analysis is performed.

[0256] That is, a silicon oxide (SiO2) layer with a target thickness of 100 nm, 150 nm, and 200 nm was formed on a PET substrate with a thickness of 50 μm to prepare a test body. The SiKa intensity of each test body (the value obtained by subtracting the SiKa intensity from the PET substrate) was measured using each X-ray fluorescence analyzer. In addition, the actual film thickness of the silicon oxide layer of each test body was obtained using a transmission electron microscope. A standard curve was made from the SiKa intensity value and the actual film thickness thus obtained, and the thickness of the inorganic layer 4 was obtained from the SiKa intensity.

[0257] (3) Etching time and etchability

[0258] Twenty sheets of the light-transmitting conductive film 1 cut into a size of 5 cm square are immersed in an etching solution (manufactured by ADEKA Corporation, product name "ADEKA CERUMICA SET-500") heated to 40°C. Thereafter, every 15 seconds of the immersion time, one sheet is taken out, washed with water and wiped with water (dried), the appearance of the light-transmitting conductive film 1 is confirmed, and the resistance between two terminals at any three locations is measured. It should be noted that the measurement of the resistance between two terminals is carried out using a measuring instrument, and the distance between the terminals during measurement is set to 1.5 cm. And in the evaluation of the etching time, the moment when no residue from the light-transmitting conductive layer 3 or the inorganic layer 4 can be visually confirmed within the 5 cm square light-transmitting conductive film 1 and the resistance between two terminals at any three locations exceeds 60 MΩ is judged as the end of etching.

[0259] The etchability is evaluated according to the following criteria.

[0260] ◎: The etching time is less than 60 seconds.

[0261] ○: The etching time is 60 seconds or more and 180 seconds or less.

[0262] △: The etching time exceeds 180 seconds and is 300 seconds or less.

[0263] ×: The etching time exceeds 300 seconds.

[0264] (4) Surface resistance value of the light-transmitting conductive layer

[0265] The surface resistance value of the light-transmitting conductive layer 3 is measured by the four-terminal method based on JIS K 7194 (1994).

[0266] (5) Crystallinity

[0267] The light-transmitting conductive layer 3 in Example 9 is heat-treated at 140°C to evaluate the crystallinity of the light-transmitting conductive layer 3. Specifically, after immersing the light-transmitting conductive films of each example in hydrochloric acid (concentration: 5% by mass) for 15 minutes, they are washed with water and dried, the resistance between terminals at about 15 mm is measured, and the crystallization rate is evaluated according to the following criteria.

[0268] ○: The resistance between terminals at 15 mm is 10 kΩ or less.

[0269] ×: The resistance between terminals at 15 mm exceeds 10 kΩ.

[0270] For Comparative Example 1, the crystallization rate is also evaluated in the same manner as in Example 9.

[0271] (6) Repellency

[0272] An aqueous solution prepared by dissolving 5 mg of sodium chloride in 100 mL of water was dropped onto the transparent conductive layer 3 of each of the examples and comparative examples, or onto the transparent substrate 2 in the absence of the transparent conductive layer 3, and the repellency was visually evaluated according to the following criteria.

[0273] ○: No repellency was observed.

[0274] △: Slight repellency was observed, but the aqueous solution was well integrated with the transparent conductive layer 3 or the transparent substrate 2 as a whole.

[0275] ×: Repellency was observed.

[0276] (7) Peeling

[0277] The inorganic layers of Examples 1 to 10 were observed, and the peelability was evaluated as follows.

[0278] ○: No peeling sites were visible everywhere on the inorganic layer 4.

[0279] △: Peeling sites were visible everywhere on the inorganic layer 4.

[0280] [Table 1]

[0281]

[0282] It should be noted that the above invention is provided as an exemplary embodiment of the present invention, but it is only a simple example and is not to be construed as limiting. Variations of the present invention that are obvious to those skilled in the art are also included in the foregoing claims.

[0283] Industrial Applicability

[0284] The transparent conductive film of the present invention is included in, for example, a light control film.

[0285] Explanation of Reference Numerals

[0286] 1 Transparent conductive film

[0287] 2 Transparent substrate

[0288] 3 Transparent conductive layer

[0289] 4 Inorganic layer

[0290] 5 Light control functional layer

[0291] T4 Thickness of the inorganic layer

[0292] T8 Thickness of the first inorganic oxide layer

[0293] T10 Thickness of the second inorganic oxide layer

Claims

1. A light-transmissive conductive film, characterized in that, It sequentially includes a light-transmissive substrate, a light-transmissive conductive layer, and an inorganic layer. The thickness of the inorganic layer is 0.5 nm or more and 4.5 nm or less. The water contact angle of the inorganic layer is 50 degrees or less. The light-transmissive conductive layer is disposed by a dry process. The inorganic layer is a sputtered layer.

2. The transparent conductive film according to claim 1, wherein The water contact angle of the inorganic layer after 80 hours or more from the formation of the inorganic layer is 50 degrees or less.

3. The transparent conductive film according to claim 1, characterized in that, The inorganic layer is formed of an inorganic oxide.

4. The transparent conductive film according to claim 1, wherein The light-transmissive conductive layer has an indium-based conductive oxide layer. The thickness of the indium-based conductive oxide layer is 50 nm or less.

5. A method for manufacturing a light-transmissive conductive film, which includes the following steps: Step (1) of preparing a light-transmissive substrate; Step (2) of forming a light-transmissive conductive layer on the surface of the light-transmissive substrate by a dry process; Step (3) of forming an inorganic layer as a sputtered layer on the surface of the light-transmissive conductive layer by sputtering; Step (4) of etching the light-transmissive conductive layer after step (3); The thickness of the inorganic layer is 0.5 nm or more and 4.5 nm or less. The water contact angle of the inorganic layer after 80 hours or more from the formation of the inorganic layer is 50 degrees or less.

6. The manufacturing method of the light-transmissive conductive film according to claim 5, characterized in that, In step (2), the amorphous light-transmissive conductive layer is formed. It further includes: step (5) of crystallizing the amorphous light-transmissive conductive layer after step (3).

7. A dimming film, characterized in that, It sequentially includes a first light-transmissive conductive film, a light control function layer, and a second light-transmissive conductive film. The first light-transmissive conductive film and / or the second light-transmissive conductive film is the light-transmissive conductive film according to claim 1. The light control function layer is in contact with the inorganic layer included in the light-transmissive conductive film.

8. A manufacturing method of a dimming film, characterized in that, It includes the following steps: Step (6) of manufacturing two light-transmissive conductive films; Step (7) of sandwiching the light control function layer with two light-transmissive conductive films; In step (6), at least one of the light-transmissive conductive films is manufactured by the manufacturing method according to claim 5. In step (7), the light control function layer is brought into contact with the inorganic layer of at least one of the light-transmissive conductive films.

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